Science.gov

Sample records for harli jrgenson ene

  1. The aromatic ene reaction

    NASA Astrophysics Data System (ADS)

    Niu, Dawen; Hoye, Thomas R.

    2014-01-01

    The ene reaction is a pericyclic process in which an alkene with an allylic hydrogen atom (the ene donor) reacts with a second unsaturated species (the enophile) to form a new product with a transposed π-bond. The aromatic ene reaction, in which the alkene component is embedded in an aromatic ring, has only been reported in a few (four) instances and has proceeded in low yield (≤6%). Here, we show efficient aromatic ene reactions in which a thermally generated aryne intermediate engages a pendant m-alkylarene substituent to produce a dearomatized isotoluene, itself another versatile but rare reactive intermediate. Our experiments were guided by computational studies that revealed structural features conducive to the aromatic ene process. We proceeded to identify a cascade comprising three reactions: (1) hexadehydro-Diels-Alder (for aryne generation), (2) intramolecular aromatic ene and (3) bimolecular Alder ene. The power of this cascade is evident from the structural complexity of the final products, the considerable scope, and the overall efficiency of these multistage, reagent- and by-product-free, single-pot transformations.

  2. The aromatic ene reaction

    PubMed Central

    Niu, Dawen; Hoye, Thomas R.

    2014-01-01

    The ene reaction is a pericyclic process in which an alkene having an allylic hydrogen atom (the ene donor) reacts with a second unsaturated species (the enophile) to form a new product with a transposed π-bond. The aromatic ene reaction, in which the alkene component is embedded in an aromatic ring, has only been reported in a few (four) instances and has proceeded in low yield (≤6%). Here we show efficient aromatic ene reactions in which a thermally generated aryne engages a pendant m-alkylarene substituent to produce a dearomatized isotoluene, itself another versatile but rare reactive intermediate. Our experiments were guided by computational studies that revealed structural features conducive to the aromatic ene process. We proceeded to identify a cascade comprising three reactions: (i) hexadehydro-Diels-Alder (for aryne generation), (ii) intramolecular aromatic ene, and (iii) bimolecular Alder ene. The power of this cascade is evident from the structural complexity of the final products, the considerable scope, and the overall efficiency of these multi-stage, reagent- and byproduct-free, single-pot transformations. PMID:24345944

  3. Safety harness

    SciTech Connect

    Gunter, L.W.

    1991-04-08

    A safety harness to be worn by a worker, especially a worker wearing a plastic suit thereunder for protection in a radioactive or chemically hostile environment. The safety harness comprises a torso surrounding portion with at least one horizontal strap for adjustably securing the harness about the torso, two vertical shoulder straps with rings just forward of the of the peak of the shoulders for attaching a life-line and a pair of adjustable leg supporting straps releasibly attachable to the torso surrounding portion. In the event of a fall, the weight of the worker, when his fall is broken and he is suspended from the rings with his body angled slightly back and chest up, will be borne by the portion of the leg straps behind his buttocks rather than between his legs. Furthermore, the supporting straps do not restrict the air supplied through hoses into his suit when so suspended.

  4. Safety harness

    DOEpatents

    Gunter, Larry W.

    1993-01-01

    A safety harness to be worn by a worker, especially a worker wearing a plastic suit thereunder for protection in a radioactive or chemically hostile environment, which safety harness comprises a torso surrounding portion with at least one horizontal strap for adjustably securing the harness about the torso, two vertical shoulder straps with rings just forward of the of the peak of the shoulders for attaching a life-line and a pair of adjustable leg supporting straps releasibly attachable to the torso surrounding portion. In the event of a fall, the weight of the worker, when his fall is broken and he is suspended from the rings with his body angled slightly back and chest up, will be borne by the portion of the leg straps behind his buttocks rather than between his legs. Furthermore, the supporting straps do not restrict the air supplied through hoses into his suit when so suspended.

  5. Harnessing inequality

    NASA Astrophysics Data System (ADS)

    Eliazar, Iddo

    2016-09-01

    Living in the era of "big-data" information, we are ubiquitously inundated by overabundances of sizes-non-negative numerical values representing count, score, length, area, volume, duration, mass, energy, etc. Datasets of sizes display numerous types of statistical variability that are commonly quantified either by the standard deviation, or by the Boltzmann-Gibbs-Shannon entropy. The standard deviation measures the sizes' Euclidean divergence from their mean, the Boltzmann-Gibbs-Shannon entropy measures the sizes' informational divergence from the benchmark of pure determinism, and both these gauges are one-dimensional. In this paper we overview a methodology that harnesses inequality in order to quantify statistical variability. The methodology follows a socioeconomic approach of measuring the sizes' inequality-their divergence from the benchmark of pure egalitarianism-and yields frameworks that gauge statistical variability in a multi-dimensional fashion. The aim of this overview is to serve both researchers and practitioners as a crash-introduction to the "harnessing inequality" methodology, and as a crash-manual to the implementation of this methodology.

  6. Computerized Interactive Harness Engineering

    NASA Technical Reports Server (NTRS)

    Billitti, J. W.

    1985-01-01

    Computerized interactive harness engineering program inexpensive, interactive system for learning and using engineering approach to interconnection systems. Basically data-base system that stores information as files of individual connectors and handles wiring information in circuit groups stored as records.

  7. Wire harness twisting aid

    NASA Technical Reports Server (NTRS)

    Casey, E. J.; Commadore, C. C.; Ingles, M. E.

    1980-01-01

    Long wire bundles twist into uniform spiral harnesses with help of simple apparatus. Wires pass through spacers and through hand-held tool with hole for each wire. Ends are attached to low speed bench motor. As motor turns, operator moves hand tool away forming smooth twists in wires between motor and tool. Technique produces harnesses that generate less radio-frequency interference than do irregularly twisted cables.

  8. Wire harness twisting aid

    NASA Technical Reports Server (NTRS)

    Casey, E. J.; Commadore, C. C.; Ingles, M. E.

    1980-01-01

    Long wire bundles twist into uniform spiral harnesses with help of simple apparatus. Wires pass through spacers and through hand-held tool with hole for each wire. Ends are attached to low speed bench motor. As motor turns, operator moves hand tool away forming smooth twists in wires between motor and tool. Technique produces harnesses that generate less radio-frequency interference than do irregularly twisted cables.

  9. Harnessing vision for computation.

    PubMed

    Changizi, Mark

    2008-01-01

    Might it be possible to harness the visual system to carry out artificial computations, somewhat akin to how DNA has been harnessed to carry out computation? I provide the beginnings of a research programme attempting to do this. In particular, new techniques are described for building 'visual circuits' (or 'visual software') using wire, NOT, OR, and AND gates in a visual 6modality such that our visual system acts as 'visual hardware' computing the circuit, and generating a resultant perception which is the output.

  10. Hopkins installs wire harnesses

    NASA Image and Video Library

    2013-11-24

    ISS038-E-008291 (24 Nov. 2013) --- NASA astronaut Michael Hopkins, Expedition 38 flight engineer, installs wire harnesses in the International Space Station?s Harmony node to support the installation of Ethernet video cables for the station?s local area network. These new cables will provide Ethernet connectivity to the visiting vehicles that dock to Harmony?s Earth-facing port.

  11. NCCS Regression Test Harness

    SciTech Connect

    Tharrington, Arnold N.

    2015-09-09

    The NCCS Regression Test Harness is a software package that provides a framework to perform regression and acceptance testing on NCCS High Performance Computers. The package is written in Python and has only the dependency of a Subversion repository to store the regression tests.

  12. NCCS Regression Test Harness

    SciTech Connect

    Tharrington, Arnold N.

    2015-09-09

    The NCCS Regression Test Harness is a software package that provides a framework to perform regression and acceptance testing on NCCS High Performance Computers. The package is written in Python and has only the dependency of a Subversion repository to store the regression tests.

  13. Reliable Wiring Harness

    NASA Technical Reports Server (NTRS)

    Gaspar, Kenneth C.

    1987-01-01

    New harness for electrical wiring includes plugs that do not loosen from vibration. Ground braids prevented from detaching from connectors and constrained so braids do not open into swollen "birdcage" sections. Spring of stainless steel encircles ground braid. Self-locking connector contains ratchet not only preventing connector from opening, but tightens when vibrated.

  14. Quick-donning backpack harness

    NASA Technical Reports Server (NTRS)

    Thomas, D. F., Jr.

    1972-01-01

    Harness device permits user to quickly put on or take off load carried in backpack arrangement. It can be attached with one hand; has controlled deformation belt that automatically encircles user upon application of pressure; has rigid shoulder harness elements which move automatically into place; and primary attachment components cannot be displaced while harness is in place.

  15. Harnessing Team Work. Close Call.

    ERIC Educational Resources Information Center

    Journal of Adventure Education and Outdoor Leadership, 1995

    1995-01-01

    Experienced teams competing in multiple adventure activities, several of which involved ropes, kept their harnesses on all day. Safety procedures included an initial check of buckles and harnesses by an instructor, but failed to recognize that participants would remove their harnesses for toilet purposes. Lists other possible safety errors for…

  16. Catalytic Conia-ene and related reactions.

    PubMed

    Hack, Daniel; Blümel, Marcus; Chauhan, Pankaj; Philipps, Arne R; Enders, Dieter

    2015-10-07

    Since its initial inception, the Conia-ene reaction, known as the intramolecular addition of enols to alkynes or alkenes, has experienced a tremendous development and appealing catalytic protocols have emerged. This review fathoms the underlying mechanistic principles rationalizing how substrate design, substrate activation, and the nature of the catalyst work hand in hand for the efficient synthesis of carbocycles and heterocycles at mild reaction conditions. Nowadays, Conia-ene reactions can be found as part of tandem reactions, and the road for asymmetric versions has already been paved. Based on their broad applicability, Conia-ene reactions have turned into a highly appreciated synthetic tool with impressive examples in natural product synthesis reported in recent years.

  17. JWST ISIM Harness Thermal Evaluation

    NASA Technical Reports Server (NTRS)

    Kobel, Mark; Glazer, Stuart; Tuttle, Jim; Martins, Mario; Ruppel, Sean

    2008-01-01

    The James Webb Space Telescope (JWST) will be a large infrared telescope with a 6.5-meter primary mirror. Launch is planned for 2013. JWST wl1 be the premier observatory of the next decade serving thousands of astronomers worldwide. The Integrated Science Instrument Module (ISIM) is the unit that will house thc four main JWST instruments. The ISIM enclosure passively cooled to 37 Kelvin and has a tightly managed thermal budget. A significant portion of the ISIM heat load is due to parasitic heat gains from the instrument harnesses. These harnesses provide a thermal path from the Instrument Electronics Control (IEC) to the ISIM. Because of the impact of this load to the ISIM thermal design, understanding the harness parasitic heat gains is critical. To this effect, a thermal test program has been conducted in order to characterize these parasitic loads and verify harness thermal models. Recent parasitic heat loads tests resulted in the addition of a dedicated multiple stage harness radiator. In order for the radiator to efficiently reject heat from the harness, effective thermal contact conductance values for multiple harnesses had to be determined. This presentation will describe the details and the results of this test program.

  18. ENES the European Network for Earth System modelling and its infrastructure projects IS-ENES

    NASA Astrophysics Data System (ADS)

    Guglielmo, Francesca; Joussaume, Sylvie; Parinet, Marie

    2016-04-01

    The scientific community working on climate modelling is organized within the European Network for Earth System modelling (ENES). In the past decade, several European university departments, research centres, meteorological services, computer centres, and industrial partners engaged in the creation of ENES with the purpose of working together and cooperating towards the further development of the network, by signing a Memorandum of Understanding. As of 2015, the consortium counts 47 partners. The climate modelling community, and thus ENES, faces challenges which are both science-driven, i.e. analysing of the full complexity of the Earth System to improve our understanding and prediction of climate changes, and have multi-faceted societal implications, as a better representation of climate change on regional scales leads to improved understanding and prediction of impacts and to the development and provision of climate services. ENES, promoting and endorsing projects and initiatives, helps in developing and evaluating of state-of-the-art climate and Earth system models, facilitates model inter-comparison studies, encourages exchanges of software and model results, and fosters the use of high performance computing facilities dedicated to high-resolution multi-model experiments. ENES brings together public and private partners, integrates countries underrepresented in climate modelling studies, and reaches out to different user communities, thus enhancing European expertise and competitiveness. In this need of sophisticated models, world-class, high-performance computers, and state-of-the-art software solutions to make efficient use of models, data and hardware, a key role is played by the constitution and maintenance of a solid infrastructure, developing and providing services to the different user communities. ENES has investigated the infrastructural needs and has received funding from the EU FP7 program for the IS-ENES (InfraStructure for ENES) phase I and II

  19. Organocatalyzed Intramolecular Carbonyl-Ene Reactions.

    PubMed

    Dahlmann, Heidi A; McKinney, Amanda J; Santos, Maria P; Davis, Lindsey O

    2016-05-31

    An organocatalyzed intramolecular carbonyl-ene reaction was developed to produce carbocyclic and heterocyclic 5- and 6-membered rings from a citronellal-derived trifluoroketone and a variety of aldehydes. A phosphoramide derivative was found to promote the cyclization of the trifluoroketone, whereas a less acidic phosphoric acid proved to be a superior catalyst for the aldehyde substrates.

  20. Environmental Control Unit Harness Project

    NASA Technical Reports Server (NTRS)

    Oliva-Buisson, Yvette J.

    2014-01-01

    Testing four new Environmental Control Unit Harnesses for improved user comfort during SCAPE operations. Phase I, testing in a lab environment, Phase II will continue testing the best candidates in a field environment.

  1. IS-ENES project management - lessons learnt

    NASA Astrophysics Data System (ADS)

    Parinet, Marie; Guglielmo, Francesca; Joussaume, Sylvie

    2017-04-01

    IS-ENES is the distributed e-infrastructure of models, model data and metadata of the European Network for Earth System Modelling (ENES). It has benefitted from two EC FP7 grants and aims towards further European and national funding to achieve sustainability. We highlight here several challenges related to project management that have risen in the course of these two project-phases spanning 8 years. Some challenges are related to the heterogeneity of the activities within IS-ENES, with different groups working on very diverse activities, not necessarily strictly interdependent. An immediate consequence is the need of implementing and setting up in early phases of the project efficient collection and circulation of information to preserve and reinforce the systemic view of the infrastructure as a whole and the pursuit of common goals, including coordinated provision of services. Toward and beyond such common goals, managing IS-ENES, covering both scientific and more strictly management-related aspects, implies a double-paced approach: besides setting up efficient project workflow, there is the need of setting up longer term objectives. This implies, within the project lifetime, to elaborate and implement a coherent organizational (consistent with scientific goals, funding schemes, research and technology landscape) strategy to pursue these goals beyond the project itself. Furthermore, a series of more generic project management challenges will also be listed and can be gathered around 3 main objectives: ease the internal processes in order to optimize the work, anticipate delays and budget issues, and motivate the project teams by ensuring an efficient internal and external communication.

  2. Harness the Power of Technology

    ERIC Educational Resources Information Center

    Duncan, Arne

    2011-01-01

    Today, U.S. educators are teaching in the midst of a technological revolution. Technology promises to provide innovative solutions in the nation's classrooms, just as it has transformed the way people communicate, socialize, and conduct business. In this article, the author argues that now is the time to harness technology to revolutionize the way…

  3. 14 CFR 91.521 - Shoulder harness.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... combined safety belt and shoulder harnesses that were approved and installed before March 6, 1980, may... belt and shoulder harnesses that were approved and installed before March 6, 1980, may continue to be...

  4. Positioning bars for large wire harnesses

    NASA Technical Reports Server (NTRS)

    Glessner, J. R.

    1978-01-01

    By tying positioning bars to harness, its configuration can be preserved during transport, thus facilitating installation. Harness can also be showed temporarily by placing hanging hooks on end of bar.

  5. Moving Large Wiring-Harness Boards

    NASA Technical Reports Server (NTRS)

    Shepherd, Samuel D.; Gurman, Isaac

    1990-01-01

    Carrier for wiring-harness fabrication boards enables lone operator to move board easily and safely. Holds harness while operator fabricating, while being stored, and being transported to equipment frame for mounting. When positioned for assembly of wiring harness, board and carrier give operator easy and convenient access to wires and cables, when positioned for transfer of wiring harness to or from storage area, carrier holds board securely while moved by one person.

  6. Photopolymerized Thiol-Ene Systems as Shape Memory Polymers.

    PubMed

    Nair, Devatha P; Cramer, Neil B; Scott, Timothy F; Bowman, Christopher N; Shandas, Robin

    2010-09-03

    In this study we introduce the use of thiol-ene photopolymers as shape memory polymer systems. The thiol-ene polymer networks are compared to a commonly utilized acrylic shape memory polymer and shown to have significantly improved properties for two different thiol-ene based polymer formulations. Using thermomechanical and mechanical analysis, we demonstrate that thiol-ene based shape memory polymer systems have comparable thermomechanical properties while also exhibiting a number of advantageous properties due to the thiol-ene polymerization mechanism which results in the formation of a homogenous polymer network with low shrinkage stress and negligible oxygen inhibition. The resulting thiol-ene shape memory polymer systems are tough and flexible as compared to the acrylic counterparts. The polymers evaluated in this study were engineered to have a glass transition temperature between 30 and 40 °C, exhibited free strain recovery of greater than 96% and constrained stress recovery of 100%. The thiol-ene polymers exhibited excellent shape fixity and a rapid and distinct shape memory actuation response.

  7. Thiol-ene-methacrylate composites as dental restorative materials

    PubMed Central

    Boulden, Jordan E.; Cramer, Neil B.; Schreck, Kathleen M.; Couch, Charles L.; Bracho-Troconis, Cora; Stansbury, Jeffrey W.; Bowman, Christopher N.

    2010-01-01

    Objectives The objective of this study was to evaluate composite methacrylate-thiol-ene formulations with varying thiol:ene stoichiometry relative to composite dimethacrylate control formulations. It was hypothesized that the methacrylate-thiol-ene systems would exhibit superior properties relative to the dimethacrylate control resins and that excess thiol relative to ene would further enhance shrinkage and conversion associated properties. Methods Polymerization kinetics and functional group conversions were determined by Fourier transform infrared spectroscopy (FTIR). Volume shrinkage was measured with a linometer and shrinkage stress was measured with a tensometer. Flexural modulus and strength, depth of cure, water sorption and solubility tests were all performed according to ISO 4049. Results All of the methacrylate-thiol-ene systems exhibited improvements in methacrylate conversion, flexural strength, shrinkage stress, depth of cure, and water solubility, while maintaining equivalent flexural modulus and water sorption relative to the dimethacrylate control systems. Increasing the thiol to ene stoichiometry resulted in further increased methacrylate functional group conversion and decreased volume shrinkage. Flexural modulus and strength, shrinkage stress, depth of cure, water sorption and solubility did not exhibit statistically significant changes with excess thiol . Significance Due to their improved overall functional group conversion and reduced water sorption, the methacrylate-thiol-ene formulations are expected to exhibit improved biocompatibility relative to the dimethacrylate control systems. Improvements in flexural strength and reduced shrinkage stress may be expected to result in composite restorations with superior longevity and performance. PMID:21122904

  8. Microfluidic devices using thiol-ene polymers

    NASA Astrophysics Data System (ADS)

    Bou, Simon J. M. C.; Ellis, Amanda V.

    2013-12-01

    Here, a new polymeric microfluidic platform using off-stoichiometric thiol-ene (OSTE) polymers was developed. Thiolene polymers were chosen as they afford rapid UV curing, low volume shrinkage and optical transparency for use in microfluidic devices. Three different off-stoichiometric thiol-ene polymers with 30% excess allyl, 50% excess thiol and a 90% excess thiol (OSTE Allyl-30, OSTE-50 and OSTE-90, respectively) were fabricated. Attenuated reflectance Fourier transform infrared (ATR-FTIR) spectroscopy and solid-state cross polarisation-magic angle spinning (CP-MAS) nuclear magnetic resonance (NMR) spectroscopy confirmed which functional groups (thiol or allyl) were present in excess in the OSTE polymers. The polymers were shown to have a more hydrophilic surface (water contact angle of 65°+/- 3) compared to polydimethylsiloxane (water contact angle of 105° +/- 5). Testing of the mechanical properties showed the glass transition temperatures to be 15.09 °C, 43.15 °C and, 57.48 °C for OSTE-90, OSTE Allyl-30 and, OSTE-50, respectively. The storage modulus was shown to be less than 10 MPa for the OSTE-90 polymer and approximately 1750 MPa for the OSTE Allyl-30 and OSTE-50 polymers. The polymers were then utilised to fabricate microfluidic devices via soft lithography practices and devices sealed using a one-step UV lamination "click" reaction technique. Finally, gold nanoparticles were used to form gold films on the OSTE-90 and OSTE-50 polymers as potential electrodes. Atomic force microscopy and sheet resistances were used to characterise the films.

  9. Harnessing spin precession with dissipation.

    PubMed

    Crisan, A D; Datta, S; Viennot, J J; Delbecq, M R; Cottet, A; Kontos, T

    2016-01-27

    Non-collinear spin transport is at the heart of spin or magnetization control in spintronics devices. The use of nanoscale conductors exhibiting quantum effects in transport could provide new paths for that purpose. Here we study non-collinear spin transport in a quantum dot. We use a device made out of a single-wall carbon nanotube connected to orthogonal ferromagnetic electrodes. In the spin transport signals, we observe signatures of out of equilibrium spin precession that are electrically tunable through dissipation. This could provide a new path to harness spin precession in nanoscale conductors.

  10. Harnessing spin precession with dissipation

    NASA Astrophysics Data System (ADS)

    Crisan, A. D.; Datta, S.; Viennot, J. J.; Delbecq, M. R.; Cottet, A.; Kontos, T.

    2016-01-01

    Non-collinear spin transport is at the heart of spin or magnetization control in spintronics devices. The use of nanoscale conductors exhibiting quantum effects in transport could provide new paths for that purpose. Here we study non-collinear spin transport in a quantum dot. We use a device made out of a single-wall carbon nanotube connected to orthogonal ferromagnetic electrodes. In the spin transport signals, we observe signatures of out of equilibrium spin precession that are electrically tunable through dissipation. This could provide a new path to harness spin precession in nanoscale conductors.

  11. Oblique view showing western abutment, looking ENE along main line. ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    Oblique view showing western abutment, looking ENE along main line. Septa commuter train in foreground. - Pennsylvania Railroad, Whitford Bridge, Spanning Amtrak tracks at Whitford Road, Whitford, Chester County, PA

  12. 4. VIEW LOOKING ENE OF UNDERSIDE SHOWING RIBS AND BEAMS. ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    4. VIEW LOOKING ENE OF UNDERSIDE SHOWING RIBS AND BEAMS. NOTE SPALLING ON NORTHERN EDGE AND EXPOSED REBAR. - Morris Run Bridge, Rickert Road (TR 417) spanning Morris Run in Hilltown Township, Dublin, Bucks County, PA

  13. Preparation of Novel Hydrolyzing Urethane Modified Thiol-Ene Networks

    DTIC Science & Technology

    2011-10-25

    and the formation of a newly substituted organo-silicate [13]. This methodology can be used in the synthesis of organo-silicates having...forming reactions. Both systems, allyl and vinyl, produce fast-curing films having high monomer conversions. Scheme 3. Synthesis of tetra-ene...equivalent with pentaerythritol allyl ether (tri-ene) possesses an average hardness of 72 ± 2 g and tack of 18 ± 2 g, respectively. Physical properties

  14. Concise Total Synthesis of Lundurines A-C Enabled by Gold Catalysis and a Homodienyl Retro-Ene/Ene Isomerization.

    PubMed

    Kirillova, Mariia S; Muratore, Michael E; Dorel, Ruth; Echavarren, Antonio M

    2016-03-23

    The total synthesis of lundurines A-C has been accomplished in racemic and enantiopure forms in 11-13 and 12-14 steps, respectively, without protection/deprotection of functional groups, by a novel tandem double condensation/Claisen rearrangement, a gold(I)-catalyzed alkyne hydroarylation, a cyclopropanation via formal [3 + 2] cycloaddition/nitrogen extrusion, and a remarkable olefin migration through a vinylcyclopropane retro-ene/ene reaction that streamlines the endgame.

  15. Concise Total Synthesis of Lundurines A–C Enabled by Gold Catalysis and a Homodienyl Retro-Ene/Ene Isomerization

    PubMed Central

    2016-01-01

    The total synthesis of lundurines A–C has been accomplished in racemic and enantiopure forms in 11–13 and 12–14 steps, respectively, without protection/deprotection of functional groups, by a novel tandem double condensation/Claisen rearrangement, a gold(I)-catalyzed alkyne hydroarylation, a cyclopropanation via formal [3 + 2] cycloaddition/nitrogen extrusion, and a remarkable olefin migration through a vinylcyclopropane retro-ene/ene reaction that streamlines the endgame. PMID:26963149

  16. Intermolecular Aryne Ene Reaction of Hantzsch Esters: Stable Covalent Ene Adducts from a 1,4-Dihydropyridine Reaction.

    PubMed

    Trinchera, Piera; Sun, Weitao; Smith, Jane E; Palomas, David; Crespo-Otero, Rachel; Jones, Christopher R

    2017-09-01

    The reaction of arynes with 1,4-dihydropyridines affords 2-aryl-1,2-dihydropyridines or 2-methylene-3-aryl-1,2,3,4-tetrahydropyridines via a regioselective C-2 or C-3 arylation. These compounds are the first series of isolable and bench-stable covalent ene adducts formed between dihydropyridines and unsaturated substrates. Experimental studies and DFT calculations provide mechanistic support for a concerted intermolecular aryne ene process, which may have implications for NAD(P)H model reactions.

  17. Spring control of wire harness loops

    NASA Technical Reports Server (NTRS)

    Curcio, P. J.

    1979-01-01

    Negator spring control guides wire harness between movable and fixed structure. It prevents electrical wire harness loop from jamming or being severed as wire moves in response to changes in position of aircraft rudder. Spring-loaded coiled cable controls wire loop regardless of rudder movement.

  18. Hexaarylbiimidazoles as Visible Light Thiol–Ene Photoinitiators

    PubMed Central

    Clarkson, Brian H.; Scott, Timothy F.

    2015-01-01

    Objectives The aim of this study is to determine if hexaarylbiimidazoles (HABIs) are efficient, visible light-active photoinitiators for thiol–ene systems. We hypothesize that, owing to the reactivity of lophyl radicals with thiols and the necessarily high concentration of thiol in thiol–ene formulations, HABIs will effectively initiate thiol–ene polymerization upon visible light irradiation. Methods UV-vis absorption spectra of photoinitiator solutions were obtained using UV-vis spectroscopy, while EPR spectroscopy was used to confirm radical species generation upon HABI photolysis. Functional group conversions during photopolymerization were monitored using FTIR spectroscopy, and thermomechanical properties were determined using dynamic mechanical analysis. Results The HABI derivatives investigated exhibit less absorptivity than camphorquinone at 469 nm; however, they afford increased sensitivity at this wavelength when compared with bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide. Photolysis of the investigated HABIs affords lophyl radicals. Affixing hydroxyhexyl functional groups to the HABI core significantly improved solubility. Thiol–ene resins formulated with HABI photoinitiators polymerized rapidly upon irradiation with 469 nm. The glass transition temperatures of the thiol–ene resin formulated with a bis(hydroxyhexyl)-functionalized HABI and photopolymerized at room and body temperature were 49.5±0.5°C and 52.2±0.1°C, respectively. Significance Although thiol–enes show promise as continuous phases for composite dental restorative materials, they show poor reactivity with the conventional camphorquinone/tertiary amine photoinitiation system. Conversely, despite their relatively low visible light absorptivity, HABI photoinitiators afford rapid thiol–ene photopolymerization rates. Moreover, minor structural modifications suggest pathways for improved HABI solubility and visible light absorption. PMID:26119702

  19. Fullerenes produced by harnessing sunlight

    SciTech Connect

    Not Available

    1993-08-01

    Two independent groups of researchers have demonstrated that fullerenes can be produced by harnessing focused sunlight to vaporize carbon. Adapted to a large scale, generation of the carbon-cage molecules in solar furnaces might overcome yield-limiting problems associated with other fullerene production techniques, the researchers suggest. At Rice University, Houston, chemistry professor Richard E. Smalley and graduate students L.P. Felipe Chibante, Andreas Thess, J. Michael Alford, and Michael D. Diener used a parabolic mirror to focus sunlight on a graphite target to produce what appears to be a high yield of fullerenes. At the National Renewable Energy Laboratory (NREL), Golden, Colo., Roland R. Pitts, Mary Jane Hale, Carl Bingham, Allan Lewandowski, and David E.King, working in collaboration with Clark L. Fields, a chemistry professor at the University of Northern Colorado, Greeley, used NREL's high-flux solar furnace to produce soot that contains C[sub 60] and C[sub 70]. Papers describing the Rice and NREL results appeared together in last week's Journal of Physical Chemistry (97, 8696 and 8701 (1993)).

  20. The Optical Harness: a light-weight EMI-immune replacement for legacy electrical wiring harnesses

    NASA Astrophysics Data System (ADS)

    Stark, Jason B.; Jackson, B. Scott; Trethewey, William

    2006-05-01

    Electrical wiring harnesses have been used to interconnect control and communication equipment in mobile platforms for over a century. Although they have served this function successfully, they have three problems that are inherent in their design: they are mechanically heavy and stiff, and they are prone to electrical faults, including arcing and Electro-Magnetic Interference (EMI), and they are difficult to maintain when faults occur. These properties are all aspects of the metallic conductors used to build the harnesses. The Optical Harness TM is a photonic replacement for the legacy electrical wiring harness. The Optical Harness TM uses light-weight optical fiber to replace signal wires in an electrical harness. The original electrical connections to the equipment remain, making the Optical Harness TM a direct replacement for the legacy wiring harness. In the backshell of each connector, the electrical signals are converted to optical, and transported on optical fiber, by a deterministic, redundant and fault-tolerant optical network. The Optical Harness TM: * Provides weight savings of 40-50% and unsurpassed flexibility, relative to legacy signal wiring harnesses; * Carries its signals on optical fiber that is free from arcing, EMI, RFI and susceptibility to HPM weapons; * Is self-monitoring during operation, providing non-intrusive predictive and diagnostic capabilities.

  1. The hydrocarbon potential of the Ene Basin (Peru)

    SciTech Connect

    Fabre, A.D.; Alvarez, D.U.

    1993-02-01

    The Ene basin is located between 10[degrees]30' and 12[degrees] latitude south in the foothills of the Eastern Cordillera. Geochemical analysis indicate the presence of mature organic-rich source rocks in the Upper Paleozoic. In particular the Ene formation includes mature (Ro = 0.7 to 0.9%) oil-prone shale with mixed type I/II kerogen. Geohistory models show that the Ene formation entered into the oil window some 5 to 3 m.y. ago in the deep part of the basin and could generate hydrocarbons until the present time. Good reservoir sandstones (Oriente gr., Vivian Fm.) were deposited during the Cretaceous sandstones. The Ene basin extends in a northwest-southeast direction between the Eastern Cordillera to the west and the Shiro-Vilcabamba uplift to the east. The Late Miocene-Pliocene Quechua phase III deformed the sedimentary series producing east verging imbricated thrust sheets and large anticlines which could trap the hydrocarbons generated by the Upper Paleozoic source rocks. Several anticlines are still sealed by the Tertiary cover and represent attractive prospects for hydrocarbon exploration. With a prospective area close to 8000 km[sup 2] the unexplored Ene basin is awaiting imaginative geologists and geophysicists to demonstrate its potential.

  2. A TCP-Over-UDP Test Harness

    SciTech Connect

    Dunigan, TH

    2002-10-31

    This report describes an implementation of a TCP-like protocol that runs over UDP. This TCP-like implementation, which does not require kernel modifications, provides a test harness for evaluating variations of the TCP transport protocol over the Internet. The test harness provides a tunable and instrumented version of TCP that supports Reno, NewReno, and SACK/FACK. The test harness can also be used to characterize the TCP-performance of a network path. Several case studies illustrate how one can tune the transport protocol to improve performance.

  3. Cysteine-functional polymers via thiol-ene conjugation.

    PubMed

    Kuhlmann, Matthias; Reimann, Oliver; Hackenberger, Christian P R; Groll, Jürgen

    2015-03-01

    A thiofunctional thiazolidine is introduced as a new low-molar-mass building block for the introduction of cysteine residues via a thiol-ene reaction. Allyl-functional polyglycidol (PG) is used as a model polymer to demonstrate polymer-analogue functionalization through reaction with the unsaturated side-chains. A modified trinitrobenzenesulfonic acid (TNBSA) assay is used for the redox-insensitive quantification and a precise final cysteine content can be predetermined at the polymerization stage. Native chemical ligation at cysteine-functional PG is performed as a model reaction for a chemoselective peptide modification of this polymer. The three-step synthesis of the thiofunctional thiazolidine reactant, together with the standard thiol-ene coupling and the robust quantification assay, broadens the toolbox for thiol-ene chemistry and offers a generic and straightforward approach to cysteine-functional materials. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Reactive superhydrophobic surface and its photoinduced disulfide-ene and thiol-ene (bio)functionalization.

    PubMed

    Li, Junsheng; Li, Linxian; Du, Xin; Feng, Wenqian; Welle, Alexander; Trapp, Oliver; Grunze, Michael; Hirtz, Michael; Levkin, Pavel A

    2015-01-14

    Reactive superhydrophobic surfaces are highly promising for biotechnological, analytical, sensor, or diagnostic applications but are difficult to realize due to their chemical inertness. In this communication, we report on a photoactive, inscribable, nonwettable, and transparent surface (PAINTS), prepared by polycondensation of trichlorovinylsilane to form thin transparent reactive porous nanofilament on a solid substrate. The PAINTS shows superhydrophobicity and can be conveniently functionalized with the photoclick thiol-ene reaction. In addition, we show for the first time that the PAINTS bearing vinyl groups can be easily modified with disulfides under UV irradiation. The effect of superhydrophobicity of PAINTS on the formation of high-resolution surface patterns has been investigated. The developed reactive superhydrophobic coating can find applications for surface biofunctionalization using abundant thiol or disulfide bearing biomolecules, such as peptides, proteins, or antibodies.

  5. Intelligent electrical harness connector assembly using Bell Helicopter Textron's 'Wire Harness Automated Manufacturing System'

    NASA Astrophysics Data System (ADS)

    Springer, D. W.

    Bell Helicopter Textron, Incorporated (BHTI) installed two Digital Equipment Corporation PDP-11 computers and an American Can Inc. Ink Jet printer in 1980 as the cornerstone of the Wire Harness Automated Manufacturing System (WHAMS). WHAMS is based upon the electrical assembly philosophy of continuous filament harness forming. This installation provided BHTI with a 3 to 1 return-on-investment by reducing wire and cable identification cycle time by 80 percent and harness forming, on dedicated layout tooling, by 40 percent. Yet, this improvement in harness forming created a bottle neck in connector assembly. To remove this bottle neck, BHTI has installed a prototype connector assembly cell that integrates the WHAMS' data base and innovative computer technologies to cut harness connector assembly cycle time. This novel connector assembly cell uses voice recognition, laser identification, and animated computer graphics to help the electrician in the correct assembly of harness connectors.

  6. Harness: The Next Generation Beyond PVM

    SciTech Connect

    Geist, G.A.

    1998-09-05

    Abstract. Harness is the next generation heterogeneous distributed computing package being developed by the PVM team at Oak Ridge National Laboratory, University of Tennessee, and Emory University. This paper describes the changing trends in cluster computing and how Harness is being designed to address the future needs of PVM and MPI application developers. Harness (which will support both PVM and MPI) will allow users to dynamically customize, adapt, and extend a virtual machine's features to more closely match the needs of their application and to optimize for the underlying computer resources. This paper will describe the architecture and core services of this new virtual machine paradgm, our progress on this project, and our experiences with early prototypes of Harness.

  7. 14 CFR 91.521 - Shoulder harness.

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ... inertia load factors established under the certification basis of the airplane. (b) No person may operate... used; and (2) Safety belt and shoulder harness restraint systems may be designed to the inertia load...

  8. 14 CFR 91.521 - Shoulder harness.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... inertia load factors established under the certification basis of the airplane. (b) No person may operate... used; and (2) Safety belt and shoulder harness restraint systems may be designed to the inertia load...

  9. 14 CFR 91.521 - Shoulder harness.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... inertia load factors established under the certification basis of the airplane. (b) No person may operate... used; and (2) Safety belt and shoulder harness restraint systems may be designed to the inertia load...

  10. 14 CFR 91.521 - Shoulder harness.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... inertia load factors established under the certification basis of the airplane. (b) No person may operate... used; and (2) Safety belt and shoulder harness restraint systems may be designed to the inertia load...

  11. Distributed Real-Time Computing with Harness

    SciTech Connect

    Di Saverio, Emanuele; Cesati, Marco; Di Biagio, Christian; Pennella, Guido; Engelmann, Christian

    2007-01-01

    Modern parallel and distributed computing solutions are often built onto a ''middleware'' software layer providing a higher and common level of service between computational nodes. Harness is an adaptable, plugin-based middleware framework for parallel and distributed computing. This paper reports recent research and development results of using Harness for real-time distributed computing applications in the context of an industrial environment with the needs to perform several safety critical tasks. The presented work exploits the modular architecture of Harness in conjunction with a lightweight threaded implementation to resolve several real-time issues by adding three new Harness plug-ins to provide a prioritized lightweight execution environment, low latency communication facilities, and local timestamped event logging.

  12. 78 FR 717 - ENE (Environment Northeast); Greater Boston Real Estate Board; National Consumer Law Center...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2013-01-04

    ... From the Federal Register Online via the Government Publishing Office DEPARTMENT OF ENERGY Federal Energy Regulatory Commission ENE (Environment Northeast); Greater Boston Real Estate Board; National..., ENE (Environment Northeast), Greater Boston Real Estate Board, National Consumer Law Center, and...

  13. Efficient curing of vinyl carbonates by thiol-ene polymerization.

    PubMed

    Mautner, Andreas; Qin, Xiaohua; Kapeller, Barbara; Russmueller, Guenter; Koch, Thomas; Stampfl, Juergen; Liska, Robert

    2012-12-13

    Vinyl carbonates have recently been identified as a suitable alternative to (meth)acrylates, especially due to the low irritancy and cytotoxicity of these monomers. The drawback of some vinyl carbonates containing abstractable hydrogens arises through their moderate reactivity compared with acrylates. Within this paper, we use the thiol-ene concept to enhance the photoreactivity of vinyl carbonates to a large extent to reach the level of those of similar acrylates. Mechanical properties of the final thiol-ene polymers were determined by nanoindentation. Furthermore, low toxicity of all components was confirmed by osteoblast cell culture experiments.

  14. Derivatives of cardanol through the ene reaction with diethyl azodicarboxylate

    USDA-ARS?s Scientific Manuscript database

    Cardanol is an alkyl/alkenyl phenolic material obtained from cashew nut shell liquid (CNSL), which is a byproduct of cashew nut processing. In an effort to develop new uses, cardanol was derivatized for the first time with diethyl azodicarboxylate (DEAD) through the ene reaction. The reaction was fa...

  15. Hybrid Organic/Inorganic Thiol-ene-Based Photopolymerized Networks

    PubMed Central

    Schreck, Kathleen M.; Leung, Diana; Bowman, Christopher N.

    2011-01-01

    The thiol-ene reaction serves as a more oxygen tolerant alternative to traditional (meth)acrylate chemistry for forming photopolymerized networks with numerous desirable attributes including energy absorption, optical clarity, and reduced shrinkage stress. However, when utilizing commercially available monomers, many thiol-ene networks also exhibit decreases in properties such as glass transition temperature (Tg) and crosslink density. In this study, hybrid organic/inorganic thiol-ene resins incorporating silsesquioxane (SSQ) species into the photopolymerized networks were investigated as a route to improve these properties. Thiol- and ene-functionalized SSQs (SH-SSQ and allyl-SSQ, respectively) were synthesized via alkoxysilane hydrolysis/condensation chemistry, using a photopolymerizable monomer [either pentaerythriol tetrakis(3-mercaptopropionate) (PETMP) or 1,3,5-triallyl-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (TATATO)] as the reaction solvent. The resulting SSQ-containing solutions (SSQ-PETMP and SSQ-TATATO) were characterized, and their incorporation into photopolymerized networks was evaluated. PMID:21984847

  16. 23. (Credit JTL) View looking ENE at west end of ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    23. (Credit JTL) View looking ENE at west end of station. End addition houses chlorination equipment; to extreme right is north end of filter building built in 1942. - McNeil Street Pumping Station, McNeil Street & Cross Bayou, Shreveport, Caddo Parish, LA

  17. Evidence for distinct dehydrogenase and isomerase sites within a single 3. beta. -hydroxysteroid dehydrogenase/5-ene-4-ene isomerase protein

    SciTech Connect

    Luu-The, V.; Takahashi, Masakazu; de Launoit, Y.; Dumont, M.; Lachance, Y.; Labrie, F. )

    1991-09-10

    Complementary DNA encoding human 3{beta}-hydroxysteroid dehydrogenase/5-ene-4-ene isomerase (3-{beta}-HSD) has been expressed in transfected GH{sub 4}C{sub 1} with use of the cytomegalovirus promoter. The activity of the expressed protein clearly shows that both dehydrogenase and isomerase enzymatic activities are present within a single protein. However, such findings do not indicate whether the two activities reside within one or two closely related catalytic sites. With use of ({sup 3}H)-5-androstenedione, the intermediate compound in dehydroepiandrosterone (DHEA) transformation into 4-androstenedione by 3{beta}-HSD, the present study shows that 4MA (N,N-diethyl-4-methyl-3-oxo-4-aza-5{alpha}-androstane-17{beta}-carboxamide) and its analogues of 5-androstenedione to 4-androstenedione with an approximately 1,000-fold higher K{sub i} value. The present results thus strongly suggest that dehydrogenase and isomerase activities are present at separate sites on the 3-{beta}-HSD protein. Such data suggest that the irreversible step in the transformation of DHEA to 4-androstenedione is due to a separate site possessing isomerase activity that converts the 5-ene-3-keto to a much more stable 4-ene-3-keto configuration.

  18. Syntheses and fully diastereospecific photochromic reactions of thiophenophan-1-enes with chiral bridges.

    PubMed

    Jin-nouchi, Hirotsugu; Takeshita, Michinori

    2012-07-27

    Thiophenophan-1-enes with chiral polyether bridges were prepared and their diastereospecific photochromic reactions were studied. The coupling reaction of substituted dithienylethenes and various chiral synthons afforded thiophenophan-1-enes, namely, bridged dithienylethenes, as single enantiomers without optical resolution, thus indicating that these reactions occurred diastereoselectively. Upon UV irradiation, each optically active thiophenophan-1-ene isomerized to the corresponding enantiomer of the closed form and returned to the initial enantiomer of the open form upon visible irradiation. Because thiophenophan-1-enes never isomerized to other diastereomers even at a high temperature, they underwent diastereospecific photochromic reactions. Large changes were observed in the measurement of the optical rotations of the solutions of thiophenophan-1-enes at 588 nm according to their photochromic reactions. As there was no absorption at this wavelength for both isomers of each thiophenophan-1-enes, the nondestructive readout of the photochromic reaction could be carried out by using these chiral thiophenophan-1-enes.

  19. Design Process Improvement for Electric CAR Harness

    NASA Astrophysics Data System (ADS)

    Sawatdee, Thiwarat; Chutima, Parames

    2017-06-01

    In an automobile parts design company, the customer satisfaction is one of the most important factors for product design. Therefore, the company employs all means to focus its product design process based on the various requirements of customers resulting in high number of design changes. The objective of this research is to improve the design process of the electric car harness that effects the production scheduling by using Fault Tree Analysis (FTA) and Failure Mode and Effect Analysis (FMEA) as the main tools. FTA is employed for root cause analysis and FMEA is used to ranking a High Risk Priority Number (RPN) which is shows the priority of factors in the electric car harness that have high impact to the design of the electric car harness. After the implementation, the improvements are realized significantly since the number of design change is reduced from 0.26% to 0.08%.

  20. Harnessing Collaborative Annotations on Online Formative Assessments

    ERIC Educational Resources Information Center

    Lin, Jian-Wei; Lai, Yuan-Cheng

    2013-01-01

    This paper harnesses collaborative annotations by students as learning feedback on online formative assessments to improve the learning achievements of students. Through the developed Web platform, students can conduct formative assessments, collaboratively annotate, and review historical records in a convenient way, while teachers can generate…

  1. Harnessing Collective Knowledge Inherent in Tag Clouds

    ERIC Educational Resources Information Center

    Cress, U.; Held, C.

    2013-01-01

    Tagging systems represent the conceptual knowledge of a community. We experimentally tested whether people harness this collective knowledge when navigating through the Web. As a within-factor we manipulated people's prior knowledge (no knowledge vs. prior knowledge that was congruent/incongruent to the collective knowledge inherent in the tags).…

  2. Seizing the Moment: Harnessing the Information Technologies

    DTIC Science & Technology

    1992-01-01

    avoiding the dangers require understanding future directions the technology may take. THE FUTURE OF INFORMATION TEC.!NOLOGY Any forecast of the...but positive effects are evident and pose apparent opportunities to deliberately harness the information technologies to promote desired outcomes ...analyze how the spread and application of the new information and communications technologies could affect the prospects for conflict and cooperation

  3. SRB Altitude Switch Assembly Wire Harness Failure

    NASA Technical Reports Server (NTRS)

    Blanche, Jim

    2002-01-01

    This paper presents an assessment of two wire harness failures that had occurred in Solid Rocket Booster Altitude Switch Assemblies S/N 200001 and S/N 20002. A list of modifications to EDU #4 and modification of qualification units 2000001 and 2000002 are also presented.

  4. Harnessing Collaborative Annotations on Online Formative Assessments

    ERIC Educational Resources Information Center

    Lin, Jian-Wei; Lai, Yuan-Cheng

    2013-01-01

    This paper harnesses collaborative annotations by students as learning feedback on online formative assessments to improve the learning achievements of students. Through the developed Web platform, students can conduct formative assessments, collaboratively annotate, and review historical records in a convenient way, while teachers can generate…

  5. Harnessing Collective Knowledge Inherent in Tag Clouds

    ERIC Educational Resources Information Center

    Cress, U.; Held, C.

    2013-01-01

    Tagging systems represent the conceptual knowledge of a community. We experimentally tested whether people harness this collective knowledge when navigating through the Web. As a within-factor we manipulated people's prior knowledge (no knowledge vs. prior knowledge that was congruent/incongruent to the collective knowledge inherent in the tags).…

  6. Properties of methacrylate-thiol-ene formulations as dental restorative materials

    PubMed Central

    Cramer, Neil B.; Couch, Charles L.; Schreck, Kathleen M.; Boulden, Jordan E.; Wydra, Robert; Stansbury, Jeffrey W.; Bowman, Christopher N.

    2010-01-01

    Objectives The objective of this study was to evaluate ternary methacrylate-thiol-ene systems, with varying thiol-ene content and thiol:ene stoichiometry, as dental restorative resin materials. It was hypothesized that an off-stoichiometric thiol-ene component would enhance interactions between the methacrylate and thiol-ene processes to reduce shrinkage stress while maintaining equivalent mechanical properties. Methods Polymerization kinetics and functional group conversions were determined by Fourier transform infrared spectroscopy (FTIR). Cured resin mechanical properties were evaluated using a three-point flexural test, carried out with a hydraulic universal test system. Polymerization shrinkage stress was measured with a tensometer coupled with simultaneous real-time conversion monitoring. Results The incorporation of thiol-ene mixtures as reactive diluents into conventional dimethacrylate resins previously was shown to combine synergistically advantageous methacrylate mechanical properties with the improved polymerization kinetics and reduced shrinkage stress of thiol-ene systems. In these systems, due to thiol consumption resultant from both the thiol-ene reaction and chain transfer involving the methacrylate polymerization, the optimum thiol:ene stoichiometry deviates from the traditional 1:1 ratio. Increasing the thiol:ene stoichiometry up to 3:1 results in systems with equivalent flexural modulus, 6 – 20 % reduced flexural strength, and 5 – 33 % reduced shrinkage stress relative to 1:1 stoichiometric thiol:ene systems. Significance Due to their improved overall functional group conversion, and shrinkage stress reduction while maintaining equivalent flexural modulus, methacrylate-thiol-ene resins, particularly those with excess thiol, beyond the conventional 1:1 thiol:ene molar ratio, yield superior dental restorative materials compared with purely dimethacrylate resins. PMID:20553973

  7. Microwave Spectrum of 1-SILA-1-ISOCYANOCYCLOPENT-3-ENE

    NASA Astrophysics Data System (ADS)

    Marshall, Frank E.; Hickman, Daniel V.; Guirgis, Gamil A.; Palmer, Michael H.; Wurrey, Charles J.; Moon, Nicole; Persinger, Thomas D.; Grubbs, G. S., II

    2017-06-01

    The microwave spectrum of synthesized molecule, 1-sila-1-isocyanocyclopent-3-ene has been studied using chirped pulse and cavity Fourier transform microwave (CP-FTMW and FTMW) techniques. The rotational spectrum has been assigned along with hyperfine splitting due to the ^{14}N nucleus. Very limited sample could be synthesized at a time with this molecule, demonstrating the power of the CP-FTMW technique. Analysis of the molecule, along with structural possibilities will be discussed.

  8. Thiol–ene click hydrogels for therapeutic delivery

    PubMed Central

    Kharkar, Prathamesh M.; Rehmann, Matthew S.; Skeens, Kelsi M.; Maverakis, Emanual; Kloxin, April M.

    2016-01-01

    Hydrogels are of growing interest for the delivery of therapeutics to specific sites in the body. For use as a delivery vehicle, hydrophilic precursors are usually laden with bioactive moieties and then directly injected to the site of interest for in situ gel formation and controlled release dictated by precursor design. Hydrogels formed by thiol–ene click reactions are attractive for local controlled release of therapeutics owing to their rapid reaction rate and efficiency under mild aqueous conditions, enabling in situ formation of gels with tunable properties often responsive to environmental cues. Herein, we will review the wide range of applications for thiol–ene hydrogels, from the prolonged release of anti-inflammatory drugs in the spine to the release of protein-based therapeutics in response to cell-secreted enzymes, with a focus on their clinical relevance. We will also provide a brief overview of thiol–ene click chemistry and discuss the available alkene chemistries pertinent to macromolecule functionalization and hydrogel formation. These chemistries include functional groups susceptible to Michael type reactions relevant for injection and radically-mediated reactions for greater temporal control of formation at sites of interest using light. Additionally, mechanisms for the encapsulation and controlled release of therapeutic cargoes are reviewed, including i) tuning the mesh size of the hydrogel initially and temporally for cargo entrapment and release and ii) covalent tethering of the cargo with degradable linkers or affinity binding sequences to mediate release. Finally, myriad thiol–ene hydrogels and their specific applications also are discussed to give a sampling of the current and future utilization of this chemistry for delivery of therapeutics, such as small molecule drugs, peptides, and biologics. PMID:28361125

  9. Oxygen-Mediated Enzymatic Polymerization of Thiol–Ene Hydrogels

    PubMed Central

    Zavada, S.R.; McHardy, N. R.; Scott, T. F.

    2014-01-01

    Materials that solidify in response to an initiation stimulus are currently utilized in several biomedical and surgical applications; however, their clinical adoption would be more widespread with improved physical properties and biocompatibility. One chemistry that is particularly promising is based on the thiol–ene addition reaction, a radical-mediated step-growth polymerization that is resistant to oxygen inhibition and thus is an excellent candidate for materials that polymerize upon exposure to aerobic conditions. Here, thiol–ene-based hydrogels are polymerized by exposing aqueous solutions of multi-functional thiol and allyl ether PEG monomers, in combination with enzymatic radical initiating systems, to air. An initiating system based on glucose oxidase, glucose, and Fe2+ is initially investigated where, in the presence of glucose, the glucose oxidase reduces oxygen to hydrogen peroxide which is then further reduced by Fe2+ to yield hydroxyl radicals capable of initiating thiol–ene polymerization. While this system is shown to effectively initiate polymerization after exposure to oxygen, the polymerization rate does not monotonically increase with raised Fe2+ concentration owing to inhibitory reactions that retard polymerization at higher Fe2+ concentrations. Conversely, replacing the Fe2+ with horseradish peroxidase affords an initiating system is that is not subject to the iron-mediated inhibitory reactions and enables increased polymerization rates to be attained. PMID:24995128

  10. Fragrance material review on oxacycloheptadec-10-ene-2-one.

    PubMed

    McGinty, D; Letizia, C S; Api, A M

    2011-12-01

    A toxicologic and dermatologic review of oxacycloheptadec-10-ene-2-one when used as a fragrance ingredient is presented. Oxacycloheptadec-10-ene-2-one is a member of the fragrance structural group macrocyclic lactone and lactide derivatives. The fragrance ingredient described herein is one of 12 structurally diverse C14, C15, and C16 compounds that include (7) saturated mono- and (2) saturated di-ester lactones and (3) unsaturated lactones. For the latter, the double bond is not adjacent to (in conjugation with) the ester group. This review contains a detailed summary of all available toxicology and dermatology papers that are related to oxacycloheptadec-10-ene-2-one and is not intended as a stand-alone document. Available data were evaluated, then summarized, and includes: physical properties; skin irritation; mucous membrane (eye) irritation; skin sensitization; phototoxicity; and genotoxicity data. A safety assessment of the entire macrocyclic lactone and lactide derivatives will be published simultaneously with this document. Please refer to Belsito et al. (2011) for an overall assessment of the safe use of this material and all macrocyclic lactone and lactide derivatives in fragrances. Belsito, D., Bickers, D., Bruze, M., Calow, P., Dagli, M., Fryer, A.D., Greim, H., Hanifin, J.H., Miyachi, Y., Saurat, J.H., Sipes, I.G., 2011. A toxicologic and dermatologic assessment of macrocylic lactones and lactide derivatives when used as fragrance ingredients. Copyright © 2011. Published by Elsevier Ltd.

  11. 42 CFR 84.1138 - Head harnesses; minimum requirements.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... Gas Masks § 84.1138 Head harnesses; minimum requirements. (a) All facepieces shall be equipped with... of pressure over the entire area in contact with the face. (b) Facepiece head harnesses, except those...

  12. 42 CFR 84.1138 - Head harnesses; minimum requirements.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... Gas Masks § 84.1138 Head harnesses; minimum requirements. (a) All facepieces shall be equipped with... of pressure over the entire area in contact with the face. (b) Facepiece head harnesses, except those...

  13. 42 CFR 84.1138 - Head harnesses; minimum requirements.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... Gas Masks § 84.1138 Head harnesses; minimum requirements. (a) All facepieces shall be equipped with... of pressure over the entire area in contact with the face. (b) Facepiece head harnesses, except those...

  14. 46 CFR 197.324 - Diver's safety harness.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... GENERAL PROVISIONS Commercial Diving Operations Equipment § 197.324 Diver's safety harness. Each safety harness used in surface-supplied diving must have— (a) A positive buckling device; and (b) An...

  15. 42 CFR 84.151 - Harness test; minimum requirements.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ...) The arrangement and suitability of all harness accessories and fittings will be considered. (b)(1) The... and suitability of all harness accessories and fittings will be considered. (c) The harness employed... of a simple arrangement for attaching the hose to a part of the wearer's clothing in a...

  16. 42 CFR 84.1138 - Head harnesses; minimum requirements.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... 42 Public Health 1 2011-10-01 2011-10-01 false Head harnesses; minimum requirements. 84.1138... Gas Masks § 84.1138 Head harnesses; minimum requirements. (a) All facepieces shall be equipped with head harnesses designed and constructed to provide adequate tension during use and an even...

  17. 42 CFR 84.178 - Head harnesses; minimum requirements.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... 42 Public Health 1 2012-10-01 2012-10-01 false Head harnesses; minimum requirements. 84.178... Air-Purifying Particulate Respirators § 84.178 Head harnesses; minimum requirements. (a) All facepieces shall be equipped with head harnesses designed and constructed to provide adequate tension...

  18. 42 CFR 84.138 - Head harnesses; minimum requirements.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... 42 Public Health 1 2012-10-01 2012-10-01 false Head harnesses; minimum requirements. 84.138... Respirators § 84.138 Head harnesses; minimum requirements. Facepieces shall be equipped with adjustable and replaceable head harnesses which are designed and constructed to provide adequate tension during use, and...

  19. 42 CFR 84.178 - Head harnesses; minimum requirements.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... 42 Public Health 1 2011-10-01 2011-10-01 false Head harnesses; minimum requirements. 84.178... Air-Purifying Particulate Respirators § 84.178 Head harnesses; minimum requirements. (a) All facepieces shall be equipped with head harnesses designed and constructed to provide adequate tension...

  20. 42 CFR 84.138 - Head harnesses; minimum requirements.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... 42 Public Health 1 2013-10-01 2013-10-01 false Head harnesses; minimum requirements. 84.138... Respirators § 84.138 Head harnesses; minimum requirements. Facepieces shall be equipped with adjustable and replaceable head harnesses which are designed and constructed to provide adequate tension during use, and...

  1. 42 CFR 84.78 - Head harnesses; minimum requirements.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... 42 Public Health 1 2010-10-01 2010-10-01 false Head harnesses; minimum requirements. 84.78 Section...-Contained Breathing Apparatus § 84.78 Head harnesses; minimum requirements. (a) Facepieces shall be equipped with adjustable and replaceable head harnesses designed and constructed to provide adequate...

  2. 42 CFR 84.178 - Head harnesses; minimum requirements.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... 42 Public Health 1 2014-10-01 2014-10-01 false Head harnesses; minimum requirements. 84.178... Air-Purifying Particulate Respirators § 84.178 Head harnesses; minimum requirements. (a) All facepieces shall be equipped with head harnesses designed and constructed to provide adequate tension...

  3. 42 CFR 84.138 - Head harnesses; minimum requirements.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... 42 Public Health 1 2011-10-01 2011-10-01 false Head harnesses; minimum requirements. 84.138... Respirators § 84.138 Head harnesses; minimum requirements. Facepieces shall be equipped with adjustable and replaceable head harnesses which are designed and constructed to provide adequate tension during use, and...

  4. 42 CFR 84.178 - Head harnesses; minimum requirements.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... 42 Public Health 1 2013-10-01 2013-10-01 false Head harnesses; minimum requirements. 84.178... Air-Purifying Particulate Respirators § 84.178 Head harnesses; minimum requirements. (a) All facepieces shall be equipped with head harnesses designed and constructed to provide adequate tension...

  5. 42 CFR 84.201 - Head harnesses; minimum requirements.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... 42 Public Health 1 2013-10-01 2013-10-01 false Head harnesses; minimum requirements. 84.201... Cartridge Respirators § 84.201 Head harnesses; minimum requirements. (a)(1) Facepieces for chemical... head harnesses designed and constructed to provide adequate tension during use and an even...

  6. 42 CFR 84.138 - Head harnesses; minimum requirements.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... 42 Public Health 1 2010-10-01 2010-10-01 false Head harnesses; minimum requirements. 84.138... Respirators § 84.138 Head harnesses; minimum requirements. Facepieces shall be equipped with adjustable and replaceable head harnesses which are designed and constructed to provide adequate tension during use, and...

  7. 42 CFR 84.178 - Head harnesses; minimum requirements.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... 42 Public Health 1 2010-10-01 2010-10-01 false Head harnesses; minimum requirements. 84.178... Air-Purifying Particulate Respirators § 84.178 Head harnesses; minimum requirements. (a) All facepieces shall be equipped with head harnesses designed and constructed to provide adequate tension...

  8. 42 CFR 84.201 - Head harnesses; minimum requirements.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... 42 Public Health 1 2014-10-01 2014-10-01 false Head harnesses; minimum requirements. 84.201... Cartridge Respirators § 84.201 Head harnesses; minimum requirements. (a)(1) Facepieces for chemical... head harnesses designed and constructed to provide adequate tension during use and an even...

  9. 42 CFR 84.78 - Head harnesses; minimum requirements.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... 42 Public Health 1 2011-10-01 2011-10-01 false Head harnesses; minimum requirements. 84.78 Section...-Contained Breathing Apparatus § 84.78 Head harnesses; minimum requirements. (a) Facepieces shall be equipped with adjustable and replaceable head harnesses designed and constructed to provide adequate...

  10. 42 CFR 84.201 - Head harnesses; minimum requirements.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... 42 Public Health 1 2012-10-01 2012-10-01 false Head harnesses; minimum requirements. 84.201... Cartridge Respirators § 84.201 Head harnesses; minimum requirements. (a)(1) Facepieces for chemical... head harnesses designed and constructed to provide adequate tension during use and an even...

  11. 42 CFR 84.78 - Head harnesses; minimum requirements.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... 42 Public Health 1 2014-10-01 2014-10-01 false Head harnesses; minimum requirements. 84.78 Section...-Contained Breathing Apparatus § 84.78 Head harnesses; minimum requirements. (a) Facepieces shall be equipped with adjustable and replaceable head harnesses designed and constructed to provide adequate...

  12. 42 CFR 84.78 - Head harnesses; minimum requirements.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... 42 Public Health 1 2013-10-01 2013-10-01 false Head harnesses; minimum requirements. 84.78 Section...-Contained Breathing Apparatus § 84.78 Head harnesses; minimum requirements. (a) Facepieces shall be equipped with adjustable and replaceable head harnesses designed and constructed to provide adequate...

  13. 42 CFR 84.121 - Head harnesses; minimum requirements.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... 42 Public Health 1 2010-10-01 2010-10-01 false Head harnesses; minimum requirements. 84.121... § 84.121 Head harnesses; minimum requirements. (a) Facepieces shall be equipped with adjustable and replaceable head harnesses, designed and constructed to provide adequate tension during use and an...

  14. 42 CFR 84.201 - Head harnesses; minimum requirements.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... 42 Public Health 1 2010-10-01 2010-10-01 false Head harnesses; minimum requirements. 84.201... Cartridge Respirators § 84.201 Head harnesses; minimum requirements. (a)(1) Facepieces for chemical... head harnesses designed and constructed to provide adequate tension during use and an even...

  15. 42 CFR 84.78 - Head harnesses; minimum requirements.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... 42 Public Health 1 2012-10-01 2012-10-01 false Head harnesses; minimum requirements. 84.78 Section...-Contained Breathing Apparatus § 84.78 Head harnesses; minimum requirements. (a) Facepieces shall be equipped with adjustable and replaceable head harnesses designed and constructed to provide adequate...

  16. 42 CFR 84.138 - Head harnesses; minimum requirements.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... 42 Public Health 1 2014-10-01 2014-10-01 false Head harnesses; minimum requirements. 84.138... Respirators § 84.138 Head harnesses; minimum requirements. Facepieces shall be equipped with adjustable and replaceable head harnesses which are designed and constructed to provide adequate tension during use, and...

  17. Functional Microcapsules via Thiol-Ene Photopolymerization in Droplet-Based Microfluidics.

    PubMed

    Amato, Douglas V; Lee, Hyomin; Werner, Jörg G; Weitz, David A; Patton, Derek L

    2017-02-01

    Thiol-ene chemistry was exploited in droplet-based microfluidics to fabricate advanced microcapsules with tunable encapsulation, degradation, and thermal properties. In addition, by utilizing the thiol-ene photopolymerization with tunable cross-link density, we demonstrate the importance of monomer conversion on the retention of omniphilic cargo in double emulsion templated microcapsules. Furthermore, we highlight the rapid cure kinetics afforded by thiol-ene chemistry in a continuous flow photopatterning device for hemispherical microparticle production.

  18. Harnessing Light: the study and an update

    NASA Astrophysics Data System (ADS)

    Guenther, Arthur H.

    2002-05-01

    The completion of the report 'Harnessing Light: Optical Science and Engineering for the 21st Century' by COSE (Committee on Optical Science and Engineering) by the National Academy in 1998 has had a profound effect on optics related activities and the recognition of optics as a most pervasive and enabling field of technology. After a brief summary of the report - an update on its principal recommendations and other significant U.S. and global activities will be highlighted.

  19. Manufacturing and quality control of FCC harnesses

    NASA Technical Reports Server (NTRS)

    Malohm, W. L.; Vandergriff, J.

    1972-01-01

    The Saturn 5 program contractors encountered many technological challenges and problems relative to inter-connecting wiring and cabling during the development stages of the Saturn program. The knowledge gained from solving these problems, plus recently developed state-of-the-art techniques, materials, and processes were documented in a report prepared for NASA/MSFC. The portions of that report which deal with FCC harnesses are presented.

  20. Harnessing the wisdom of the inner crowd.

    PubMed

    Herzog, Stefan M; Hertwig, Ralph

    2014-10-01

    Ever since Galton's classic demonstration of the wisdom of crowds in estimating the weight of a slaughtered ox, scholars of the mind and the public alike have been fascinated by the counterintuitive accuracy achieved by simply averaging a number of people's estimates. Surprisingly, individuals can, to some extent, harness the wisdom of crowds within the confines of their own mind by averaging self-generated, nonredundant estimates.

  1. Harnessing the Potential of Additive Manufacturing

    DTIC Science & Technology

    2016-12-01

    31 Defense AT&L: November-December 2016 Harnessing the Potential of Additive Manufacturing Bill Decker Decker is director of Technology...achieve its goal of competition throughout the acquisition life cycle. When we look at additive manufacturing , we have a much different environment. To...Titanium-6 Aluminum-4 Vanadium with Powder Bed Fusion. This specification covers additively manufactured titanium-6 aluminum-4 vanadium (Ti-6Al-4V

  2. Behavior of sandhill cranes harnessed with different satellite transmitters

    USGS Publications Warehouse

    Olsen, G.H.; Ellis, D.H.; Landfried, S.E.; Miller, L.H.; Klugman, S.S.; Fuller, M.R.; Vermillion, C.H.

    1992-01-01

    The effectiveness of various attachment methods and designs of platform transmitting terminals (PTT's) was tested on captive sandhill cranes (Grus canadensis) at the Patuxent Wildlife Research Center, Laurel, Maryland, during 1989-91. Combinations of attachment and transmitter designs included neoprene cord harness with batteries separate from the transmitter (2 harness designs), Teflon ribbon harness with batteries incorporated into the transmitter package (4 transmitter models), and a package attached directly to the bird with epoxy glue only. Physical effects seen on cranes wearing PTT's ranged from skin lacerations (caused by rubbing of harness material) to no observed effects (other than feather wear). The most successful harness material and design utilized a Teflon ribbon harness with the 4 ribbon ends from the transmitter forming a neck loop and a body loop joined at the sternum. Time spent by sandhill cranes performing most activities did not change after transmitter attachment using this harness method.

  3. Functional Conducting Polymers via Thiol-ene Chemistry

    PubMed Central

    Feldman, Kathleen E.; Martin, David C.

    2012-01-01

    We demonstrate here that thiol-ene chemistry can be used to provide side-chain functionalized monomers based on 3,4-propylenedioxythiophene (ProDOT) containing ionic, neutral, hydrophobic, and hydrophilic side chains. All reactions gave high yields and purification could generally be accomplished through precipitation. These monomers were polymerized either chemically or electro-chemically to give soluble materials or conductive films, respectively. This strategy provides for facile tuning of the solubility, film surface chemistry, and film morphology of this class of conducting polymers. PMID:25585932

  4. Biotransformation of 7alpha-hydroxy- and 7-oxo-ent-atis-16-ene derivatives by the fungus Gibberella fujikuroi.

    PubMed

    Fraga, Braulio M; Gonzalez, Pedro; Gonzalez-Vallejo, Victoria; Guillermo, Ricardo; Diaz, Luz N

    2010-08-01

    The microbiological transformation of 7alpha,19-dihydroxy-ent-atis-16-ene by the fungus Gibberella fujikuroi gave 19-hydroxy-7-oxo-ent-atis-16-ene, 13(R),19-dihydroxy-7-oxo-ent-atis-16-ene, 7alpha,11beta,19-trihydroxy-ent-atis-16-ene and 7alpha,16beta,19-trihydroxy-ent-atis-16-ene, while the incubation of 19-hydroxy-7-oxo-ent-atis-16-ene afforded 13(R),19-dihydroxy-7-oxo-ent-atis-16-ene and 16beta,17-dihydroxy-7-oxo-ent-atisan-19-al. The biotransformation of 7-oxo-ent-atis-16-en-19-oic acid gave 6beta-hydroxy-7-oxo-ent-atis-16-en-19-oic acid, 6beta,16beta,17-trihydroxy-7-oxo-19-nor-ent-atis-4(18)-ene and 3beta,7alpha-dihydroxy-6-oxo-ent-atis-16-en-19-oic acid.

  5. Sizing and fit of fall-protection harnesses.

    PubMed

    Hsiao, Hongwei; Bradtmiller, Bruce; Whitestone, Jennifer

    2003-10-10

    Full-body fall-protection harnesses have been a critical work-practice control technology for reducing the number of fall-related injuries and fatalities among construction workers; yet, very little is known about the fit of these harnesses to the population that wears them. This study evaluated the fit and sizing efficacy of a harness system. Seventy-two male and 26 female construction workers participated in the study. Their body size-and-shape information was measured while they were suspended (with a harness) and standing (with and without a harness), using a 3-D full-body laser scanner and traditional anthropometric calipers. Fisher's discriminant analysis results did not point to the need for a change in the current sizing selection scheme by body height and weight for end users. However, an integrated redesign of harness components is needed because 40% of subjects did not pass fit-performance criteria in either the standing or suspended condition. A multivariate accommodation analysis has identified 15 representative body models for the 'standard-size' harness design. These models can serve as a useful population to test harness design until a larger survey of the nation's construction workers can be done. Finally, further developments in 3-D shape quantification methods are recommended to improve the harness design process; the point-to-point anthropometric information currently used seems to be insufficient for harness design.

  6. Harnessing microbial activities for environmental cleanup.

    PubMed

    Löffler, Frank E; Edwards, Elizabeth A

    2006-06-01

    Human activities have released large amounts of toxic organic and inorganic chemicals into the environment. Toxic waste streams threaten dwindling drinking water supplies and impact terrestrial, estuarine and marine ecosystems. Cleanup is technically challenging and the costs based on traditional technologies are exceeding the economic capabilities of even the richest countries. Recent advances in our understanding of the microbiology contributing to contaminant transformation and detoxification has led to successful field demonstrations. Hence, harnessing the activity of naturally occurring bacteria, particularly the power of anaerobic reductive processes, is a promising approach to restore contaminated subsurface environments, protect drinking water reservoirs and to safeguard ecosystem health.

  7. Harnessing the Microbiome to Enhance Cancer Immunotherapy

    PubMed Central

    Nelson, Michelle H.; Diven, Marshall A.; Huff, Logan W.; Paulos, Chrystal M.

    2015-01-01

    The microbiota plays a key role in regulating the innate and adaptive immune system. Herein, we review the immunological aspects of the microbiota in tumor immunity in mice and man, with a focus on toll-like receptor (TLR) agonists, vaccines, checkpoint modulators, chemotherapy, and adoptive T cell transfer (ACT) therapies. We propose innovative treatments that may safely harness the microbiota to enhance T cell-based therapies in cancer patients. Finally, we highlight recent developments in tumor immunotherapy, particularly novel ways to modulate the microbiome and memory T cell responses to human malignancies. PMID:26101781

  8. Stereochemistry of bistricyclic aromatic enes and related polycyclic systems.

    PubMed

    Biedermann, P Ulrich; Agranat, Israel

    2014-01-01

    Bistricyclic aromatic enes (BAEs) and related polycyclic systems are a class of molecular materials that display a rich variety of conformations, dynamic stereochemistry and switchable chirality, color, and spectroscopic properties. This is due to the a subtle interplay of the inherent preference for planarity of aromatic systems and the competing necessity of non-planarity due to intramolecular overcrowding in the fjord regions built into the general molecular structure of BAEs. The conformational, dynamic, and spectroscopic properties may be designed and fine-tuned, e.g., by variation of the bridging groups X and Y, the overcrowding in the fjord regions, extensions of the aromatic system, or other modifications of the general BAE structure, based on the fundamental understanding of the structure-property relationships (SPR). The present review provides an analysis of the conformational spaces and the dynamic stereochemistry of overcrowded bistricyclic aromatic enes applying fundamental symmetry considerations. The symmetry analysis presented here allows deeper insight into the conformations, chirality, and the mechanisms of the dynamic stereochemistry, and will be instrumental in future computational studies.

  9. Rapid photochemical surface patterning of proteins in thiol-ene based microfluidic devices.

    PubMed

    Lafleur, Josiane P; Kwapiszewski, Radoslaw; Jensen, Thomas G; Kutter, Jörg P

    2013-02-21

    The suitable optical properties of thiol-ene polymers combined with the ease of modifying their surface for the attachment of recognition molecules make them ideal candidates in many biochip applications. This paper reports the rapid one-step photochemical surface patterning of biomolecules in microfluidic thiol-ene chips. This work focuses on thiol-ene substrates featuring an excess of thiol groups at their surface. The thiol-ene stoichiometric composition can be varied to precisely control the number of surface thiol groups available for surface modification up to an average surface density of 136 ± 17 SH nm(-2). Biotin alkyne was patterned directly inside thiol-ene microchannels prior to conjugation with fluorescently labelled streptavidin. The surface bound conjugates were detected by evanescent wave-induced fluorescence (EWIF), demonstrating the success of the grafting procedure and its potential for biochip applications.

  10. Harnessing microtubule dynamic instability for nanostructure assembly

    NASA Astrophysics Data System (ADS)

    Bouchard, Ann M.; Warrender, Christina E.; Osbourn, Gordon C.

    2006-10-01

    Intracellular molecular machines synthesize molecules, tear apart others, transport materials, transform energy into different forms, and carry out a host of other coordinated processes. Many molecular processes have been shown to work outside of cells, and the idea of harnessing these molecular machines to build nanostructures is attractive. Two examples are microtubules and motor proteins, which aid cell movement, help determine cell shape and internal structure, and transport vesicles and organelles within the cell. These molecular machines work in a stochastic, noisy fashion: microtubules switch randomly between growing and shrinking in a process known as dynamic instability; motor protein movement along microtubules is randomly interrupted by the motor proteins falling off. A common strategy in attempting to gain control over these highly dynamic, stochastic processes is to eliminate some processes (e.g., work with stabilized microtubules) in order to focus on others (interaction of microtubules with motor proteins). In this paper, we illustrate a different strategy for building nanostructures, which, rather than attempting to control or eliminate some dynamic processes, uses them to advantage in building nanostructures. Specifically, using stochastic agent-based simulations, we show how the natural dynamic instability of microtubules can be harnessed in building nanostructures, and discuss strategies for ensuring that “unreliable” stochastic processes yield a robust outcome.

  11. Harnessing microtubule dynamic instability for nanostructure assembly.

    SciTech Connect

    Bouchard, Ann Marie; Osbourn, Gordon Cecil

    2004-06-01

    Intracellular molecular machines synthesize molecules, tear apart others, transport materials, transform energy into different forms, and carry out a host of other coordinated processes. Many molecular processes have been shown to work outside of cells, and the idea of harnessing these molecular machines to build nanostructures is attractive. Two examples are microtubules and motor proteins, which aid cell movement, help determine cell shape and internal structure, and transport vesicles and organelles within the cell. These molecular machines work in a stochastic, noisy fashion: microtubules switch randomly between growing and shrinking in a process known as dynamic instability; motor protein movement along microtubules is randomly interrupted by the motor proteins falling off. A common strategy in attempting to gain control over these highly dynamic, stochastic processes is to eliminate some processes (e.g., work with stabilized microtubules) in order to focus on others (interaction of microtubules with motor proteins). In this paper, we illustrate a different strategy for building nanostructures, which, rather than attempting to control or eliminate some dynamic processes, uses them to advantage in building nanostructures. Specifically, using stochastic agent-based simulations, we show how the natural dynamic instability of microtubules can be harnessed in building nanostructures, and discuss strategies for ensuring that 'unreliable' stochastic processes yield a robust outcome.

  12. Thiol-ene clickable hyaluronans: from macro-to nanogels.

    PubMed

    Hachet, Emilie; Sereni, Nicolas; Pignot-Paintrand, Isabelle; Ravaine, Valérie; Szarpak-Jankowska, Anna; Auzély-Velty, Rachel

    2014-04-01

    The fabrication of hyaluronic acid (HA) nanogels using a thiol-ene reaction has been demonstrated. HA was modified with pentenoate groups and then cross-linked with poly(ethylene glycol)-bis(thiol) by exposure to UV light. The cross-linking density and thereby the rigidity of the obtained gels were precisely controlled by the degree of substitution of pentenoate-modified HA. Their swelling properties also depended on cross-linking density. To produce hydrogels at the nanoscale, hyaluronic acid precursors were solely confined inside liposomes before cross-linking and purified after cross-linking. The size of the resulting nanogels followed their swelling properties and was also affected by their cross-linking density. Such bionanogels with tunable mechanical and swelling properties have potential in drug delivery.

  13. Tetramethyl-1-silacycloprop-2-ene: its characterization and reactions

    SciTech Connect

    Cornett, B.J.

    1980-05-01

    The object of this research is to fully characterize and study some of the reactions of tetramethyl-1-silacycloprop-2-ene. The final characterization of this compound was accomplished by obtaining both Si29 and 13C nuclear magnetic resonance spectra. The reactions studied included those with fluorenone, acetone, styrene, phenylacetylene, acetonitrile, t-butylcyanide, methyl isocyanate, phenyl azide, and azobenzene. Product analyses suggest that aside from addition reactions tetramethylsilacyclopropene can react either via a radical chain polymerization or an anionic chain polymerization mechanism with the latter being the more prevalent. Other reactions studied included the photolysis of tetramethylsilacyclopropene and its reactions in the presence of Pd(PPh/sub 3/)/sub 2/Cl/sub 2/. An appendix includes a study of trimethylsilyl radical disproportionation in the liquid phase to a sila olefin. Trimethylsilyl radicals in solution undergo disproportionation as well as recombination in a 1:5 ratio. The sila olefin formed by disproportionation was trapped by alcohols.

  14. Hydrolytically Stable Thiol-ene Networks for Flexible Bioelectronics.

    PubMed

    Reit, Radu; Zamorano, Daniel; Parker, Shelbi; Simon, Dustin; Lund, Benjamin; Voit, Walter; Ware, Taylor H

    2015-12-30

    Hydrolytically stable, tunable modulus polymer networks are demonstrated to survive harsh alkaline environments and offer promise for use in long-term implantable bioelectronic medicines known as electroceuticals. Today's polymer networks (such as polyimides or polysiloxanes) succeed in providing either stiff or soft substrates for bioelectronics devices; however, the capability to significantly tune the modulus of such materials is lacking. Within the space of materials with easily modified elastic moduli, thiol-ene copolymers are a subset of materials that offer a promising solution to build next generation flexible bioelectronics but have typically been susceptible to hydrolytic degradation chronically. In this inquiry, we demonstrate a materials space capable of tuning the substrate modulus and explore the mechanical behavior of such networks. Furthermore, we fabricate an array of microelectrodes that can withstand accelerated aging environments shown to destroy conventional flexible bioelectronics.

  15. Ester-free Thiol-ene Dental Restoratives – Part A: Resin Development

    PubMed Central

    Podgórski, Maciej; Becka, Eftalda; Claudino, Mauro; Flores, Alexander; Shah, Parag K.; Stansbury, Jeffrey W.; Bowman, Christopher N.

    2015-01-01

    Objectives To detail the development of ester-free thiol-ene dental resins with enhanced mechanical performance, limited potential for water uptake/leachables/degradation and low polymerization shrinkage stress. Methods Thiol-terminated oligomers were prepared via a thiol-Michael reaction and a bulky tetra-allyl monomer containing urethane linkages was synthesized. The experimental oligomers and/or monomers were photopolymerized using visible light activation. Several thiol-ene formulations were investigated and their performance ranked by comparisons of the thermo-mechanical properties, polymerization shrinkage stress, water sorption/solubility, and reactivity with respect to a control comprising a conventional BisGMA/TEGDMA dental resin. Results The ester-free thiol-ene formulations had significantly lower viscosities, water sorption and solubility than the BisGMA/TEGDMA control. Depending on the resin, the limiting functional conversions were equivalent to or greater than that of BisGMA/TEGDMA. At comparable conversions, lower shrinkage stress values were achieved by the thiol-ene systems. The polymerization shrinkage stress was dramatically reduced when the tetra-allyl monomer was used as the ene in ester-free thiol-ene mixtures. Although exhibiting lower Young’s modulus, flexural strength, and glass transition temperatures, the toughness values associated with thiol-ene resins were greater than that of the BisGMA/TEGDMA control. In addition, the thiol-ene polymerization resulted in highly uniform polymer networks as indicated by the narrow tan delta peak widths. Significance Employing the developed thiol-ene resins in dental composites will reduce shrinkage stress and moisture absorption and form tougher materials. Furthermore, their low viscosities are expected to enable higher loadings of functionalized micro/nano-scale filler particles relevant for practical dental systems. PMID:26360013

  16. Harnessing supramolecular peptide nanotechnology in biomedical applications.

    PubMed

    Chan, Kiat Hwa; Lee, Wei Hao; Zhuo, Shuangmu; Ni, Ming

    2017-01-01

    The harnessing of peptides in biomedical applications is a recent hot topic. This arises mainly from the general biocompatibility of peptides, as well as from the ease of tunability of peptide structure to engineer desired properties. The ease of progression from laboratory testing to clinical trials is evident from the plethora of examples available. In this review, we compare and contrast how three distinct self-assembled peptide nanostructures possess different functions. We have 1) nanofibrils in biomaterials that can interact with cells, 2) nanoparticles that can traverse the bloodstream to deliver its payload and also be bioimaged, and 3) nanotubes that can serve as cross-membrane conduits and as a template for nanowire formation. Through this review, we aim to illustrate how various peptides, in their various self-assembled nanostructures, possess great promise in a wide range of biomedical applications and what more can be expected.

  17. Harnessing yeast organelles for metabolic engineering.

    PubMed

    Hammer, Sarah K; Avalos, José L

    2017-08-01

    Each subcellular compartment in yeast offers a unique physiochemical environment and metabolite, enzyme, and cofactor composition. While yeast metabolic engineering has focused on assembling pathways in the cell cytosol, there is growing interest in embracing subcellular compartmentalization. Beyond harnessing distinct organelle properties, physical separation of organelles from the cytosol has the potential to eliminate metabolic crosstalk and enhance compartmentalized pathway efficiency. In this Perspective we review the state of the art in yeast subcellular engineering, highlighting the benefits of targeting biosynthetic pathways to subcellular compartments, including mitochondria, peroxisomes, the ER and/or Golgi, vacuoles, and the cell wall, in different yeast species. We compare the performances of strains developed with subcellular engineering to those of native producers or yeast strains previously engineered with cytosolic pathways. We also identify important challenges that lie ahead, which need to be addressed for organelle engineering to become as mainstream as cytosolic engineering in academia and industry.

  18. Harnessing supramolecular peptide nanotechnology in biomedical applications

    PubMed Central

    Chan, Kiat Hwa; Lee, Wei Hao; Zhuo, Shuangmu; Ni, Ming

    2017-01-01

    The harnessing of peptides in biomedical applications is a recent hot topic. This arises mainly from the general biocompatibility of peptides, as well as from the ease of tunability of peptide structure to engineer desired properties. The ease of progression from laboratory testing to clinical trials is evident from the plethora of examples available. In this review, we compare and contrast how three distinct self-assembled peptide nanostructures possess different functions. We have 1) nanofibrils in biomaterials that can interact with cells, 2) nanoparticles that can traverse the bloodstream to deliver its payload and also be bioimaged, and 3) nanotubes that can serve as cross-membrane conduits and as a template for nanowire formation. Through this review, we aim to illustrate how various peptides, in their various self-assembled nanostructures, possess great promise in a wide range of biomedical applications and what more can be expected. PMID:28223805

  19. Readout fidelity of coaxial holographic digital data page recording in nanoparticle-(thiol-ene) polymer composites

    NASA Astrophysics Data System (ADS)

    Nagaya, Kohta; Hata, Eiji; Tomita, Yasuo

    2016-09-01

    We report on an experimental investigation of nanoparticle-concentration and thiol-to-ene stoichiometric ratio dependences of symbol error rates (SERs) and signal-to-noise ratios (SNRs) of digital data pages recorded at a wavelength of 532 nm in thiol-ene based nanoparticle-polymer composite (NPC) films by using a coaxial holographic digital data storage method. We show that SERs and SNRs at the optimized material condition can be lower than 1 × 10-4 and higher than 10, respectively, without error correction coding. These results show the usefulness of thiol-ene based NPCs as coaxial holographic data storage media.

  20. 46 CFR 197.324 - Diver's safety harness.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... 46 Shipping 7 2012-10-01 2012-10-01 false Diver's safety harness. 197.324 Section 197.324 Shipping COAST GUARD, DEPARTMENT OF HOMELAND SECURITY (CONTINUED) MARINE OCCUPATIONAL SAFETY AND HEALTH STANDARDS GENERAL PROVISIONS Commercial Diving Operations Equipment § 197.324 Diver's safety harness. Each...

  1. Body-fitted harness provides safe and easy component handling

    NASA Technical Reports Server (NTRS)

    Miller, E. G.; Rothwell, G. E.

    1966-01-01

    Body-fitted restraint harness enables workers to safely and conveniently handle critical components during their installation or removal. Since the harness supports the components, the worker is able to maneuver through restricted areas with his hands free. It is easily put on, adjusted, and removed, or comfortably worn without interfering with normal activities.

  2. Accessory child safety harnesses: do the risks outweigh the benefits?

    PubMed

    Brown, Julie; Wainohu, Derek; Aquilina, Peter; Suratno, Basuki; Kelly, Paul; Bilston, Lynne E

    2010-01-01

    Accessory child safety harnesses are available in some countries as alternative restraints for young children or as an accessory restraint used with booster seats. Their use, in Australia at least, is becoming more common. There have been concerns that the risk of misuse of these restraints outweighs any potential benefit this system might have over a retractable lap-shoulder belt system used with a booster seat. However to date there is no evidence to confirm or deny this. This study used laboratory simulated frontal crash tests to examine the performance of accessory child safety harness systems compared to the lap-shoulder belt when used alone and when used with two common designs of Australian booster seat. The performance of the child safety harness system when misused was also investigated. The results demonstrate that the correctly used child safety harness system performed no better than the lap-shoulder system, and in fact allows for a greater risk of submarining. Furthermore, one common form of child safety harness misuse, where the harness is over-tightened causing the lap belt to be positioned high over the abdomen, allowed extremely undesirable dummy motion. This involved gross submarining and direct contact between the harness system and the dummy's neck. These findings suggest that the risks associated with accessory child safety harness systems most likely outweigh any potential benefits, in frontal impacts at least.

  3. 46 CFR 197.324 - Diver's safety harness.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... 46 Shipping 7 2014-10-01 2014-10-01 false Diver's safety harness. 197.324 Section 197.324 Shipping... GENERAL PROVISIONS Commercial Diving Operations Equipment § 197.324 Diver's safety harness. Each safety... diver's body; and (2) Prevents strain on the mask or helmet. ...

  4. Manufacturing and quality control of interconnecting wire harnesses, Volume 4

    NASA Technical Reports Server (NTRS)

    1972-01-01

    The document covers interconnecting wire harnesses defined in the design standard, including type 8, flat conductor cable. Volume breadth covers installations of groups of harnesses in a major assembly and the associated post installation inspections and electrical tests. Knowledge gained through experience on the Saturn 5 program coupled with recent advances in techniques, materials, and processes was incorporated into this document.

  5. Dynamic Testing and Automatic Repair of Reconfigurable Wiring Harnesses

    DTIC Science & Technology

    2006-11-27

    made it possible to consider the construction of reconfigurable manifolds - essentially, wiring harnesses that behave like macroscopic FPGA routing...must withstand extreme temperatures, hard vacuum and high levels of radiation for years without maintenance. Conventionally, spacecraft wiring ... harnesses are built with architectures that are fixed at the time of manufacture. They must therefore be designed to endure the lifetime of the mission

  6. Registration of two double rust resistant germplasms, HA-R12 and HA-R13 for confection sunflower

    USDA-ARS?s Scientific Manuscript database

    The confection sunflower (Helianthus annuus L.) germplasms HA-R12 (Reg. No. ______, PI 673104) and HA-R13 (Reg. No. ______, PI 673105) were developed by the USDA-ARS, Sunflower and Plant Biology Research Unit in collaboration with the North Dakota Agricultural Experiment Station, and released in Jul...

  7. Registration of two confection sunflower germplasm Lines, HA-R10 and HA-R11, Resistant to sunflower rust

    USDA-ARS?s Scientific Manuscript database

    Two confection sunflower (Helianthus annuus L.) germplasm lines, HA-R10 (Reg. No.xxx, PI670043) and HA-R11 (Reg. No.xxx, PI670044) were developed by the USDA-ARS Sunflower and Plant Biology Research Unit in collaboration with the North Dakota Agricultural Experiment Station and released December, 20...

  8. Harnessing adolescent values to motivate healthier eating

    PubMed Central

    Bryan, Christopher J.; Yeager, David S.; Hinojosa, Cintia P.; Chabot, Aimee; Bergen, Holly; Kawamura, Mari; Steubing, Fred

    2016-01-01

    What can be done to reduce unhealthy eating among adolescents? It was hypothesized that aligning healthy eating with important and widely shared adolescent values would produce the needed motivation. A double-blind, randomized, placebo-controlled experiment with eighth graders (total n = 536) evaluated the impact of a treatment that framed healthy eating as consistent with the adolescent values of autonomy from adult control and the pursuit of social justice. Healthy eating was suggested as a way to take a stand against manipulative and unfair practices of the food industry, such as engineering junk food to make it addictive and marketing it to young children. Compared with traditional health education materials or to a non–food-related control, this treatment led eighth graders to see healthy eating as more autonomy-assertive and social justice-oriented behavior and to forgo sugary snacks and drinks in favor of healthier options a day later in an unrelated context. Public health interventions for adolescents may be more effective when they harness the motivational power of that group’s existing strongly held values. PMID:27621440

  9. Harnessing adolescent values to motivate healthier eating.

    PubMed

    Bryan, Christopher J; Yeager, David S; Hinojosa, Cintia P; Chabot, Aimee; Bergen, Holly; Kawamura, Mari; Steubing, Fred

    2016-09-27

    What can be done to reduce unhealthy eating among adolescents? It was hypothesized that aligning healthy eating with important and widely shared adolescent values would produce the needed motivation. A double-blind, randomized, placebo-controlled experiment with eighth graders (total n = 536) evaluated the impact of a treatment that framed healthy eating as consistent with the adolescent values of autonomy from adult control and the pursuit of social justice. Healthy eating was suggested as a way to take a stand against manipulative and unfair practices of the food industry, such as engineering junk food to make it addictive and marketing it to young children. Compared with traditional health education materials or to a non-food-related control, this treatment led eighth graders to see healthy eating as more autonomy-assertive and social justice-oriented behavior and to forgo sugary snacks and drinks in favor of healthier options a day later in an unrelated context. Public health interventions for adolescents may be more effective when they harness the motivational power of that group's existing strongly held values.

  10. Harnessing nanomedicine for therapeutic intervention in glioblastoma.

    PubMed

    Gutkin, Anna; Cohen, Zvi R; Peer, Dan

    2016-11-01

    Glioblastoma is a type of brain cancer arises from glial cells. Glioblastoma multiforme (GBM), a subtype of glioblastoma, is the most common and most aggressive primary brain tumor. Currently, GBM therapy includes surgery and post-operative high-doses of radiation and chemotherapy. This therapeutic strategy has a limited contribution in extending the survival rate of GBM patients. Areas covered: Herein, we focus on harnessing nanoscale drug delivery strategies to treat brain malignancies. Specifically, we briefly discuss the challenges facing GBM therapy such as restricted passage across the blood-brain barrier (BBB) and low enhanced permeability and retention effect. Next, we describe different pathways to address these challenges. Finally, we discuss the field of nanomedicine, which emerged as a promising platform for drug delivery to brain malignancies. Expert opinion: Countless strategies have been applied in preclinical and clinical settings to treat GBM. Among them is the use of different types of nanoparticles (NPs) and viruses with different approaches to cross or bypass the BBB. We suggest here a paradigm shift in thinking about crossing the BBB and tumor penetration as fundamental issues that need to be address in order to improve the therapeutic outcome in GBM.

  11. Harnessing Regulatory T cells to Suppress Asthma

    PubMed Central

    Thorburn, Alison N.; Hansbro, Philip M.

    2010-01-01

    Regulatory T cells (Tregs) play an essential role in maintaining the homeostatic balance of immune responses. Asthma is an inflammatory condition of the airways that is driven by dysregulated immune responses toward normally innocuous antigens. Individuals with asthma have fewer and less functional Tregs, which may lead to uncontrolled effector cell responses and promote proasthmatic responses of T helper type 2, T helper 17, natural killer T, antigen-presenting, and B cells. Tregs have the capacity to either directly or indirectly suppress these responses. Hence, the induced expansion of functional Tregs in predisposed or individuals with asthma is a potential approach for the prevention and treatment of asthma. Infection by a number of micro-organisms has been associated with reduced prevalence of asthma, and many infectious agents have been shown to induce Tregs and reduce allergic airways disease in mouse models. The translation of the regulatory and therapeutic properties of infectious agents for use in asthma requires the identification of key modulatory components and the development and trial of effective immunoregulatory therapies. Further translational and clinical research is required for the induction of Tregs to be harnessed as a therapeutic strategy for asthma. PMID:20097830

  12. SSME Electrical Harness and Cable Development and Evolution

    NASA Technical Reports Server (NTRS)

    Abrams, Russ; Heflin, Johnny; Burns, Bob; Camper, Scott J.; Hill, Arthur J.

    2010-01-01

    The Space Shuttle Main Engine (SSME) electrical harness and cable system consists of the various interconnecting devices necessary for operation of complex rocket engine functions. Thirty seven harnesses incorporate unique connectors, backshell adapters, conductors, insulation, shielding, and physical barriers for a long maintenance-free life while providing the means to satisfy performance requirements and to mitigate adverse environmental influences. The objective of this paper is to provide a description of the SSME electrical harness and cable designs as well as the development history and lessons learned.

  13. SSME Electrical Harness and Cable Development and Evolution

    NASA Technical Reports Server (NTRS)

    Abrams, Russ; Heflin, Johnny; Burns, Bob; Camper, Scott J.; Hill, Arthur J.

    2010-01-01

    The Space Shuttle Main Engine (SSME) electrical harness and cable system consists of the various interconnecting devices necessary for operation of complex rocket engine functions. Thirty seven harnesses incorporate unique connectors, backshell adapters, conductors, insulation, shielding, and physical barriers for a long maintenance-free life while providing the means to satisfy performance requirements and to mitigate adverse environmental influences. The objective of this paper is to provide a description of the SSME electrical harness and cable designs as well as the development history and lessons learned.

  14. High Performance Computing with Harness over InfiniBand

    SciTech Connect

    Valentini, Alessandro; Di Biagio, Christian; Batino, Fabrizio; Pennella, Guido; Palma, Fabrizio; Engelmann, Christian

    2009-01-01

    Harness is an adaptable and plug-in-based middleware framework able to support distributed parallel computing. By now, it is based on the Ethernet protocol which cannot guarantee high performance throughput and real time (determinism) performance. During last years, both, the research and industry environments have developed new network architectures (InfiniBand, Myrinet, iWARP, etc.) to avoid those limits. This paper concerns the integration between Harness and InfiniBand focusing on two solutions: IP over InfiniBand (IPoIB) and Socket Direct Protocol (SDP) technology. They allow the Harness middleware to take advantage of the enhanced features provided by the InfiniBand Architecture.

  15. Thiol-ene Clickable Poly(glycidol) Hydrogels for Biofabrication.

    PubMed

    Stichler, Simone; Jungst, Tomasz; Schamel, Martha; Zilkowski, Ilona; Kuhlmann, Matthias; Böck, Thomas; Blunk, Torsten; Teßmar, Jörg; Groll, Jürgen

    2017-01-01

    In this study we introduce linear poly(glycidol) (PG), a structural analog of poly(ethylene glycol) bearing side chains at each repeating unit, as polymer basis for bioink development. We prepare allyl- and thiol-functional linear PG that can rapidly be polymerized to a three-dimensionally cross-linked hydrogel network via UV mediated thiol-ene click reaction. Influence of polymer concentration and UV irradiation on mechanical properties and swelling behavior was examined. Thiol-functional PG was synthesized in two structural variations, one containing ester groups that are susceptible to hydrolytic cleavage, and the other one ester-free and stable against hydrolysis. This allowed the preparation of degradable and non-degradable hydrogels. Cytocompatibility of the hydrogel was demonstrated by encapsulation of human bone marrow-derived mesenchymal stem cells (hBMSCs). Rheological properties of the hydrogels were adjusted for dispense plotting by addition of high molecular weight hyaluronic acid. The optimized formulation enabled highly reproducible plotting of constructs composed of 20 layers with an overall height of 3.90 mm.

  16. Hepatic metabolism of 3-oxoandrost-4-ene-17-carboxylic acid

    SciTech Connect

    Zimniak, P.; Radominska-Pyrek, A.; Little, J.M.; Lester, R.; Pyrek, J.S.

    1986-05-01

    3-oxoandrost-4-ene-17..beta..-carboxylic acid (etienic acid), a likely catabolite of deoxycorticosterone, was synthesized in the radioactive form and injected intravenously into rats prepared with a biliary fistula. The biliary metabolites (77% of the dose) were isolated, separated into individual compounds, and identified by high-field /sup 1/H-NMR and by gas chromatographic comparison with standards. After deconjugation, aglycones were characterized by GC-MS. The administered etienic acid underwent full reduction, yielding three of the four possible distereomers: 3..cap alpha..- and 3..beta..-hydroxy-5..cap alpha..-etianic acids and 3..cap alpha..-hydroxy-5..beta..-etianic acid, accounting together for at least one third of the biliary radioactivity. In addition to the reduction, a sizeable fraction (> 25% of the recovered dose) underwent additional hydroxylation to at least two di- and one trihydroxy acid. Most (approx. 75%) of the recovered metabolites were present in conjugated form. Ester glucuronidation (conjugation on the steroidal carboxyl group) predominated, followed by ether glucuronidation (on a steroidal hydroxyl group). By the criteria of structure and biliary, rather than urinary, excretion, the saturated steroidal acids derived from etienic acid can be classified as short-chain bile acids. They conclude that degradation to short-chain bile acids followed by glucuronidation is likely to be an important catabolic pathway for certain steroid hormones.

  17. 16-Ene-steroids in the human testis.

    PubMed

    Smals, A G; Weusten, J J

    1991-01-01

    Incubation of human testicular homogenates with [4-14C]pregnenolone gave substantial amounts of an unknown metabolite within 1 min, reaching plateau values of 17-23% of total radioactivity added within 5 min. Mass spectrometry of the metabolite showed it to be identical to the boar sex pheromone precursor androsta-5, 16-diene-3 beta-ol (ADL). In cell cultures the major source of ADL and its dehydrogenated metabolite androsta-4, 16-diene-3-one (ADN) was the Leydig cell. In rat and monkey testicular homogenates 16-ene-synthetase activity, a prerequisite for the synthesis of ADL and ADN, was completely lacking, limiting the presence of 16-androstenes to boars and men. In contrast to boars, however, in the human testis no 5 alpha-reductase activity was found and consequently no 5 alpha-reduced-16-androstenes, e.g. androstenol (AL, musk like) and androstenone (AN, urine like), known sex pheromones in pigs. As both sex pheromones have been identified in urine, plasma, sweat and saliva of men and (especially hirsute) women we hypothesize that AL and AN are synthesized from ADL via ADN peripherically in tissues rich in 5 alpha-reductase, i.e. skin, axillary sweat glands and probably also the salivary glands. So far, there is some evidence that both sex pheromones may have similar functions in humans as in boars.

  18. Harnessing Earth Observations for Disaster Application Science

    NASA Astrophysics Data System (ADS)

    Green, D. S.

    2015-12-01

    Earth observations have made substantive contributions to the understanding of natural hazards, answering key science questions on the mechanisms, processes and dynamics of changes in the land, air and water. This has been achieved through the ability to advance models and interpret the results through maps and assessments. Disaster application science is focused on the two-way flow of data and information between hazard understanding and the knowledge required for disaster response, relief and recovery. This presentation will examine the integration of results from mature science and technology development in areas including optical imagery, synthetic-aperture radar and geodetic sensors, which together provide new levels of situational awareness. Specific examples will be highlighted from the recent Nepal "Gorkha" earthquake. Optical imagery from a host of satellite missions was used to create a comprehensive mosaic across the region, which when analyzed by a global network of volunteer scientists yielded insight into the extent of induced hazards and impacts. In some cases unique day/night band images provided guidance on areas where energy-dependent infrastructure of livelihoods were disrupted. Earthquake modeling and historical trend analysis revealed areas of potential vulnerability and combined with aftershock analysis to guide areas for urgent analysis and action. The combination of SAR and GPS data, innovative integration and processing approaches and nontraditional data integration approaches resulted in damage proxy maps or where combination with airborne photography, field sightings and crowd sourced reports to assess susceptibility to induced hazards (floods and landslides). Opportunities and challenges to build the science and community relationships, harness the earth observations from multiple agencies and institutions and co-develop timely applications to users will be areas for ongoing collaboration and study.Earth observations have made

  19. Harnessing Scientific Literature Reports for Pharmacovigilance

    PubMed Central

    Ripple, Anna; Tonning, Joseph; Munoz, Monica; Hasan, Rashedul; Ly, Thomas; Francis, Henry; Bodenreider, Olivier

    2017-01-01

    Summary Objectives We seek to develop a prototype software analytical tool to augment FDA regulatory reviewers’ capacity to harness scientific literature reports in PubMed/MEDLINE for pharmacovigilance and adverse drug event (ADE) safety signal detection. We also aim to gather feedback through usability testing to assess design, performance, and user satisfaction with the tool. Methods A prototype, open source, web-based, software analytical tool generated statistical disproportionality data mining signal scores and dynamic visual analytics for ADE safety signal detection and management. We leveraged Medical Subject Heading (MeSH) indexing terms assigned to published citations in PubMed/MEDLINE to generate candidate drug-adverse event pairs for quantitative data mining. Six FDA regulatory reviewers participated in usability testing by employing the tool as part of their ongoing real-life pharmacovigilance activities to provide subjective feedback on its practical impact, added value, and fitness for use. Results All usability test participants cited the tool’s ease of learning, ease of use, and generation of quantitative ADE safety signals, some of which corresponded to known established adverse drug reactions. Potential concerns included the comparability of the tool’s automated literature search relative to a manual ‘all fields’ PubMed search, missing drugs and adverse event terms, interpretation of signal scores, and integration with existing computer-based analytical tools. Conclusions Usability testing demonstrated that this novel tool can automate the detection of ADE safety signals from published literature reports. Various mitigation strategies are described to foster improvements in design, productivity, and end user satisfaction. PMID:28326432

  20. Harnessing quantum transport by transient chaos.

    PubMed

    Yang, Rui; Huang, Liang; Lai, Ying-Cheng; Grebogi, Celso; Pecora, Louis M

    2013-03-01

    Chaos has long been recognized to be generally advantageous from the perspective of control. In particular, the infinite number of unstable periodic orbits embedded in a chaotic set and the intrinsically sensitive dependence on initial conditions imply that a chaotic system can be controlled to a desirable state by using small perturbations. Investigation of chaos control, however, was largely limited to nonlinear dynamical systems in the classical realm. In this paper, we show that chaos may be used to modulate or harness quantum mechanical systems. To be concrete, we focus on quantum transport through nanostructures, a problem of considerable interest in nanoscience, where a key feature is conductance fluctuations. We articulate and demonstrate that chaos, more specifically transient chaos, can be effective in modulating the conductance-fluctuation patterns. Experimentally, this can be achieved by applying an external gate voltage in a device of suitable geometry to generate classically inaccessible potential barriers. Adjusting the gate voltage allows the characteristics of the dynamical invariant set responsible for transient chaos to be varied in a desirable manner which, in turn, can induce continuous changes in the statistical characteristics of the quantum conductance-fluctuation pattern. To understand the physical mechanism of our scheme, we develop a theory based on analyzing the spectrum of the generalized non-Hermitian Hamiltonian that includes the effect of leads, or electronic waveguides, as self-energy terms. As the escape rate of the underlying non-attracting chaotic set is increased, the imaginary part of the complex eigenenergy becomes increasingly large so that pointer states are more difficult to form, making smoother the conductance-fluctuation pattern.

  1. Harnessing Power from Tides: State of the Art.

    ERIC Educational Resources Information Center

    Ryan, Paul R.

    1979-01-01

    Discussed is the current, world-wide status of tidal energy as a potential power source. Potential sites and global tidal power prospects are identified. New engineering concepts relevant to the harnessing of tidal power are identified and described. (BT)

  2. Harnessing Energy from the Sun for Six Billion People

    ScienceCinema

    Daniel Nocera

    2016-07-12

    Daniel Nocera, a Massachusetts Institute of Technology professor whose recent research focuses on solar-powered fuels, presents a Brookhaven Science Associates Distinguished Lecture, titled "Harnessing Energy from the Sun for Six Billion People -- One at a Time."

  3. Harnessing Power from Tides: State of the Art.

    ERIC Educational Resources Information Center

    Ryan, Paul R.

    1979-01-01

    Discussed is the current, world-wide status of tidal energy as a potential power source. Potential sites and global tidal power prospects are identified. New engineering concepts relevant to the harnessing of tidal power are identified and described. (BT)

  4. Harnessing Energy from the Sun for Six Billion People

    SciTech Connect

    Daniel Nocera

    2011-09-12

    Daniel Nocera, a Massachusetts Institute of Technology professor whose recent research focuses on solar-powered fuels, presents a Brookhaven Science Associates Distinguished Lecture, titled "Harnessing Energy from the Sun for Six Billion People -- One at a Time."

  5. HARNESS END OF ELECTRIC TURBINE IN LOWER LEVEL OF HYDROELECTRIC ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    HARNESS END OF ELECTRIC TURBINE IN LOWER LEVEL OF HYDROELECTRIC POWER HOUSE - St. Lucie Canal, Lock No. 1, Hydroelectric Power House, St. Lucie, Cross State Canal, Okeechobee Intracoastal Waterway, Stuart, Martin County, FL

  6. 42 CFR 84.201 - Head harnesses; minimum requirements.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... of pressure over the entire area in contact with the face. (2) Facepieces for single-use vinyl... face. (b) Mouthpieces shall be equipped where applicable, with an adjustable and replaceable harness...

  7. Manufacturing and quality control of interconnecting wire harnesses, Volume 2

    NASA Technical Reports Server (NTRS)

    1972-01-01

    Interconnecting wire harnesses defined in the design standard are considered, including type 4, open bundle (not enclosed). Knowledge gained through experience on the Saturn 5 program coupled with recent advances in techniques, materials, and processes was incorporated into the document.

  8. Preparation and Preliminary Dielectric Characterization of Structured C60-Thiol-Ene Polymer Nanocomposites Assembled Using the Thiol-Ene Click Reaction

    PubMed Central

    Ahmed, Hanaa M.; Windham, Amber D.; Al-Ejji, Maryam M.; Al-Qahtani, Noora H.; Hassan, Mohammad K.; Mauritz, Kenneth A.; Buchanan, Randy K.; Buchanan, J. Paige

    2015-01-01

    Fullerene-containing materials have the ability to store and release electrical energy. Therefore, fullerenes may ultimately find use in high-voltage equipment devices or as super capacitors for high electric energy storage due to this ease of manipulating their excellent dielectric properties and their high volume resistivity. A series of structured fullerene (C60) polymer nanocomposites were assembled using the thiol-ene click reaction, between alkyl thiols and allyl functionalized C60 derivatives. The resulting high-density C60-urethane-thiol-ene (C60-Thiol-Ene) networks possessed excellent mechanical properties. These novel networks were characterized using standard techniques, including infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and thermal gravimetric analysis (TGA). The dielectric spectra for the prepared samples were determined over a broad frequency range at room temperature using a broadband dielectric spectrometer and a semiconductor characterization system. The changes in thermo-mechanical and electrical properties of these novel fullerene-thiol-ene composite films were measured as a function of the C60 content, and samples characterized by high dielectric permittivity and low dielectric loss were produced. In this process, variations in chemical composition of the networks were correlated to performance characteristics. PMID:28793678

  9. Preparation and Preliminary Dielectric Characterization of Structured C60-Thiol-Ene Polymer Nanocomposites Assembled Using the Thiol-Ene Click Reaction.

    PubMed

    Ahmed, Hanaa M; Windham, Amber D; Al-Ejji, Maryam M; Al-Qahtani, Noora H; Hassan, Mohammad K; Mauritz, Kenneth A; Buchanan, Randy K; Buchanan, J Paige

    2015-11-18

    Fullerene-containing materials have the ability to store and release electrical energy. Therefore, fullerenes may ultimately find use in high-voltage equipment devices or as super capacitors for high electric energy storage due to this ease of manipulating their excellent dielectric properties and their high volume resistivity. A series of structured fullerene (C60) polymer nanocomposites were assembled using the thiol-ene click reaction, between alkyl thiols and allyl functionalized C60 derivatives. The resulting high-density C60-urethane-thiol-ene (C60-Thiol-Ene) networks possessed excellent mechanical properties. These novel networks were characterized using standard techniques, including infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and thermal gravimetric analysis (TGA). The dielectric spectra for the prepared samples were determined over a broad frequency range at room temperature using a broadband dielectric spectrometer and a semiconductor characterization system. The changes in thermo-mechanical and electrical properties of these novel fullerene-thiol-ene composite films were measured as a function of the C60 content, and samples characterized by high dielectric permittivity and low dielectric loss were produced. In this process, variations in chemical composition of the networks were correlated to performance characteristics.

  10. Army Social Media: Harnessing the Power of Networked Communications

    DTIC Science & Technology

    2011-09-01

    blogging. AAFES Blog Posts from across AAFES; links to other social media products . Twitter WWW.TWITTER.COM Twitter is a micro- blogging tool that...9/1/2011 Army Social Media : harnessing the power of networked communications Report Documentation Page Form ApprovedOMB No. 0704-0188 Public...4. TITLE AND SUBTITLE Army Social Media : harnessing the power of networked communications 5a. CONTRACT NUMBER 5b. GRANT NUMBER 5c. PROGRAM

  11. Thermal and Mechanical Properties of Sequential and Simultaneous Thiol-Ene-Isocyanate Networks

    NASA Astrophysics Data System (ADS)

    McNair, Olivia; Brent, Davis; Savin, Daniel

    2011-03-01

    Ternary networks containing having stoichiometrically balanced thiol /(ene+isocyanate) ranging from 0 to 20 mol% isocyanate were synthesized via sequential or simultaneous thiol/ene and thiol/isocyanate click reactions. The effects of cross-link density were studied using three thiols, GDMP (difunctional), 3T (trifunctional) and 4T (tetrafunctional) respectively. TEA catalyzes the isocyanate-thiol coupling and chain extension, while the photoinitiator DMPA initiates a radical thiol-ene crosslinking process. Real-time FTIR was used to study kinetics of both light and dark reactions utilizing thiol, ene and isocyanate peaks which appear independently. It was found that difunctional thiols and isocyanates reacted initially, forming chain extended prepolymers end-capped with thiol functionalities. Upon UV irradiation, thiol functionalized prepolymers reacted with TTT, a trifunctional ene, forming networks containing incorporated thiourethane linkages. Initial DSC results indicated higher Tgs for higher cross-linked networks; however, isocyanate content has significant effects on each system. Films were also be thermally characterized via DMA and mechanical properties measured using MTS.

  12. Pore surface engineering in a zirconium metal–organic framework via thiol-ene reaction

    SciTech Connect

    Gui, Bo; Hu, Guiping; Zhou, Tailin; Wang, Cheng

    2015-03-15

    A porous olefin-functionalized Zr(IV)-based metal–organic framework, denoted as UiO-68-allyl, has been constructed. Our results clearly demonstrated that the surface of UiO-68-allyl could be decorated with organic molecule (ethanethiol) via thiol-ene reaction. More importantly, the crystallinity of the framework were maintained during the post-synthetic modification process. However, the microporosity of the framework is retained but the surface area decreased, due to the grafting of ethylthio groups into the pores. From our studies, we can conclude that the strategy of post-synthetic modification of UiO-68-allyl via thiol-ene reaction may be general. Furthermore, we may anchor other desired functional group onto the pore walls in Zr-MOFs via thiol-ene reaction, enabling more potential applications. - graphical abstract: In this manuscript, we reported the post-synthetic modification of an olefin-functionalized Zr(IV)-based metal–organic framework via thiol-ene reaction. - Highlights: • A porous olefin-functionalized Zr(IV)-based metal–organic framework has been constructed. • The surface of olefin-functionalized Zr-MOF could be decorated with organic molecules via thiol-ene reaction. • The crystallinity and permanent porosity of the framework were maintained during the post-synthetic modification process.

  13. Pore surface engineering in a zirconium metal-organic framework via thiol-ene reaction

    NASA Astrophysics Data System (ADS)

    Gui, Bo; Hu, Guiping; Zhou, Tailin; Wang, Cheng

    2015-03-01

    A porous olefin-functionalized Zr(IV)-based metal-organic framework, denoted as UiO-68-allyl, has been constructed. Our results clearly demonstrated that the surface of UiO-68-allyl could be decorated with organic molecule (ethanethiol) via thiol-ene reaction. More importantly, the crystallinity of the framework were maintained during the post-synthetic modification process. However, the microporosity of the framework is retained but the surface area decreased, due to the grafting of ethylthio groups into the pores. From our studies, we can conclude that the strategy of post-synthetic modification of UiO-68-allyl via thiol-ene reaction may be general. Furthermore, we may anchor other desired functional group onto the pore walls in Zr-MOFs via thiol-ene reaction, enabling more potential applications.

  14. Advances and limitations of visual conditioning protocols in harnessed bees.

    PubMed

    Avarguès-Weber, Aurore; Mota, Theo

    2016-12-18

    Bees are excellent invertebrate models for studying visual learning and memory mechanisms, because of their sophisticated visual system and impressive cognitive capacities associated with a relatively simple brain. Visual learning in free-flying bees has been traditionally studied using an operant conditioning paradigm. This well-established protocol, however, can hardly be combined with invasive procedures for studying the neurobiological basis of visual learning. Different efforts have been made to develop protocols in which harnessed honey bees could associate visual cues with reinforcement, though learning performances remain poorer than those obtained with free-flying animals. Especially in the last decade, the intention of improving visual learning performances of harnessed bees led many authors to adopt distinct visual conditioning protocols, altering parameters like harnessing method, nature and duration of visual stimulation, number of trials, inter-trial intervals, among others. As a result, the literature provides data hardly comparable and sometimes contradictory. In the present review, we provide an extensive analysis of the literature available on visual conditioning of harnessed bees, with special emphasis on the comparison of diverse conditioning parameters adopted by different authors. Together with this comparative overview, we discuss how these diverse conditioning parameters could modulate visual learning performances of harnessed bees.

  15. Evaluation of Cable Harness Post-Installation Testing. Part B

    NASA Technical Reports Server (NTRS)

    King, M. S.; Iannello, C. J.

    2011-01-01

    The Cable Harness Post-Installation Testing Report was written in response to an action issued by the Ares Project Control Board (PCB). The action for the Ares I Avionics & Software Chief Engineer and the Avionics Integration and Vehicle Systems Test Work Breakdown Structure (WBS) Manager in the Vehicle Integration Office was to develop a set of guidelines for electrical cable harnesses. Research showed that post-installation tests have been done since the Apollo era. For Ares I-X, the requirement for post-installation testing was removed to make it consistent with the avionics processes used on the Atlas V expendable launch vehicle. Further research for the report involved surveying government and private sector launch vehicle developers, military and commercial aircraft, spacecraft developers, and harness vendors. Responses indicated crewed launch vehicles and military aircraft perform post-installation tests. Key findings in the report were as follows: Test requirements identify damage, human-rated vehicles should be tested despite the identification of statistically few failures, data does not support the claim that post-installation testing damages the harness insulation system, and proper planning can reduce overhead associated with testing. The primary recommendation of the report is for the Ares projects to retain the practice of post-fabrication and post-installation cable harness testing.

  16. Anterior axial ultrasound in monitoring infants with Pavlik harness.

    PubMed

    El Ferzli, Julie; Abuamara, Saad; Eurin, Danielle; Le Dosseur, Patrick; Dacher, Jean-Nicolas

    2004-01-01

    Real-time ultrasonography has been used for diagnosis and screening of developmental dysplasia of the hip for several years. If diagnostic criteria are well established, the use of sonography in follow-up of treated infants remains extremely variable. The aims of this study were (a). to describe the normal sonographic anatomy of the infant abducted hip on an anterior axial view, and (b). to define the role of this approach in the follow-up of developmental dysplasia treated by Pavlik harness. Thirty-eight patients with Pavlik harness had anterior axial sonograms in addition to their usual clinical and sonographic follow-up. Normal anatomy was inferred from the examination of 25 clinically proven normal hips in the same population. The best criterion of a normal positioning of the femoral head appears to be the alignment of the pubic bone and the femoral metaphysis. Pavlik harness was the only treatment in 32 patients. It was directly efficient in 22, after readjustment in 10 patients. Reduction was shown by anterior sonography in all of them. In 6 children, sonography showed no reduction and subsequent treatment by closed or open reduction was carried out. Anterior axial sonogram can show reduction of a dislocated hip in children with Pavlik harness, but it does not evaluate its stability. It helps optimize the settings of the harness, and may predict a poor outcome, but it does not identify the cause of non-reducibility.

  17. Thiol-Ene functionalized siloxanes for use as elastomeric dental impression materials

    PubMed Central

    Cole, Megan A.; Jankousky, Katherine C.; Bowman, Christopher N.

    2014-01-01

    Objectives Thiol- and allyl-functionalized siloxane oligomers are synthesized and evaluated for use as a radical-mediated, rapid set elastomeric dental impression material. Thiol-ene siloxane formulations are crosslinked using a redox-initiated polymerization scheme, and the mechanical properties of the thiol-ene network are manipulated through the incorporation of varying degrees of plasticizer and kaolin filler. Formulations with medium and light body consistencies are further evaluated for their ability to accurately replicate features on both the gross and microscopic levels. We hypothesize that thiol-ene functionalized siloxane systems will exhibit faster setting times and greater detail reproduction than commercially available polyvinylsiloxane (PVS) materials of comparable consistencies. Methods Thiol-ene functionalized siloxane mixtures formulated with varying levels of redox initiators, plasticizer, and kaolin filler are made and evaluated for their polymerization speed (FTIR), consistency (ISO4823.9.2), and surface energy (goniometer). Feature replication is evaluated quantitatively by SEM. The Tg, storage modulus, and creep behavior are determined by DMA. Results Increasing redox initiation rate increases the polymerization rate but at high levels also limits working time. Combining 0.86 wt% oxidizing agent with up to 5 wt% plasticizer gave a working time of 3 min and a setting time of 2 min. The selected medium and light body thiol-ene formulations also achieved greater qualitative detail reproduction than the commercial material and reproduced micrometer patterns with 98% accuracy. Significance Improving detail reproduction and setting speed is a primary focus of dental impression material design and synthesis. Radical-mediated polymerizations, particularly thiol-ene reactions, are recognized for their speed, reduced shrinkage, and ‘click’ nature. PMID:24553250

  18. Visible-Light-Mediated Thiol-Ene Reactions through Organic Photoredox Catalysis.

    PubMed

    Zhao, Gaoyuan; Kaur, Sarbjeet; Wang, Ting

    2017-06-16

    Synthetically useful radical thiol-ene reactions can be initiated by visible-light irradiation in the presence of an organic photocatalyst, 9-mesityl-10-methylacridinum tetrafluoroborate. The key thiyl radical intermediates are generated upon quenching of the photoexcited catalyst with a variety of thiols. The success of this method requires only the use of near-stoichiometric levels of alkene coupling partners. Using these highly efficient metal-free conditions, thiol-ene reactions between carbohydrates and peptides can be accomplished in excellent yields.

  19. Modified thiol-ene networks: Tuning the glass transition temperature and energy damping capabilities

    NASA Astrophysics Data System (ADS)

    Sun, Ning; Rafailovich, Miriam; Gersappe, Dilip

    2013-03-01

    Utilizing thiol-ene `click' reactions, it is possible to produce thermoset networks that are highly homogeneous and thus exhibit enhanced energy damping capabilities. This talk will present recent results in the characterization and impact testing of modified thiol-ene networks with tunable physical properties. In particular, we synthesize ternary networks containing (1) bulky side-chain substituents, (2) isocyanate functionality, or (3) dual thiol components to improve control over the glass transition temperature and strain at break. In addition, we present results in the high-impact compression testing to demonstrate the energy damping capabilities of these materials.

  20. IMPROVEMENTS TO POLAR CAMPS - JAMESWAY ELECTRICAL WIRING HARNESS.

    DTIC Science & Technology

    A new wiring harness was developed to increase the speed of installation of electrical power in a Jamesway and to improve the quality of lighting...previously. Based on the average cost of Seabee labor in Antarctica, this represents a saving of $256 in outfitting a 64-foot-long Jamesway . It is planned...to use the new electrical wiring harness to outfit a 64-foot Jamesway as a 12-bedroom quarters for in-service test at McMurdo, Antarctica, during Deep Freeze 67. (Author)

  1. Thiol-ene click chemistry: computational and kinetic analysis of the influence of alkene functionality.

    PubMed

    Northrop, Brian H; Coffey, Roderick N

    2012-08-22

    The influence of alkene functionality on the energetics and kinetics of radical initiated thiol-ene click chemistry has been studied computationally at the CBS-QB3 level. Relative energetics (ΔH°, ΔH(++), ΔG°, ΔG(++)) have been determined for all stationary points along the step-growth mechanism of thiol-ene reactions between methyl mercaptan and a series of 12 alkenes: propene, methyl vinyl ether, methyl allyl ether, norbornene, acrylonitrile, methyl acrylate, butadiene, methyl(vinyl)silanediamine, methyl crotonate, dimethyl fumarate, styrene, and maleimide. Electronic structure calculations reveal the underlying factors that control activation barriers for propagation and chain-transfer processes of the step-growth mechanism. Results are further extended to predict rate constants for forward and reverse propagation and chain-transfer steps (k(P), k(-P), k(CT), k(-CT)) and used to model overall reaction kinetics. A relationship between alkene structure and reactivity in thiol-ene reactions is derived from the results of kinetic modeling and can be directly related to the relative energetics of stationary points obtained from electronic structure calculations. The results predict the order of reactivity of alkenes and have broad implications for the use and applications of thiol-ene click chemistry.

  2. Covalent Incorporation of Ionic Liquid into Ion-Conductive Networks via Thiol-Ene Photopolymerization.

    PubMed

    Tibbits, Andrew C; Yan, Yushan S; Kloxin, Christopher J

    2017-07-01

    Ene-functionalized ionic liquids with a range of different cationic groups and counteranions react stoichiometrically within a tetrathiol-divinyl ether formulation within 20 minutes to form thiol-ene polymers with measurable ionic conductivities via a photoinitiated polymerization and crosslinking reaction. Dynamic mechanical analysis indicates that these networks are more spatially heterogeneous and possess higher glass transition temperatures (Tg ) compared with thiol-ene formulations without charge. While tuning the molar content of ionic liquid monomer is one method for adjusting the crosslink and charge densities of the thiol-ene polymeric ionic liquid networks, the presence of cation-anion interactions also plays a critical role in dictating the thermomechanical and conductive properties. Particularly, while cationic structure effects are not significant on the polymer properties, the use of a weakly coordinating hydrophobic anion (bistriflimide) instead of bromide-based networks results in an apparent decrease in hydrated ion conductivity (7.4 to 1.5 mS cm(-1) ) and Tg (-9.6 to -17.8 °C). © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Harnessing Linguistic Variation to Improve Education. Rethinking Education. Volume 5

    ERIC Educational Resources Information Center

    Yiakoumetti, Androula, Ed.

    2012-01-01

    This volume brings together research carried out in a variety of geographic and linguistic contexts including Africa, Asia, Australia, Canada, the Caribbean, Europe and the United States and explores efforts to incorporate linguistic diversity into education and to "harness" this diversity for learners' benefit. It challenges the largely…

  4. Manufacture and quality control of interconnecting wire harnesses

    NASA Technical Reports Server (NTRS)

    1973-01-01

    Four-volume series of documents has been prepared as standard reference. Each volume may be used separately and covers wire and cable preparation as well as harness fabrication and installation. Series should be useful addition to libraries of manufactures of electrical and electronic equipment.

  5. Harnessing Linguistic Variation to Improve Education. Rethinking Education. Volume 5

    ERIC Educational Resources Information Center

    Yiakoumetti, Androula, Ed.

    2012-01-01

    This volume brings together research carried out in a variety of geographic and linguistic contexts including Africa, Asia, Australia, Canada, the Caribbean, Europe and the United States and explores efforts to incorporate linguistic diversity into education and to "harness" this diversity for learners' benefit. It challenges the largely…

  6. Understanding and Harnessing the Power of Ideas, Persuasion, and Trust

    DTIC Science & Technology

    2013-09-17

    University, Korea Human rights & political culture Malaysia Prof. Dr. Abdul Rahman Embong nstitut Kajian Malaysia & Antarabangsa (IKMAS) Institute...Modeling of how to Harness Trust and Influence in Cyber- space Sing Syed Adnan Ali Shah BUKHARI Assoc Res Fellow & Team Leader South & Central Asia

  7. Using Discussion Methods to Inspire Diversity: Harnessing Social & Cultural Capital

    ERIC Educational Resources Information Center

    Raison, Brian; Gordon, Beverly

    2012-01-01

    How can you better harness the powerful social capital that exists within diverse individuals, families, businesses, and schools to make positive impacts in your community? What could you add to your next meeting--a Chamber strategic planning session, an employee wellness program, a non-profit board development--to better connect participants with…

  8. Using Discussion Methods to Inspire Diversity: Harnessing Social & Cultural Capital

    ERIC Educational Resources Information Center

    Raison, Brian; Gordon, Beverly

    2012-01-01

    How can you better harness the powerful social capital that exists within diverse individuals, families, businesses, and schools to make positive impacts in your community? What could you add to your next meeting--a Chamber strategic planning session, an employee wellness program, a non-profit board development--to better connect participants with…

  9. Harnessing the crowd to accelerate molecular medicine research.

    PubMed

    Smith, Robert J; Merchant, Raina M

    2015-07-01

    Crowdsourcing presents a novel approach to solving complex problems within molecular medicine. By leveraging the expertise of fellow scientists across the globe, broadcasting to and engaging the public for idea generation, harnessing a scalable workforce for quick data management, and fundraising for research endeavors, crowdsourcing creates novel opportunities for accelerating scientific progress.

  10. Manufacture and quality control of interconnecting wire harnesses, Volume 3

    NASA Technical Reports Server (NTRS)

    1972-01-01

    The document covers interconnecting wire harnesses defined in the design standard, including type 6, enclosed in TFE heat shrink tubing; and type 7, flexible armored. Knowledge gained through experience on the Saturn 5 program coupled with recent advances in techniques, materials, and processes was incorporated into this document.

  11. 42 CFR 84.1138 - Head harnesses; minimum requirements.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... 42 Public Health 1 2010-10-01 2010-10-01 false Head harnesses; minimum requirements. 84.1138 Section 84.1138 Public Health PUBLIC HEALTH SERVICE, DEPARTMENT OF HEALTH AND HUMAN SERVICES OCCUPATIONAL..., and Mist; Pesticide; Paint Spray; Powered Air-Purifying High Efficiency Respirators and Combination...

  12. Program for improved electrical harness documentation and fabrication

    NASA Technical Reports Server (NTRS)

    1971-01-01

    Computer program provides automated print-out of harness interconnection table and automated cross-check of reciprocal pin/connector assignments, and improves accuracy and reliability of final documented data. Programs and corresponding library tapes are successfully and continuously employed on Nimbus spacecraft programs.

  13. Thiol-ene microfluidic devices for microchip electrophoresis: Effects of curing conditions and monomer composition on surface properties.

    PubMed

    Tähkä, Sari M; Bonabi, Ashkan; Nordberg, Maria-Elisa; Kanerva, Meeri; Jokinen, Ville P; Sikanen, Tiina M

    2015-12-24

    Thiol-ene polymer formulations are raising growing interest as new low-cost fabrication materials for microfluidic devices. This study addresses their feasibility for microchip electrophoresis (MCE) via characterization of the effects of UV curing conditions and aging on the surface charge and wetting properties. A detailed comparison is made between stoichiometric thiol-ene (1:1) and thiol-ene formulations bearing 50% molar excess of allyls ("enes"), both prepared without photoinitiator or other polymer modifiers. Our results show that the surface charge of thiol-ene 1:1 increases along with increasing UV exposure dose until a threshold (here, about 200J/cm(2)), whereas the surface charge of thiol-ene 2:3 decreases as a function of increasing UV dose. However, no significant change in the surface charge upon storage in ambient air was observed over a period of 14 days (independent of the curing conditions). The water contact angles of thiol-ene 2:3 (typically 70-75°) were found to be less dependent on the UV dose and storing time. Instead, water contact angles of thiol-ene 1:1 slightly decrease (from initial 90 to 95° to about 70°) as a function of UV increasing exposure dose and storing time. Most importantly, both thiol-ene formulations remain relatively hydrophilic over extended periods of time, which favors their use in MCE applications. Here, MCE separation of biologically active peptides and selected fluorescent dyes is demonstrated in combination with laser-induced fluorescence detection showing high separation efficiency (theoretical plates 8200 per 4cm for peptides and 1500-2700 per 4cm for fluorescent dyes) and lower limits of detection in the sub-μM (visible range) or low-μM (near-UV range) level. Copyright © 2015 Elsevier B.V. All rights reserved.

  14. A Study of Functional Polymer Colloids Prepared Using Thiol-Ene/Yne Click Chemistry

    NASA Astrophysics Data System (ADS)

    Durham, Olivia Z.

    This project demonstrates the first instance of thiol-ene chemistry as the polymerization method for the production of polymer colloids in two-phase heterogeneous suspensions, miniemulsions, and emulsions. This work was also expanded to thiol-yne chemistry for the production of polymer particles containing increased crosslinking density. The utility of thiol-ene and thiol-yne chemistries for polymerization and polymer modification is well established in bulk systems. These reactions are considered 'click' reactions, which can be defined as processes that are both facile and simple, offering high yields with nearly 100% conversion, no side products, easy product separation, compatibility with a diverse variety of commercially available starting materials, and orthogonality with other chemistries. In addition, thiol-ene and thiol-yne chemistry follow a step-growth mechanism for the development of highly uniform polymer networks, where polymer growth is dependent on the coupling of functional groups. These step-growth polymerization systems are in stark contrast to the chain-growth mechanisms of acrylic and styrenic monomers that have dominated the field of conventional heterogeneous polymerizations. Preliminary studies evaluated the mechanism of particle production in suspension and miniemulsion systems. Monomer droplets were compared to the final polymer particles to confirm that particle growth occurred through the polymerization of monomer droplets. Additional parameters examined include homogenization energy (mechanical mixing), diluent species and concentration, and monomer content. These reactions were conducted using photoinitiation to yield particles in a matter of minutes with diameters in the size range of several microns to hundreds of microns in suspensions or submicron particles in miniemulsions. Improved control over the particle size and size distribution was examined through variation of reaction parameters. In addition, a method of seeded suspension

  15. 42 CFR 84.173 - Harnesses; installation and construction; minimum requirements.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... 42 Public Health 1 2010-10-01 2010-10-01 false Harnesses; installation and construction; minimum... DEVICES Non-Powered Air-Purifying Particulate Respirators § 84.173 Harnesses; installation and... harness designed and constructed to hold the components of the respirator in position against the...

  16. 42 CFR 84.196 - Harnesses; installation and construction; minimum requirements.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... 42 Public Health 1 2010-10-01 2010-10-01 false Harnesses; installation and construction; minimum... DEVICES Chemical Cartridge Respirators § 84.196 Harnesses; installation and construction; minimum requirements. (a) Each respirator shall, where necessary, be equipped with a suitable harness designed...

  17. 42 CFR 84.133 - Harnesses; installation and construction; minimum requirements.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... 42 Public Health 1 2010-10-01 2010-10-01 false Harnesses; installation and construction; minimum... DEVICES Supplied-Air Respirators § 84.133 Harnesses; installation and construction; minimum requirements. (a) Each supplied-air respirator shall, where necessary, be equipped with a suitable harness...

  18. 14 CFR 137.42 - Fastening of safety belts and shoulder harnesses.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 14 Aeronautics and Space 3 2010-01-01 2010-01-01 false Fastening of safety belts and shoulder... AGRICULTURAL AIRCRAFT OPERATIONS Operating Rules § 137.42 Fastening of safety belts and shoulder harnesses. No... belt and shoulder harness properly secured about that person except that the shoulder harness need...

  19. Ibogaine analogues. Synthesis and preliminary pharmacological evaluation of 7-heteroaryl-2-azabicyclo[2.2.2]oct-7-enes.

    PubMed

    Passarella, Daniele; Favia, Raffaele; Giardini, Alessandra; Lesma, Giordano; Martinelli, Marisa; Silvani, Alessandra; Danieli, Bruno; Efange, Simon M N; Mash, Deborah C

    2003-03-20

    Synthesis of 7-heteroaryl-2-azabicyclo[2.2.2]oct-7-enes by cycloaddition and subsequent cross-coupling reaction is described. Binding affinity of these novel compounds towards the characteristic receptorial targets of ibogaine is illustrated.

  20. Uncovering Listeria monocytogenes hypervirulence by harnessing its biodiversity

    PubMed Central

    Charlier, Caroline; Touchon, Marie; Chenal-Francisque, Viviane; Leclercq, Alexandre; Criscuolo, Alexis; Gaultier, Charlotte; Roussel, Sophie; Brisabois, Anne; Disson, Olivier; Rocha, Eduardo P. C.; Brisse, Sylvain; Lecuit, Marc

    2016-01-01

    Microbial pathogenesis studies are typically performed with reference strains, thereby overlooking microbial intra-species virulence heterogeneity. Here we integrated human epidemiological and clinical data with bacterial population genomics to harness the biodiversity of the model foodborne pathogen Listeria monocytogenes and decipher the basis of its neural and placental tropisms. Taking advantage of the clonal structure of this bacterial species, we identify clones epidemiologically associated with either food or human central nervous system (CNS) and maternal-neonatal (MN) listeriosis. The latter are also most prevalent in patients without immunosuppressive comorbidities. Strikingly, CNS and MN clones are hypervirulent in a humanized mouse model of listeriosis. By integrating epidemiological data and comparative genomics, we uncovered multiple novel putative virulence factors and demonstrated experimentally the contribution of the first gene cluster mediating Listeria monocytogenes neural and placental tropisms. This study illustrates the exceptional power of harnessing microbial biodiversity to identify clinically relevant microbial virulence attributes. PMID:26829754

  1. Smart warping harnesses for active mirrors and stress polishing

    NASA Astrophysics Data System (ADS)

    Lemared, Sabri; Hugot, Emmanuel; Challita, Zalpha; Schnetler, Hermine; Kroes, Gabby; Marcos, Michel; Costille, Anne; Dohlen, Kjetil; Beuzit, Jean-Luc; Cuby, Jean-Gabriel

    2016-07-01

    We present two ways to generate or compensate for first order optical aberrations using smart warping harnesses. In these cases, we used the same methodology leading to replace a previous actuation system currently on-sky and to get a freeform mirror intended to a demonstrator. Starting from specifications, a warping harness is designed, followed by a meshing model in the finite elements software. For the two projects, two different ways of astigmatism generation are presented. The first one, on the VLT-SPHERE instrument, with a single actuator, is able to generate a nearly pure astigmatism via a rotating motorization. Two actuators are sufficient to produce the same aberration for the active freeform mirror, main part of the OPTICON-FAME project, in order to use stress-polishing method.

  2. HARNESS: Heterogeneous Adaptable Reconfigurable Networked Systems. Final Progress Report

    SciTech Connect

    Fagg, G. E.

    2004-01-20

    HARNESS was proposed as a system that combined the best of emerging technologies found in current distributed computing research and commercial products into a very flexible, dynamically adaptable framework that could be used by applications to allow them to evolve and better handle their execution environment. The HARNESS system was designed using the considerable experience from previous projects such as PVM, MPI, IceT and Cumulvs. As such, the system was designed to avoid any of the common problems found with using these current systems, such as no single point of failure, ability to survive machine, node and software failures. Additional features included improved intercomponent connectivity, with full support for dynamic down loading of addition components at run-time thus reducing the stress on application developers to build in all the libraries they need in advance.

  3. Hello World: Harnessing social media for the Rosetta mission

    NASA Astrophysics Data System (ADS)

    Baldwin, E.; Mignone, C.; O'Flaherty, K. S.; Homfeld, A.-M.; Bauer, M.; McCaughrean, M. J.

    2015-10-01

    The European Space Agency's (ESA) comet-chasing Rosetta mission was launched in 2004, before social media became a popular tool for mainstream communication. By harnessing a range of platforms for communicating the key messages of this unprecedented space adventure as the spacecraft reached its destination ten years later, a wide range of new audiences were reached and could follow this once-in-a-lifetime mission.

  4. High-Density Terminal Box for Testing Wire Harness

    NASA Technical Reports Server (NTRS)

    Pierce, W. B.; Collins, W. G.

    1982-01-01

    Compact terminal box provides access to complex wiring harnesses for testing. Box accommodates more than twice as many wires as previous boxes. Box takes in wires via cable connectors and distributes them to contacts on box face. Instead of separate insulated jacks in metal face panel, box uses pairs of small military-standard metal sockets in precision-drilled plastic panel. Shorting plug provides continuity for wires when not being tested.

  5. Quick-disconnect harness system for helmet-mounted displays

    NASA Astrophysics Data System (ADS)

    Bapu, P. T.; Aulds, M. J.; Fuchs, Steven P.; McCormick, David M.

    1992-10-01

    We have designed a pilot's harness-mounted, high voltage quick-disconnect connectors with 62 pins, to transmit voltages up to 13.5 kV and video signals with 70 MHz bandwidth, for a binocular helmet-mounted display system. It connects and disconnects with power off, and disconnects 'hot' without pilot intervention and without producing external sparks or exposing hot embers to the explosive cockpit environment. We have implemented a procedure in which the high voltage pins disconnect inside a hermetically-sealed unit before the physical separation of the connector. The 'hot' separation triggers a crowbar circuit in the high voltage power supplies for additional protection. Conductor locations and shields are designed to reduce capacitance in the circuit and avoid crosstalk among adjacent circuits. The quick- disconnect connector and wiring harness are human-engineered to ensure pilot safety and mobility. The connector backshell is equipped with two hybrid video amplifiers to improve the clarity of the video signals. Shielded wires and coaxial cables are molded as a multi-layered ribbon for maximum flexibility between the pilot's harness and helmet. Stiff cabling is provided between the quick-disconnect connector and the aircraft console to control behavior during seat ejection. The components of the system have been successfully tested for safety, performance, ergonomic considerations, and reliability.

  6. Preparation of reactive three-dimensional microstructures via direct laser writing and thiol-ene chemistry.

    PubMed

    Quick, Alexander S; Fischer, Joachim; Richter, Benjamin; Pauloehrl, Thomas; Trouillet, Vanessa; Wegener, Martin; Barner-Kowollik, Christopher

    2013-02-25

    Three-dimensional microstructures are fabricated employing the direct laser writing process and radical thiol-ene polymerization. The resin system consists of a two-photon photoinitiator and multifunctional thiols and olefins. Woodpile photonic crystals with 22 layers and a rod distance of 2 μm are fabricated. The structures are characterized via scanning electron microscopy and focused ion beam milling. The thiol-ene polymerization during fabrication is verified via infrared spectroscopy. The structures are grafted in a subsequent thiol-Michael addition reaction with different functional maleimides. The success of the grafting reaction is evaluated via laser scanning microscopy and X-ray photoelectron spectroscopy. The grafting density is calculated to be close to 200 molecules μm(-2) .

  7. A versatile approach to high-throughput microarrays using thiol-ene chemistry

    NASA Astrophysics Data System (ADS)

    Gupta, Nalini; Lin, Brian F.; Campos, Luis M.; Dimitriou, Michael D.; Hikita, Sherry T.; Treat, Neil D.; Tirrell, Matthew V.; Clegg, Dennis O.; Kramer, Edward J.; Hawker, Craig J.

    2010-02-01

    Microarray technology has become extremely useful in expediting the investigation of large libraries of materials in a variety of biomedical applications, such as in DNA chips, protein and cellular microarrays. In the development of cellular microarrays, traditional high-throughput printing strategies on stiff, glass substrates and non-covalent attachment methods are limiting. We have developed a facile strategy to fabricate multifunctional high-throughput microarrays embedded at the surface of a hydrogel substrate using thiol-ene chemistry. This user-friendly method provides a platform for the immobilization of a combination of bioactive and diagnostic molecules, such as peptides and dyes, at the surface of poly(ethylene glycol)-based hydrogels. The robust and orthogonal nature of thiol-ene chemistry allows for a range of covalent attachment strategies in a fast and reliable manner, and two complementary strategies for the attachment of active molecules are demonstrated.

  8. Photocured thiol-ene based optical fluorescence sensor for determination of gold(III).

    PubMed

    Cubuk, Soner; Kahraman, Memet Vezir; Yetimoğlu, Ece Kök; Kenan, Sibel

    2014-02-17

    This study describes the preparation and the characterization of a new thiol-ene based polymeric fluorescence sensor by photo initiated polymerization of trimethylolpropane tris(3-mercaptopropionate), 2-hydroxyethylacrylate, and 2,4,6-triallyloxy-1,3,5-triazine which are used as monomers and also a photo initiator (2,2-dimethoxy-2-phenylacetophenone) for its usage as optical sensor for gold ions. The thiol-ene based polymeric membrane sensor was characterized by using attenuated total reflectance-fourier transform infrared spectroscopy (ATR-FTIR) and scanning electron microscopy (SEM). The response characteristics of the sensors including dynamic range, pH effect, response time, and the effect of foreign ions were investigated. Fluorescence spectra showed that the excitation/emission maxima of the membrane were at 379/425 nm, respectively.

  9. Hybrid thiol-ene network nanocomposites based on multi(meth)acrylate POSS.

    PubMed

    Li, Liguo; Liang, Rendong; Li, Yajie; Liu, Hongzhi; Feng, Shengyu

    2013-09-15

    First, multi(meth)acrylate functionalized POSS monomers were synthesized in this paper. Secondly, FTIR was used to evaluate the homopolymerization behaviors of multi(meth)acrylate POSS and their copolymerization behaviors in the thiol-ene reactions with octa(3-mercaptopropyl) POSS in the presence of photoinitiator. Results showed that the photopolymerization rate of multimethacrylate POSS was faster than that of multiacrylate POSS. The FTIR results also showed that the copolymerizations were dominant in the thiol-ene reactions with octa(3-mercaptopropyl) POSS, different from traditional (meth)acrylate-thiol system, in which homopolymerizations were predominant. Finally, the resulted hybrid networks based on POSS were characterized by XRD, FE-SEM, DSC, and TGA. The characterization results showed that hybrid networks based on POSS were homogeneous and exhibited high thermal stability.

  10. On the biotransformation of ent-trachylobane to ent-kaur-11-ene diterpenes.

    PubMed

    Fraga, Braulio M; Gonzalez-Vallejo, Victoria; Guillermo, Ricardo

    2011-09-23

    The microbiological transformation of trachinodiol (1) by the fungus Mucor plumbeus afforded the corresponding 1α, 2α, 3α, and 17-hydroxy derivatives (2-4 and 6), respectively. 7β,16α,18-Trihydroxy-ent-kaur-11-ene (sicanatriol) (5) was also obtained in this feeding. The biotransformation of 1 to give 5 by this fungus may occur by enzymatic abstraction of a hydrogen atom, allylic to the cyclopropane ring, and subsequent cleavage of this ring. This route is similar to that postulated by us in plants of the genus Sideritis, where ent-trachylobane and ent-kaur-11-ene diterpenes coexist. This study confirms that hydroxylation of diterpenes by M. plumbeus occurs preferably at ring A carbons.

  11. Redox Mediators in Visible Light Photocatalysis: Photocatalytic Radical Thiol–Ene Additions

    PubMed Central

    2015-01-01

    Synthetically useful radical thiol–ene reactions can be initiated by visible light irradiation in the presence of transition metal polypyridyl photocatalysts. The success of this method relies upon the use of p-toluidine as an essential additive. Using these conditions, high-yielding thiol–ene reactions of cysteine-containing biomolecules can be accomplished using biocompatibile wavelengths of visible light, under aqueous conditions, and with the thiol component as the limiting reagent. We present evidence that p-toluidine serves as a redox mediator that is capable of catalyzing the otherwise inefficient photooxidation of thiols to the key thiyl radical intermediate. Thus, we show that co-catalytic oxidants can be important in the design of synthetic reactions involving visible light photoredox catalysis. PMID:24428433

  12. Thiol-ene click reaction as a general route to functional trialkoxysilanes for surface coating applications.

    PubMed

    Tucker-Schwartz, Alexander K; Farrell, Richard A; Garrell, Robin L

    2011-07-27

    Functionalized trialkoxysilanes are widely used to modify the surface properties of materials and devices. It will be shown that the photoinitiated radical-based thiol-ene "click" reaction provides a simple and efficient route to diverse trialkoxysilanes. A total of 15 trialkoxysilanes were synthesized by reacting either alkenes with 3-mercaptopropyltrialkoxysilane or thiols with allyltrialkoxysilanes in the presence of a photoinitiator. The functionalized trialkoxysilanes were obtained in quantitative to near-quantitative yields with high purity. The photochemical reactions can be run neat in standard borosilicate glassware using a low power 15-W blacklight. A wide range of functional groups is tolerated in this approach, and even complex alkenes click with the silane precursors. To demonstrate that these silanes can be used as surface coating agents, several were reacted with iron oxide superparamagnetic nanoparticles and the loadings quantified. The photoinitiated thiol-ene reaction thus offers a facile and efficient method for preparing surface-active functional trialkoxysilanes.

  13. BCl3-mediated ene reaction of sulfur dioxide and unfunctionalized alkenes.

    PubMed

    Marković, Dean; Volla, Chandra M R; Vogel, Pierre; Varela-Alvarez, Adrián; Sordo, José A

    2010-05-25

    The first ene reactions of SO(2) and unfunctionalized alkenes are reported. Calculations suggest that the endergonic ene reactions of SO(2) with alkenes can be used to generate beta,gamma-unsaturated sulfinyl and sulfonyl compounds. Indeed, in the presence of one equivalent of BCl(3), the unstable sulfinic acid form stable sulfinic acid.BCl(3) complexes that can be reacted in situ with NCS to generate corresponding sulfonyl chlorides, or with a base to generate corresponding sulfinates. The latter can be reacted with electrophiles to generate sulfones, or with silyl chloride to form beta,gamma-unsaturated silyl sulfinates. The sulfinic acid.BCl(3) complexes can be reacted with ethers that act as oxygen nucleophiles to produce corresponding sulfinic esters. Thus one-pot, three-component synthesis of beta,gamma-unsaturated sulfonamides, sulfinyl esters and sulfones have been developed starting from alkenes and sulfur dioxide (reagent and solvent).

  14. Enantioselective intramolecular aldehyde α-alkylation with simple olefins: direct access to homo-ene products.

    PubMed

    Comito, Robert J; Finelli, Fernanda G; MacMillan, David W C

    2013-06-26

    A highly selective method for the synthesis of asymmetrically substituted carbocycles and heterocycles from unactivated aldehyde-olefin precursors has been achieved via enantioselective SOMO-catalysis. Addition of a catalytically generated enamine radical cation across a pendent olefin serves to establish a general asymmetric strategy toward the production of a wide range of formyl-substituted rings with alkene transposition. Conceptually, this novel mechanism allows direct access to "homo-ene"-type products.

  15. 100% thiol-functionalized ethylene PMOs prepared by "thiol acid-ene" chemistry.

    PubMed

    Esquivel, Dolores; van den Berg, Otto; Romero-Salguero, Francisco J; Du Prez, Filip; Van der Voort, Pascal

    2013-03-21

    A novel thiol functionalized bis-silane PMO precursor was synthesized by highly efficient thiol acid-ene chemistry between the double bonds of 1,2-(E)-bis(triethoxysilyl)ethene and thioacetic acid. After aminolysis the self-assembly process of the formed SH-precursor with Pluronic P123 under acidic conditions yields the first 100% thiol-PMO material with good structural ordering.

  16. A new solvent-dependent mechanism for a triazolinedione ene reaction.

    PubMed

    Acevedo, Orlando; Squillacote, Michael E

    2008-02-01

    The ene reaction between 4-phenyl-1,2,4-triazoline-3,5-dione (PTAD) and tetramethylethylene has been investigated using QM/MM calculations in water, methanol, DMSO, and acetonitrile. The effects of solvation on the mechanism and rates of reaction are elucidated using two-dimensional potentials of mean force (PMF) simulations utilizing free-energy perturbation theory and Monte Carlo statistical mechanics. A new mechanism is proposed where direct formation of an open dipolar intermediate following the addition of PTAD to the alkene is rate-limiting and the pathway toward ene product is significantly dependent on the reaction medium. In protic solvents, the open dipolar intermediate may proceed directly to the ene product or reversibly form an aziridinium imide (AI) intermediate that does not participate in the reaction. However, in aprotic solvents the open intermediate is short-lived (<10-11 s) and the ene product forms via the AI intermediate. The calculated free energies of activation are in close agreement with those derived from experiment, e.g., DeltaG of 14.9 kcal/mol compared to 15.0 kcal/mol in acetonitrile. Density functional theory calculations at the (U)B3LYP/6-311++G(2d,p) level using the CPCM continuum solvent model were also carried out and confirmed a zwitterionic, and not diradical, open intermediate present in the reaction. Only the QM/MM methodology was able to accurately reproduce the experimental rates and differentiate between the protic and aprotic solvents. Solute-solvent interaction energies, radial distribution functions, and charges are analyzed and show that the major factor dictating the changes in reaction path is hydrogen bond stabilization of the charge separations spanning 2 to 4 atoms in the intermediates and transition states.

  17. Heterofunctional Glycopolypeptides by Combination of Thiol-Ene Chemistry and NCA Polymerization.

    PubMed

    Krannig, Kai-Steffen; Schlaad, Helmut

    2016-01-01

    Glycopolypeptides are prepared either by the polymerization of glycosylated amino acid N-carboxyanhydrides (NCAs) or by the post-polymerization functionalization of polypeptides with suitable functional groups. Here we present a method for the in-situ functionalization and (co-) polymerization of allylglycine N-carboxyanhydride in a facile one-pot procedure, combining radical thiol-ene photochemistry and nucleophilic ring-opening polymerization techniques, to yield well-defined heterofunctional glycopolypeptides.

  18. Flight performance energetics and water turnovers of Tippler Pigeons with a harness and doorsal load

    USGS Publications Warehouse

    Gessaman, James A.; Workman, Gar W.; Fuller, Mark R.

    1991-01-01

    We measured carbon dioxide production and water efflux of 12 tippler pigeons (Columba spp.) during seven experimental flights using the doubly labeled water (DLW) method. Prior to the experiment birds were randomly assigned to one of two groups. One group flew as controls (no load or harness) on all seven flights. The other group wore a harness on two flights, a dorsal load/harness package (weighing about 5% of a birda??s mass) on two flights, and they were without a load in three flights. Plight duration of pigeons with only a harness and with a dorsal load/harness package was 21 and 26% less, respectively, than the controls. Pigeons wearing a harness, or wearing a dorsal load/harness package lost water 50-90%, and 57-100% faster, respectively, than control pigeons. The mean CO, production of pigeons wearing a harness or a load/harness package was not significantly different than pigeons without a harness or load. The small sample sizes and large variability in DLW measurements precluded a good test of the energetic cost of flying with a harness and dorsal load.

  19. Flight performance, energetics and water turnover of tippler pigeons with a harness and dorsal load

    USGS Publications Warehouse

    Gessaman, J.A.; Workman, G.W.; Fuller, M.R.

    1991-01-01

    We measured carbon dioxide production and water efflux of 12 tippler pigeons (Columba spp.) during seven experimental flights using the doubly labeled water (DLW) method. Prior to the experiment birds were randomly assigned to one of two groups. One group flew as controls (no load or harness) on all seven flights. The other group wore a harness on two flights, a dorsal load/harness package (weighing about 5% of a bird's mass) on two flights, and they were without a load in three flights. Flight duration of pigeons with only a harness and with a dorsal load/harness package was 21 and 26% less, respectively, than the controls. Pigeons wearing a harness, or wearing a dorsal load/harness package lost water 50-90%, and 57-100% faster, respectively, than control pigeons. The mean CO2 production of pigeons wearing a harness or a load/harness package was not significantly different than pigeons without a harness or load. The small sample sizes and large variability in DLW measuremets precluded a good test of the energetic cost of flying with a harness and dorsal load.

  20. A single Danio rerio hars gene encodes both cytoplasmic and mitochondrial histidyl-tRNA synthetases.

    PubMed

    Waldron, Ashley L; Cahan, Sara Helms; Franklyn, Christopher S; Ebert, Alicia M

    2017-01-01

    Histidyl tRNA Synthetase (HARS) is a member of the aminoacyl tRNA synthetase (ARS) family of enzymes. This family of 20 enzymes is responsible for attaching specific amino acids to their cognate tRNA molecules, a critical step in protein synthesis. However, recent work highlighting a growing number of associations between ARS genes and diverse human diseases raises the possibility of new and unexpected functions in this ancient enzyme family. For example, mutations in HARS have been linked to two different neurological disorders, Usher Syndrome Type IIIB and Charcot Marie Tooth peripheral neuropathy. These connections raise the possibility of previously undiscovered roles for HARS in metazoan development, with alterations in these functions leading to complex diseases. In an attempt to establish Danio rerio as a model for studying HARS functions in human disease, we characterized the Danio rerio hars gene and compared it to that of human HARS. Using a combination of bioinformatics, molecular biology, and cellular approaches, we found that while the human genome encodes separate genes for cytoplasmic and mitochondrial HARS protein, the Danio rerio genome encodes a single hars gene which undergoes alternative splicing to produce the respective cytoplasmic and mitochondrial versions of Hars. Nevertheless, while the HARS genes of humans and Danio differ significantly at the genomic level, we found that they are still highly conserved at the amino acid level, underscoring the potential utility of Danio rerio as a model organism for investigating HARS function and its link to human diseases in vivo.

  1. Thiol-Ene Induced Diphosphonic Acid Functionalization of Superparamagnetic Iron Oxide Nanoparticles

    SciTech Connect

    Rutledge, Ryan D.; Warner, Cynthia L.; Pittman, Jonathan W.; Addleman, Raymond S.; Engelhard, Mark H.; Chouyyok, Wilaiwan; Warner, Marvin G.

    2010-07-20

    Multi-functional organic molecules represent an interesting challenge for nanoparticle functionalization due to the potential for undesirable interactions between the substrate material and the variable functionalities, making it difficult to control the final orientation of the ligand. In the present study, UV-induced thiol-ene click chemistry has been utilized as a means of directed functionalization of bifunctional ligands on an iron oxide nanoparticle surface. Allyl diphosphonic acid ligand was covalently deposited on the surface of thiol-presenting iron oxide nanoparticles via the formation of a UV-induced thioether. This method of thiol-ene click chemistry offers a set of reaction conditions capable of controlling the ligand deposition and circumventing the natural affinity exhibited by the phosphonic acid moiety for the iron oxide surface. These claims are supported via a multimodal characterization platform which includes thermogravimetric analysis, x-ray photoelectron spectroscopy, and metal contact analysis and are consistent with a properly oriented, highly active ligand on the nanoparticle surface. These experiments suggest thiol-ene click chemistry as both a practical and generally applicable strategy for the directed deposition of multi-functional ligands on metal oxide nanoparticle surfaces.

  2. Surface modification of cyclomatrix polyphosphazene microsphere by thiol-ene chemistry and lectin recognition

    NASA Astrophysics Data System (ADS)

    Chen, Chen; Zhu, Xue-yan; Gao, Qiao-ling; Fang, Fei; Huang, Xiao-jun

    2016-11-01

    A new synthetic route leading to functional polyphosphazene cyclomatrix microsphere has been developed via thiol-ene click modification. Hexacholorocyclophosphazene (HCCP) was crosslinked with both bisphenol-S and 4,4‧-diallyl bisphenol-S to obtain vinyl polyphosphazene microspheres (VPZM) in order to ensure high crosslinking degree and introduce vinyl moieties. Compared to the microspheres obtained by HCCP and bisphenol-S, the size of VPZM was broadly dispersed from 400 nm to 1.40 μm. Thiol-ene click reactions were carried out to attach functional groups, such as glucosyl, carboxyl, ester and dodecyl groups onto polyphosphazene microspheres, which demonstrated no change in morphology and size after modification. Solid state NMR (SSNMR) and Fourier transform infrared spectoscopy (FT-IR) results showed that the vinyl moieties were introduced in the period of crosslinking and functionalization was also successful via click reactions. Moreover, the microspheres presented a little difference in thermal properties after modification. Concanavalin A (Con-A) fluorescent adsorption was also observed for glucosyl microspheres. Thus, the thiol-ene modified polyphosphazene microspheres displayed chemical flexibility in post-functionalization. These microspheres can be potentially applicated in enzyme immobilization, protein adsorption and chromatographic separation.

  3. Determination and potential importance of diterpene (kaur-16-ene) emitted from dominant coniferous trees in Japan.

    PubMed

    Matsunaga, Sou N; Chatani, Satoru; Nakatsuka, Seiji; Kusumoto, Dai; Kubota, Katsuyoshi; Utsumi, Yasuhiro; Enoki, Tsutomu; Tani, Akira; Hiura, Tsutom

    2012-05-01

    Reactive volatile organic compounds (VOCs) are known to affect atmospheric chemistry. Biogenic VOCs (BVOCs) have a significant impact on regional air quality due to their large emission rates and high reactivities. Diterpenes (most particularly, kaur-16-ene) were detected in all of the 205 enclosure air samples collected over multiple seasons at two different sites from Cryptomeria japonica and Chamaecyparis obtusa trees, the dominant coniferous trees in Japan,. The emission rate of kaur-16-ene, was determined to be from 0.01 to 7.1 μg dwg(-1) h(-1) (average: 0.61 μg dwg(-1) h(-1)) employing branch enclosure measurements using adsorbent sampling followed by solid phase-liquid extraction techniques. The emission rate was comparable to that of monoterpenes, which is known major BVOC emissions, collected from the same branches. In addition, total emission of kaur-16-ene at 30°C was estimated to exceed that of total anthropogenic VOC emissions. Copyright © 2012 Elsevier Ltd. All rights reserved.

  4. Graphene Oxide-Polymer Composite Langmuir Films Constructed by Interfacial Thiol-Ene Photopolymerization.

    PubMed

    Luo, Xiaona; Ma, Kai; Jiao, Tifeng; Xing, Ruirui; Zhang, Lexin; Zhou, Jingxin; Li, Bingbing

    2017-12-01

    The effective synthesis and self-assembly of graphene oxide (GO) nanocomposites are of key importance for a broad range of nanomaterial applications. In this work, a one-step chemical strategy is presented to synthesize stable GO-polymer Langmuir composite films by interfacial thiol-ene photopolymerization at room temperature, without use of any crosslinking agents and stabilizing agents. It is discovered that photopolymerization reaction between thiol groups modified GO sheets and ene in polymer molecules is critically responsible for the formation of the composite Langmuir films. The film formed by Langmuir assembly of such GO-polymer composite films shows potential to improve the mechanical and chemical properties and promotes the design of various GO-based nanocomposites. Thus, the GO-polymer composite Langmuir films synthesized by interfacial thiol-ene photopolymerization with such a straightforward and clean manner, provide new alternatives for developing chemically modified GO-based hybrid self-assembled films and nanomaterials towards a range of soft matter and graphene applications.

  5. Graphene Oxide-Polymer Composite Langmuir Films Constructed by Interfacial Thiol-Ene Photopolymerization

    NASA Astrophysics Data System (ADS)

    Luo, Xiaona; Ma, Kai; Jiao, Tifeng; Xing, Ruirui; Zhang, Lexin; Zhou, Jingxin; Li, Bingbing

    2017-02-01

    The effective synthesis and self-assembly of graphene oxide (GO) nanocomposites are of key importance for a broad range of nanomaterial applications. In this work, a one-step chemical strategy is presented to synthesize stable GO-polymer Langmuir composite films by interfacial thiol-ene photopolymerization at room temperature, without use of any crosslinking agents and stabilizing agents. It is discovered that photopolymerization reaction between thiol groups modified GO sheets and ene in polymer molecules is critically responsible for the formation of the composite Langmuir films. The film formed by Langmuir assembly of such GO-polymer composite films shows potential to improve the mechanical and chemical properties and promotes the design of various GO-based nanocomposites. Thus, the GO-polymer composite Langmuir films synthesized by interfacial thiol-ene photopolymerization with such a straightforward and clean manner, provide new alternatives for developing chemically modified GO-based hybrid self-assembled films and nanomaterials towards a range of soft matter and graphene applications.

  6. Fragrance material review on 2-(p-Menth-1-ene-10-yl) cyclopentanone.

    PubMed

    Scognamiglio, J; Jones, L; Letizia, C S; Api, A M

    2012-10-01

    A toxicologic and dermatologic review of 2-(p-Menth-1-ene-10-yl) cyclopentanone when used as a fragrance ingredient is presented. 2-(p-Menth-1-ene-10-yl) cyclopentanone is a member of the fragrance structural group ketones cyclopentanones and cyclopentenones. The common characteristic structural element of the group members is a cyclopentanone or cyclopentenone ring with a straight or branched chain alkane or alkene substituent. This review contains a detailed summary of all available toxicology and dermatology papers that are related to this individual fragrance ingredient and is not intended as a stand-alone document. Available data for 2-(p-Menth-1-ene-10-yl) cyclopentanone were evaluated then summarized and includes physical properties, acute toxicity, skin irritation, mucous membrane (eye) irritation, skin sensitization, repeated dose, and genotoxicity data. A safety assessment of the entire cyclopentanones and cyclopentenones will be published simultaneously with this document; please refer to Belsito et al. (2012) for an overall assessment of the safe use of this material and all cyclopentanones and cyclopentenones in fragrances. Copyright © 2012 Elsevier Ltd. All rights reserved.

  7. Bioconversion of car-3-ene by a dioxygenase of Pleurotus sapidus.

    PubMed

    Lehnert, Nicole; Krings, Ulrich; Sydes, Daniel; Wittig, Maximilian; Berger, Ralf G

    2012-06-30

    Mycelium of the basidiomycete Pleurotus sapidus known to contain a novel dioxygenase was used for the bioconversion of car-3-ene [I]. After 4h of incubation 25.3mgL(-1) car-3-en-5-one [V], 5.4mgL(-1) car-3-en-2-one [VII], and 7.3mgL(-1) car-2-en-4-one [XV] accumulated as major oxidation products. The identity of the respective carenones and their corresponding alcohols was confirmed by comparison with MS and NMR spectral data obtained for synthesized authentic compounds. The peak areas of oxidation products were at least five times higher as compared with autoxidation. A radical mechanism similar to lipoxygenase catalysis was proposed and substantiated with detailed product analyses. The reduction of assumed car-3-ene hydroperoxides to the corresponding alcohols evidenced the radical initiated formation of hydroperoxides and confirmed the regio- and stereo-selectivity of the dioxygenase. The introduction of molecular oxygen into the bicyclic car-3-ene [I] molecule occurred at allylic positions of a cyclic isopentenyl moiety with a pronounced preference for the position adjacent to the non-substituted carbon atom of the C-C-double bond. This co-factor independent selective oxygenation presents an alternative to P450 mono-oxygenase based approaches for the production of terpene derived flavor compounds, pharmaceuticals and other fine chemicals.

  8. Facile and Efficient Synthesis of Carbosiloxane Dendrimers via Orthogonal Click Chemistry Between Thiol and Ene.

    PubMed

    Zhang, Zhida; Feng, Shengyu; Zhang, Jie

    2016-02-01

    A combination of a thiol-Michael addition reaction and a free radical mediated thiol-ene reaction is employed as a facile and efficient approach to carbosiloxane dendrimer synthesis. For the first time, carbosiloxane dendrimers are constructed rapidly by an orthogonal click strategy without protection/deprotection procedures. The chemoselectivity of these two thiol-ene click reactions leads to a design of a new monomer containing both electron-deficient carbon-carbon double bonds and unconjugated carbon-carbon double bonds. Siloxane bonds are introduced as the linker between these two kinds of carbon-carbon double bonds. Starting from a bifunctional thiol core, the dendrimers are constructed by iterative thiol-ene click reactions under different but both mild reaction conditions. After simple purification steps the fifth dendrimer with 54 peripheral functional groups is obtained with an excellent overall yield in a single day. Furthermore, a strong blue glow is observed when the dendrimer is excited by a UV lamp.

  9. Identification of promiscuous ene-reductase activity by mining structural databases using active site constellations

    PubMed Central

    Steinkellner, Georg; Gruber, Christian C.; Pavkov-Keller, Tea; Binter, Alexandra; Steiner, Kerstin; Winkler, Christoph; Łyskowski, Andrzej; Schwamberger, Orsolya; Oberer, Monika; Schwab, Helmut; Faber, Kurt; Macheroux, Peter; Gruber, Karl

    2014-01-01

    The exploitation of catalytic promiscuity and the application of de novo design have recently opened the access to novel, non-natural enzymatic activities. Here we describe a structural bioinformatic method for predicting catalytic activities of enzymes based on three-dimensional constellations of functional groups in active sites (‘catalophores’). As a proof-of-concept we identify two enzymes with predicted promiscuous ene-reductase activity (reduction of activated C–C double bonds) and compare them with known ene-reductases, that is, members of the Old Yellow Enzyme family. Despite completely different amino acid sequences, overall structures and protein folds, high-resolution crystal structures reveal equivalent binding modes of typical Old Yellow Enzyme substrates and ligands. Biochemical and biocatalytic data show that the two enzymes indeed possess ene-reductase activity and reveal an inverted stereopreference compared with Old Yellow Enzymes for some substrates. This method could thus be a tool for the identification of viable starting points for the development and engineering of novel biocatalysts. PMID:24954722

  10. Superhydrophobic hybrid inorganic-organic thiol-ene surfaces fabricated via spray-deposition and photopolymerization.

    PubMed

    Sparks, Bradley J; Hoff, Ethan F T; Xiong, Li; Goetz, James T; Patton, Derek L

    2013-03-13

    We report a simple and versatile method for the fabrication of superhydrophobic inorganic-organic thiol-ene coatings via sequential spray-deposition and photopolymerization under ambient conditions. The coatings are obtained by spray-deposition of UV-curable hybrid inorganic-organic thiol-ene resins consisting of pentaerythritol tetra(3-mercaptopropionate) (PETMP), triallyl isocyanurate (TTT), 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane (TMTVSi), and hydrophobic fumed silica nanoparticles. The spray-deposition process and nanoparticle agglomeration/dispersion provide surfaces with hierarchical morphologies exhibiting both micro- and nanoscale roughness. The wetting behavior, dependent on the concentration of TMTVSi and hydrophobic silica nanoparticles, can be varied over a broad range to ultimately provide coatings with high static water contact angles (>150°), low contact angle hysteresis, and low roll off angles (<5°). The cross-linked thiol-ene coatings are solvent resistant, stable at low and high pH, and maintain superhydrophobic wetting behavior after extended exposure to elevated temperatures. We demonstrate the versatility of the spray-deposition and UV-cure process on a variety of substrate surfaces including glass, paper, stone, and cotton fabric.

  11. Shoot HAR1 mediates nitrate inhibition of nodulation in Lotus japonicus.

    PubMed

    Okamoto, Satoru; Kawaguchi, Masayoshi

    2015-01-01

    Nitrate is a major environmental factor in the inhibition of nodulation. In a model legume Lotus japonicus, a CLV1-like receptor kinase, HAR1, mediates nitrate inhibition and autoregulation of nodulation. Autoregulation of nodulation involves root-to-shoot-to-root long-distance communication, and HAR1 functions in shoots. However, it remains elusive where HAR1 functions in the nitrate inhibition of nodulation. We performed grafting experiments with the har1 mutant under various nitrate conditions, and found that shoot HAR1 is critical for the inhibition of nodulation at 10 mM nitrate. Combined with our recent finding that the nitrate-induced CLE-RS2 glycopeptide binds directly to the HAR1 receptor, this result suggests that CLE-RS2/HAR1 long-distance signaling plays an important role in the both nitrate inhibition and the autoregulation of nodulation.

  12. Reactivity of vegetable oil macromonomers in thiol-ene, cationic, and emulsion polymerizations

    NASA Astrophysics Data System (ADS)

    Black, Micah Stephen

    Vegetable oils were, and continue, to be a mainstay in unsaturated polyester ("alkyd") technology. Our endeavor is to use vegetable oil-based polymers in environmentally-friendly coatings. The role of vegetable oil cis-unsaturation has not been fully explored in polymers. To that end, vegetable oil macromonomers (VOMMs) in three different systems were investigated to determine the involvement of cis-unsaturation in chain transfer, auto-oxidation, and copolymerization reactions. VOMMs were incorporated into UV curable thiol-ene coatings, UV cationic coatings, and acrylic solution copolymers and fundamental studies were conducted to determine how and to what extent cis-unsaturation contributes to film performance properties. In thiol-ene UV curable coatings, cis-unsaturation was involved in the initial curing reaction and to lesser degrees, in postcure crosslinking. Its behavior was determined to be dependent on the ene component. Thiol-ene photopolymerization yielded homogeneous networks but formulations containing VOMMs exhibited greater heterogeneity due to non-uniformity in the VOMM chemical structures, and the concurrent reactions occurring during thiol-ene photopolymerization and "dark cure". Partially epoxidized soybean oil was synthesized to contain varying levels of residual cis-unsaturation. Cationic photopolymerization of partially epoxidized soybean oil yielded lightly crosslinked films, but the influence of free radical decomposition byproducts has not been fully investigated. The low involvement of the cis-unsaturation in photopolymerization was attributed to its low reactivity and/or radical combination with antioxidants and molecular oxygen dissolved in the films. When used in emulsion polymerization, VOMMs lower the minimum filming temperature during coalescence and increase the Tg after application via auto-oxidation. Free radical polymerization of VOMMs is accompanied by chain transfer reactions between polymer radicals and VOMMs that reduces

  13. On-Orbit Evaluation of a New Treadmill Harness for Improved Crewmember Comfort and Load Distribution

    NASA Technical Reports Server (NTRS)

    Perusek, G. P.; Sheehan, C. C.; Savina, M. C.; Owings, T. M.; Davis, B. L.; Ryder, J. W.

    2011-01-01

    The current design of the International Space Station (ISS) Treadmill Harness has been reported to cause pain and discomfort to crewmembers during exercise. The Harness Station Development Test Objective (SDTO) provided participating crewmembers (n = 6) with a new harness design, the "Glenn Harness," to evaluate for comfort and loading as compared to the current Treadmill Harness. A novel suite of load-sensing instrumentation was developed to noninvasively measure load distribution and provided a first-ever quantification of actual dynamic loads during treadmill exercise. In addition, crew debriefs provided feedback on harness preference and overall impressions. Conclusions: Post-flight analysis in returned Glenn Harnesses (n = 3) showed minimal wear and tear. Four of the six subjects found the Glenn Harness to be more comfortable in this on-orbit, side-by-side comparison as measured by the crew comfort questionnaire and crew debriefs. Specific areas for improvement have been identified, and forward recommendations will be provided to the Human Research Program. The protocol developed for the SDTO provided valuable insight into crew comfort issues, design improvements, and loading preferences for exercise harnessing, which lays the groundwork for better harnessing systems and training protocols.

  14. How can developing countries harness biotechnology to improve health?

    PubMed Central

    Daar, Abdallah S; Berndtson, Kathryn; Persad, Deepa L; Singer, Peter A

    2007-01-01

    Background The benefits of genomics and biotechnology are concentrated primarily in the industrialized world, while their potential to combat neglected diseases in the developing world has been largely untapped. Without building developing world biotechnology capacity to address local health needs, this disparity will only intensify. To assess the potential of genomics to address health needs in the developing world, the McLaughlin-Rotman Centre for Global Health, along with local partners, organized five courses on Genomics and Public Health Policy in the developing world. The overall objective of the courses was to collectively explore how to best harness genomics to improve health in each region. This article presents and analyzes the recommendations from all five courses. Discussion In this paper we analyze recommendations from 232 developing world experts from 58 countries who sought to answer how best to harness biotechnology to improve health in their regions. We divide their recommendations into four categories: science; finance; ethics, society and culture; and politics. Summary The Courses' recommendations can be summarized across the four categories listed above: Science - Collaborate through national, regional, and international networks - Survey and build capacity based on proven models through education, training, and needs assessments Finance - Develop regulatory and intellectual property frameworks for commercialization of biotechnology - Enhance funding and affordability of biotechnology - Improve the academic-industry interface and the role of small and medium enterprise Ethics, Society, Culture - Develop public engagement strategies to inform and educate the public about developments in genomics and biotechnology - Develop capacity to address ethical, social and cultural issues - Improve accessibility and equity Politics - Strengthen understanding, leadership and support at the political level for biotechnology - Develop policies outlining

  15. "Hello, World!" Harnessing Social Media for the Rosetta Mission

    NASA Astrophysics Data System (ADS)

    Baldwin, E.; Mignone, C.; Scuka, D.; Homfeld, A. M.; Ranero, K.; Rolfe, E.; Bennett, M.; Schepers, A.; O'Flaherty, K. S.; Bauer, M.; McCaughrean, M.

    2016-03-01

    The European Space Agency's comet-chasing Rosetta mission was launched in 2004, before social media became a popular tool for mainstream communication. As it reached its destination ten years later, new audiences were reached and inspired by this once-in-a-lifetime event by harnessing a range of outlets for communicating the key messages. These included traditional online platforms, such as news websites, blogs, and Livestream, as well as Twitter, Facebook, Instagram, Flickr, YouTube, Google+ and SoundCloud. In this article, we outline the role social media channels played in making Rosetta one of the European Space Agency's biggest communication and public engagement successes.

  16. Asymmetric Simple Exclusion Process with Open Boundaries and Quadratic Harnesses

    NASA Astrophysics Data System (ADS)

    Bryc, Włodek; Wesołowski, Jacek

    2017-04-01

    We show that the joint probability generating function of the stationary measure of a finite state asymmetric exclusion process with open boundaries can be expressed in terms of joint moments of Markov processes called quadratic harnesses. We use our representation to prove the large deviations principle for the total number of particles in the system. We use the generator of the Markov process to show how explicit formulas for the average occupancy of a site arise for special choices of parameters. We also give similar representations for limits of stationary measures as the number of sites tends to infinity.

  17. Asymmetric Simple Exclusion Process with Open Boundaries and Quadratic Harnesses

    NASA Astrophysics Data System (ADS)

    Bryc, Włodek; Wesołowski, Jacek

    2017-02-01

    We show that the joint probability generating function of the stationary measure of a finite state asymmetric exclusion process with open boundaries can be expressed in terms of joint moments of Markov processes called quadratic harnesses. We use our representation to prove the large deviations principle for the total number of particles in the system. We use the generator of the Markov process to show how explicit formulas for the average occupancy of a site arise for special choices of parameters. We also give similar representations for limits of stationary measures as the number of sites tends to infinity.

  18. Materials that harness and modulate the immune system

    PubMed Central

    Lewis, Jamal S.; Roy, Krishnendu; Keselowsky, Benjamin G.

    2016-01-01

    Recently, biomaterial scientists have married materials engineering and immunobiology to conceptualize new immunomodulatory materials. This special class of biomaterials can modulate and harness the innate properties of immune functionality for enhanced therapeutic efficacy. Generally, two fundamental strategies are followed in the design of immunomodulatory biomaterials: (1) immuno-evasive (immuno-mimetic, immuno-suppressing, or immuno-inert) biomaterials and (2) immuno-activating or immuno-enhancing biomaterials. This article highlights the development and application of a number of immunomodulatory materials, categorized by these two general approaches. PMID:26997752

  19. Peroxisystem: harnessing systems cell biology to study peroxisomes.

    PubMed

    Schuldiner, Maya; Zalckvar, Einat

    2015-04-01

    In recent years, high-throughput experimentation with quantitative analysis and modelling of cells, recently dubbed systems cell biology, has been harnessed to study the organisation and dynamics of simple biological systems. Here, we suggest that the peroxisome, a fascinating dynamic organelle, can be used as a good candidate for studying a complete biological system. We discuss several aspects of peroxisomes that can be studied using high-throughput systematic approaches and be integrated into a predictive model. Such approaches can be used in the future to study and understand how a more complex biological system, like a cell and maybe even ultimately a whole organism, works.

  20. Harnessing the natural regenerative potential of the dental pulp.

    PubMed

    Smith, Anthony J; Smith, James G; Shelton, Richard M; Cooper, Paul R

    2012-07-01

    Biological solutions for the repair and regeneration of the dental tissues offer significant potential for improved clinical treatment outcomes. Translation of dental tissue-engineering approaches to the clinic will make considerable contributions to these outcomes in the future, but exploiting the natural regenerative potential of dentin-pulp to enhance wound-healing responses offers solutions for maintaining pulp vitality now. Strategies to harness the natural regenerative potential of the pulp must be based on a sound biological understanding of the cellular and molecular events taking place, and require careful consideration of the interplay of infection, inflammation, and regeneration. Copyright © 2012 Elsevier Inc. All rights reserved.

  1. Harnessing natural product assembly lines: structure, promiscuity, and engineering

    PubMed Central

    Ladner, Christopher C; Williams, Gavin J

    2015-01-01

    Many therapeutically relevant natural products are biosynthesized by the action of giant mega-enzyme assembly lines. By leveraging the specificity, promiscuity, and modularity of assembly lines, a variety of strategies have been developed that enable the biosynthesis of modified natural products. This review briefly summarizes recent structural advances related to natural product assembly lines, discusses chemical approaches to probing assembly line structures in the absence of traditional biophysical data, and surveys efforts that harness the inherent or engineered promiscuity of assembly lines for the synthesis of non-natural polyketides and nonribosomal peptide analogues. PMID:26527577

  2. Robust, Uniform, and Highly Emissive Quantum Dot-Polymer Films and Patterns Using Thiol-Ene Chemistry.

    PubMed

    Smith, Marcus J; Malak, Sidney T; Jung, Jaehan; Yoon, Young Jun; Lin, Chun Hao; Kim, Sunghan; Lee, Kyung Min; Ma, Ruilong; White, Timothy J; Bunning, Timothy J; Lin, Zhiqun; Tsukruk, Vladimir V

    2017-05-24

    This work demonstrates a facile and versatile method for generating low scattering cross-linked quantum dot (QD)-polymer composite films and patterned highly emissive structures with ultrahigh QD loading, minimal phase separation, and tunable mechanical properties. Uniform QD-polymer films are fabricated using thiol-ene chemistry, in which cross-linked polymer networks are rapidly produced in ambient conditions via fast UV polymerization in bulk to suppress QD aggregation. UV-controlled thiol-ene chemistry limits phase separation through producing highly QD loaded cross-linked composites with loadings above majority of those reported in the literature (<1%) and approaching 30%. As the QD loading is increased, the thiol and ene conversion decreases, resulting in nanocomposites with widely variable and tailorable mechanical properties as a function of UV irradiation time with an elastic modulus decreasing to 1 GPa being characteristic of reinforced elastomeric materials, in contrast to usually observed stiff and brittle materials under these loading conditions. Furthermore, we demonstrate that the thiol-ene chemistry is compatible with soft-imprint lithography, making it possible to pattern highly loaded QD films while preserving the optical properties essential for high gain and low optical loss devices. The versatility of thiol-ene chemistry to produce high-dense QD-polymer films potentially makes it an important technique for polymer-based elastomeric optical metamaterials, where efficient light propagation is critical, like peculiar waveguides, sensors, and optical gain films.

  3. The Impact of Harness Impedance on Hall Thruster Discharge Oscillations

    NASA Technical Reports Server (NTRS)

    Pinero, Luis R.

    2017-01-01

    Hall thrusters exhibit characteristic discharge voltage and current oscillations during steady-state operation. The lower frequency breathing-mode current oscillations are inherent to each thruster and could impact thruster operation and power processing unit (PPU) design. The design of the discharge output filter, in particular, the output capacitor is important because it supplies the high peak current oscillations that the thruster demands. However, space-rated, high-voltage capacitors are not readily available and can have significant mass and volume. So, it is important for a PPU designer to know what is the minimum amount of capacitance required to operate a thruster. Through Simulation Program with Integrated Circuit Emphasis modeling and electrical measurements on the Hall Effect Rocket with Magnetic Shielding thruster, it was shown that the harness impedance between the power supply and the thruster is the main contributor towards generating voltage ripple at the thruster. Also, increasing the size of the discharge filter capacitor, as previously implemented during thruster tests, does not reduce the voltage oscillations. The electrical characteristics of the electrical harness between the discharge supply and the thruster is crucial to system performance and could have a negative impact on performance, life and operation.

  4. Advantages and drawbacks of Thiol-ene based resins for 3D-printing

    NASA Astrophysics Data System (ADS)

    Leonards, Holger; Engelhardt, Sascha; Hoffmann, Andreas; Pongratz, Ludwig; Schriever, Sascha; Bläsius, Jana; Wehner, Martin; Gillner, Arnold

    2015-03-01

    The technology of 3D printing is conquering the world and awakens the interest of many users in the most varying of applications. New formulation approaches for photo-sensitive thiol-ene resins in combination with various printing technologies, like stereolithography (SLA), projection based printing/digital light processing (DLP) or two-photon polymerization (TPP) are presented. Thiol-ene polymerizations are known for its fast and quantitative reaction and to form highly homogeneous polymer networks. As the resins are locally and temporally photo-curable the polymerization type is very promising for 3D-printing. By using suitable wavelengths, photoinitiator-free fabrication is feasible for single- and two photon induced polymerization. In this paper divinyl ethers of polyethylene glycols in combination with star-shaped tetrathiols were used to design a simple test-system for photo-curable thiol-ene resins. In order to control and improve curing depth and lateral resolution in 3D-polymerization processes, either additives in chemical formulation or process parameters can be changed. The achieved curing depth and resolution limits depend on the applied fabrication method. While two-/multiphoton induced lithography offers the possibility of micron- to sub-micron resolution it lacks in built-up speed. Hence single-photon polymerization is a fast alternative with optimization potential in sub-10-micron resolution. Absorber- and initiator free compositions were developed in order to avoid aging, yellowing and toxicity of resulting products. They can be cured with UV-laser radiation below 300 nm. The development at Fraunhofer ILT is focusing on new applications in the field of medical products and implants, technical products with respect to mechanical properties or optical properties of 3D-printed objects. Recent process results with model system (polyethylene glycol divinylether/ Pentaerithrytol tetrakis (3-mercaptopropionat), Raman measurements of polymer conversion

  5. Investigations of step-growth thiol-ene polymerizations for novel dental restoratives.

    PubMed

    Lu, Hui; Carioscia, Jacquelyn A; Stansbury, Jeffery W; Bowman, Christopher N

    2005-12-01

    The goal of this work was to investigate the feasibility of formulating novel dental restorative materials that utilize a step-growth thiol-ene photopolymerization. Particularly, we are aiming to significantly reduce the polymerization shrinkage and shrinkage stress while retaining adequate physical properties as compared to current dimethacrylatre-based systems. The thiol-ene system is composed of a 4:3 molar mixture of triallyl-1,3,5-triazine-2,4,6-trione (TATATO) and pentaerythritol tetramercaptopropionate (PETMP). The simultaneous measurement of shrinkage stress and functional group conversion was performed. Solvent extraction of unreacted monomers and dynamic mechanical analysis on the polymer networks that were formed were also studied. Flexural strength was measured for both filled and unfilled PETMP/TATATO and Bis-GMA/TEGDMA systems. Photopolymerization of PETMP/TATATO occurs at a much higher rate, with the maximum polymerization rate six times faster, than Bis-GMA/TEGDMA cured under the identical conditions. The results from the simultaneous measurement of shrinkage stress and conversion showed that the onset of shrinkage stress coincides with the delayed gel point conversion, which is predicted to be 41% for the 3:4 stoichiometric PETMP/TATATO resin composition. The maximum shrinkage stress developed for PETMP/TATATO was about 0.4 MPa, which was only approximately 14% of the maximum shrinkage stress of the Bis-GMA/TEGDMA system. Adequate flexural strength and flexural modulus values were obtained for both filled and unfilled PETMP/TATATO systems. The dramatically reduced shrinkage stress, increased polymerization rate, significance increased functional group conversion, and decreased leachable species are all benefits for the use-of thiol-ene systems as potential dental restorative materials.

  6. Gold(I)-catalysed cycloisomerisation of 1,6-cyclopropene-enes.

    PubMed

    Miege, Frédéric; Meyer, Christophe; Cossy, Janine

    2012-06-18

    The gold(I)-catalysed cycloisomerisation of appropriately substituted 1,6-cyclopropene-enes proceeds through regioselective electrophilic ring opening of the three-membered ring to generate an alkenyl gold carbenoid that achieves the intramolecular cyclopropanation of the remote olefin. This strategy allows straightforward, highly efficient and diastereoselective access to a variety of substituted 3-oxa- and 3-azabicyclo[4.1.0]heptanes, as well as to bicyclo[4.1.0]heptan-3-ol derivatives. Since the isopropylidene group in the resulting cycloisomerisation products can be subjected to ozonolysis, 3,3-dimethylcyclopropenes behave as interesting surrogates for α-diazoketones.

  7. Synthesis of new pyrazolyl-1,3-diazabicyclo[3.1.0]hexe-3-ene derivatives

    NASA Astrophysics Data System (ADS)

    Kiyani, Hamzeh; Albooyeh, Fereshteh; Fallahnezhad, Saied

    2015-07-01

    A series of new of photochromic 1,3-diazabicyclo[3.1.0]hex-3-ene derivatives based on the skeleton of five-membered pyrazole moiety have been synthesized and characterized by spectral techniques, as well as their photochromic properties were examined under UV light irradiation in various solutions. All these newly synthesized compounds showed good photochromic properties in the both solution and solid states. The UV-Visible spectral analysis of the corresponding pyrazolyl bicyclic aziridines established structure-photochromic behavior relationships.

  8. Constructing thioether-tethered cyclic peptides via on-resin intra-molecular thiol-ene reaction.

    PubMed

    Zhao, Bingchuan; Zhang, Qingzhou; Li, Zigang

    2016-08-01

    Thiol-ene reactions have been used in a variety of applications that mostly involve an inter-molecular pathway. Herein, we report a facile method to construct thioether-tethered cyclic peptides via an intra-molecular thiol-ene reaction. This reaction is efficient, selective, and has good residue compatibility. Short peptides with thioether tethers were constructed and were used to construct longer cyclic peptides. This synthetic method may be useful for constructing bioactive peptides. Copyright © 2016 European Peptide Society and John Wiley & Sons, Ltd. Copyright © 2016 European Peptide Society and John Wiley & Sons, Ltd.

  9. Synthesis and Thermomechanical Behavior of (Qua)ternary Thiol-ene(/acrylate) Copolymers.

    PubMed

    Kasprzak, Scott; Martin, Blanton; Raj, Tulika; Gall, Ken

    2009-11-03

    The objective of this work is to characterize and understand the structure-to-thermo-mechanical property relationship in thiol-ene and thiol-ene/acrylate copolymers in order to complement the existing studies on the kinetics of this polymerization reaction. Forty-one distinct three- and four-part mixtures were created with systematically varied functionality, chemical structure, type and concentration of crosslinker. The resulting polymers were subjected to dynamic mechanical analysis and tensile testing at their glass transition temperature, T(g), to quantify and understand their thermomechanical properties. The copolymer systems exhibited a broad range of T(g), rubbery modulus - E(r) and failure strain. The addition of a difunctional high-T(g) acrylate to several three-part systems increased the resultant T(g) and E(r). Higher crosslink densities generally resulted in higher stress and lower strain at failure. The tunability of the thermomechanical properties of these copolymer systems is discussed in terms of inherent advantages and limitations in light of pure acrylate systems.

  10. Thiol-ene miniemulsion polymerization of a biobased monomer for biomedical applications.

    PubMed

    Machado, Thiago O; Cardoso, Priscilla B; Feuser, Paulo Emilio; Sayer, Claudia; Araújo, Pedro H H

    2017-07-18

    Herein, we present the synthesis and characterization of poly(thioether-ester) nanoparticles via thiol-ene miniemulsion polymerization using a biobased α,ω-diene diester monomer, namely dianhydro-d-glucityl diundec-10-enoate (DGU), synthesized from 10-undecenoic acid (derived from castor oil) and isosorbide (derived from starch). DGU was copolymerized with 1,4-butanedithiol by thiol-ene miniemulsion polymerization resulting in waterborne poly(thioether-ester) particles with diameter around 200nm. Polymers with number average molecular weight up to 11kDa were obtained via miniemulsion polymerization. DSC and XRD analyses indicated a semi-crystalline polymer with a degree of crystallinity of at least 20% and Tm around 68°C. In addition, Coumarin 6 was encapsulated in the polymer particles with efficiency up to 98%. Nanoparticles presented biocompatibility in murine fibroblast (L929) and uterine colon cancer (HeLa) cells. The substantial cellular uptake of poly(thioether-ester) nanoparticles by HeLa cells suggests a potential use in uterine colon cancer treatment. Copyright © 2017. Published by Elsevier B.V.

  11. Facile Fabrication of Polymerizable Ionic Liquid Based-Gel Beads via Thiol-ene Chemistry.

    PubMed

    Taghavikish, Mona; Subianto, Surya; Dutta, Naba Kumar; Choudhury, Namita Roy

    2015-08-12

    Multipurpose gel beads prepared from natural or synthetic polymers have received significant attention in various applications such as drug delivery, coatings, and electrolytes because of their versatility and unique performance as micro- and nanocontainers.1 However, comparatively little work has been done on poly(ionic liquid)-based materials despite their unique ionic characteristics. Thus, in this contribution we report the facile preparation of polymerizable ionic liquid-based gel beads using thiol-ene click chemistry. This novel system incorporates pentaerythritol tetra (3-mercaptopropionate) (PETKMP) and 1,4-di(vinylimidazolium) butane bisbromide in a thiol-ene-based photopolymerization to fabricate the gel beads. Their chemical structure, thermal and mechanical properties have been investigated using Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and dynamic mechanical analysis (DMA). The gel beads possess low Tg and their ionic functionalities attribute self-healing properties and their ability to uptake small molecules or organic compounds offers their potential use as pH sensing material and macrocontainers.

  12. 3β-Acetoxy-6-nitrocholest-5-ene: Crystal structure, thermal, optical and dielectrical behavior

    NASA Astrophysics Data System (ADS)

    Shamsuzzaman; Mashrai, Ashraf; Khanam, Hena; Mabkhot, Yahia Nasser; Frey, Wolfgang

    2014-04-01

    3β-Acetoxy-6-nitrocholest-5-ene (2) has been synthesized from 3β-acetoxycholest-5-ene (1). We provided an analysis of the compound by means of FT-IR, FT-Raman, NMR and X-ray crystallography. In addition microstructural, thermal, optical and dielectrical properties were also investigated. The compound 2 crystallizes in the monoclinic space group P21 with cell dimensions, a = 15.7729 (13) Å, b = 9.8933 (8) Å, c = 17.8070(14) Å, α = 90.00, β = 96.176(4), γ = 90.00. The powder X-ray diffraction (PXRD) of the compound was recorded to ascertain phase homogeneity. The SEM micrograph showed the presence of brick shaped, elongated nitrocholestane particles with 177.12 × 25.53 × 5.69 μm dimensions. Thermogravimetric analysis showed stability of the compound up to 200 °C. The dielectrical studies showed that with increase in frequency, the dielectric constant decreases and becomes almost constant at high frequencies.

  13. A Theoretical Study of Ene Reactions in Solution: A Solution-Phase Translational Entropy Model.

    PubMed

    Zhao, Liu; Li, Shi-Jun; Fang, De-Cai

    2015-12-01

    Several density functional theory (DFT) methods, such as CAM-B3LYP, M06, ωB97x, and ωB97xD, are used to characterize a range of ene reactions. The Gibbs free energy, activation enthalpy, and entropy are calculated with both the gas- and solution-phase translational entropy; the results obtained from the solution-phase translational entropies are quite close to the experimental measurements, whereas the gas-phase translational entropies do not perform well. For ene reactions between the enophile propanedioic acid (2-oxo-1,3-dimethyl ester) and π donors, the two-solvent-involved explicit+implicit model can be employed to obtain accurate activation entropies and free-energy barriers, because the interaction between the carbonyl oxygen atom and the solvent in the transition state is strengthened with the formation of C-C and O-H bonds. In contrast, an implicit solvent model is adequate to calculate activation entropies and free-energy barriers for the corresponding reactions of the enophile 4-phenyl-1,2,4-triazoline-3,5-dione.

  14. Facile functionalization of PDMS elastomer surfaces using thiol-ene click chemistry.

    PubMed

    Zhang, Jianfeng; Chen, Yang; Brook, Michael A

    2013-10-08

    A variety of methods have been developed for polydimethylsiloxane (PDMS) elastomer surface functionalization, particularly for the improvement of hydrophilicity. However, in addition to difficulties in avoiding undesired physical changes to the modified surface, including surface cracking, "hydrophobic recovery" frequently leads hydrophilically modified surfaces to completely return over time to their hydrophobic nature, with accompanying loss of accessible functional groups. Thiol-ene chemistry provides a mild and robust technology for synthetic elaboration. We demonstrate the introduction of thiol groups onto the PDMS surface via base-catalyzed equilibration of MTS ((MeO)3Si(CH2)3SH). Thiols in the product elastomer were shown to be located primarily at the air interface using EDX, XPS, and fluorescence labeling initially, and after extended periods of time: total thiol concentrations at the surface and in the bulk were established by complementary chemical titrations with DTDP (4,4'-dithiodipyridine) and iodine titrations in different solvents. The surface density of thiols was readily controlled by reaction conditions: the rate of hydrophobic recovery, which led to incomplete loss of accessible functional groups, was determined. Thiol-ene click chemistry was then used to introduce a variety of hydrophilic moieties onto the surface including a silicone surfactant and maleic anhydride, respectively. In the latter case, molecular functionalization with both small (fluorescent labels) and polymeric nucleophiles (poly(ethylene glycol), chitosan) could be subsequently induced by simple ring-opening nucleophilic attack leading to permanently functional surfaces.

  15. Advanced functionalization of polyhydroxyalkanoate via the UV-initiated thiol-ene click reaction.

    PubMed

    Tajima, Kenji; Iwamoto, Kosuke; Satoh, Yasuharu; Sakai, Ryosuke; Satoh, Toshifumi; Dairi, Tohru

    2016-05-01

    Polyhydroxyalkanoates (PHAs) incorporating vinyl-bearing 3-hydroxyalkanoates were prepared in 8.5-12.9 g L(-1) yield. The molar ratios (0-16 mol%) of the vinyl-bearing 3-hydroxyalkanoate derivatives were controlled by the continuous feeding of undecylenate at various concentrations. Subsequently, the PHAs were functionalized by UV-initiated thiol-ene click reaction and chemical modification. (1)H NMR spectra suggested that 3-mercaptopropionic acid and 2-aminoethanethiol were successfully introduced into the vinyl-bearing PHA. Subsequently, chemical modification using fluorescein or a fibronectin active fragment (GRGDS) was attempted. The former yielded a PHA derivative capable of emitting fluorescence under UV irradiation, which was useful for determining the miscibility of PHA in a composite film comprising poly-ʟ-lactic acid (PLLA) and PHA. In the latter case, PHA bearing GRGDS peptides exhibited cell adhesiveness, suggesting that its biocompatibility was improved upon peptide introduction. Taken together, the UV-initiated thiol-ene click reaction was demonstrated to be useful in PHA modification.

  16. Rapid approach to biobased telechelics through two one-pot thiol-ene click reactions.

    PubMed

    Lluch, Cristina; Ronda, Joan C; Galià, Marina; Lligadas, Gerard; Cádiz, Virginia

    2010-06-14

    The application of environmentally friendly thiol-ene chemistry to the preparation of biobased telechelics is presented in this work. This methodology is based on two one-pot photoinitiated thiol-ene click processes: step-growth polymerization using a 3,6-dioxa-1,8-octanedithiol and end-group postpolymerization modification with three functional thiols: 2-mercaptoethanol, 3-mercaptopropionic acid, and 3-mercaptopropyltrimethoxysilane. We applied this approach to a potentially 100% biomass-derived monomer, allyl ester of 10-undecenoic acid (UDA). To show the generality and scope of this methodology, a series of well-defined telechelics with molecular weight ranging from 1000-3000 g/mol and hydroxyl, carboxyl, or trimethoxysilyl groups at the polymer terminus were prepared. An exhaustive (1)H NMR and MALDI-TOF MS analyses demonstrates the highly end-group fidelity of this methodology being an interesting procedure for the accelerated preparation of telechelics derived from divinyl monomers. UDA-based thelechelic diol prepared using this methodology was reacted with 4,4'-methylenebis(phenylisocyanate) and 1,4-butanediol as the chain extender to obtain multiblock poly(ester urethane).

  17. Preliminary Engineering Report contaminated groundwater seeps 317/319/ENE area

    SciTech Connect

    1996-10-01

    When the Resource Conservation and Recovery Act Facility Investigation (RFI) in the 317/319/ENE Area of Argonne National Laboratory-East (ANL-E) was being completed, groundwater was discovered moving to the surface through a series of seeps. The seeps are located approximately 600 ft south of the ANL fence line in Waterfall Glen Forest Preserve. Samples of this water were collected and analyzed for selected parameters. Two of five seeps sampled were found to contain detectable levels of organic contaminants. Three chemical species were identified: chloroform (14-25 {mu}g/L), carbon tetrachloride (56-340 {mu}g/L), and tetrachloroethylene (3-6 {mu}g/L). The other seeps did not contain detectable levels of volatile organic compounds (VOCs). The water issuing from these two contaminated seeps flows into a narrow ravine, where it is visible as a trickle of water flowing through sand and gravel deposits on the floor of the ravine. Approximately 100-ft downstream of the seep area, the contaminated water is no longer visible, having drained back into the soil in the bed of the ravine. Figure 1 shows the location of the 317/319/ENE Area in relation to the ANL-E site and the Waterfall Glen Forest Preserve.

  18. Synthesis and Thermomechanical Behavior of (Qua)ternary Thiol-ene(/acrylate) Copolymers

    PubMed Central

    Kasprzak, Scott; Martin, Blanton; Raj, Tulika; Gall, Ken

    2009-01-01

    The objective of this work is to characterize and understand the structure-to-thermo-mechanical property relationship in thiol-ene and thiol-ene/acrylate copolymers in order to complement the existing studies on the kinetics of this polymerization reaction. Forty-one distinct three- and four-part mixtures were created with systematically varied functionality, chemical structure, type and concentration of crosslinker. The resulting polymers were subjected to dynamic mechanical analysis and tensile testing at their glass transition temperature, Tg, to quantify and understand their thermomechanical properties. The copolymer systems exhibited a broad range of Tg, rubbery modulus - Er and failure strain. The addition of a difunctional high-Tg acrylate to several three-part systems increased the resultant Tg and Er. Higher crosslink densities generally resulted in higher stress and lower strain at failure. The tunability of the thermomechanical properties of these copolymer systems is discussed in terms of inherent advantages and limitations in light of pure acrylate systems. PMID:22973067

  19. Parachuting harnesses comparative evaluation on energy distribution grids.

    PubMed

    Hembecker, Paula Karina; Poletto, Angela Regina; Gontijo, Leila Amaral

    2012-01-01

    This research aims to make a comparative evaluation of three different parachuting harnesses to work at heights in the energy industry, from the electricians' point of view concerning these products under the optics of usability and ergonomic principles, and mainly justified by the high quantity of injuries at the energy industry due to high falls. According to its main target, this field research is classified as exploratory-descriptive transversal viewing study and, considering this perspective, the study was developed in four steps. Research results have enlightened the weakest spots and the potential improvement opportunities of these products, developed to assure safety of the work at heights to the energy industry, according to the opinion of the users. Still, results point that, regardless of the model, these devices have adapting issues to fulfill the electrical sector user's needs.

  20. Response of Cable Harnesses Subjected to High-velocity Impacts

    NASA Astrophysics Data System (ADS)

    Nitta, Kumi; Kawakita, Shirou; Takeba, Atsushi; Katayama, Masahide

    We compared numerical simulation results obtained using AUTODYN-3D, which is used for impact analysis of complex physical systems including fluid and solid materials, with experimental results obtained using a two-stage light gas gun. The response of electric power supply cable harnesses subjected to high-velocity impact at 4.01 km/s is shown and discussed. In addition, AUTODYN-3D was applied to the numerical simulation of the hypervelocity impact of micrometeoroids and space debris (M/OD) at 15 km/s and 20 km/s, respectively. Material models used in the numerical simulation are also discussed and investigated in order to cover a wide range of impact velocities, including shock-induced vaporization.

  1. Bispecific antibodies and CARs: generalized immunotherapeutics harnessing T cell redirection

    PubMed Central

    Zhukovsky, Eugene A.; Morse, Richard J.; Maus, Marcela V.

    2016-01-01

    To realize the full potential of cancer immunotherapy, the latest generation immunotherapeutics are designed to harness the potent tumor-killing capacity of T cells. Thus, to mobilize T cells, new optimized bispecific antibody (BsAb) designs, enabling efficient polyclonal redirection of cytotoxic activity through binding to CD3 and a Tumor Associated Antigen (TAA) and refined genetically-modified T cells have recently expanded the arsenal of available options for cancer treatment. This review presents the current understanding of the parameters crucial to the design of optimal T cell redirecting BsAb and chimeric antigen receptor (CAR)-modified T cells. However, there are additional questions that require thorough elucidation. Both modalities will benefit from design changes that may increase the therapeutic window. One such approach could employ the discrimination afforded by multiple TAA to significantly increase selectivity. PMID:26963133

  2. Bispecific antibodies and CARs: generalized immunotherapeutics harnessing T cell redirection.

    PubMed

    Zhukovsky, Eugene A; Morse, Richard J; Maus, Marcela V

    2016-06-01

    To realize the full potential of cancer immunotherapy, the latest generation immunotherapeutics are designed to harness the potent tumor-killing capacity of T cells. Thus, to mobilize T cells, new optimized bispecific antibody (BsAb) designs, enabling efficient polyclonal redirection of cytotoxic activity through binding to CD3 and a Tumor Associated Antigen (TAA) and refined genetically modified T cells have recently expanded the arsenal of available options for cancer treatment. This review presents the current understanding of the parameters crucial to the design of optimal T cell redirecting BsAb and chimeric antigen receptor (CAR)-modified T cells. However, there are additional questions that require thorough elucidation. Both modalities will benefit from design changes that may increase the therapeutic window. One such approach could employ the discrimination afforded by multiple TAA to significantly increase selectivity. Copyright © 2016 Elsevier Ltd. All rights reserved.

  3. Harnessing plant-microbe interactions for enhancing farm productivity.

    PubMed

    Macdonald, Catriona; Singh, Brajesh

    2014-01-01

    Declining soil fertility and farm productivity is a major global concern in order to achieve food security for a burgeoning world population. It is reported that improving soil health alone can increase productivity by 10-15% and in combination with efficient plant traits, farm productivity can be increased up to 50-60%. In this article we explore the emerging microbial and bioengineering technologies, which can be employed to achieve the transformational increase in farm productivity and can simultaneously enhance environmental outcomes i.e., low green house gas (GHG) emissions. We argue that metagenomics, meta-transcriptomics and metabolomics have potential to provide fundamental knowledge on plant-microbes interactions necessary for new innovations to increase farm productivity. Further, these approaches provide tools to identify and select novel microbial/gene resources which can be harnessed in transgenic and designer plant technologies for enhanced resource use efficiencies.

  4. Harnessing power from tides - State of the art

    NASA Astrophysics Data System (ADS)

    Ryan, P. R.

    1980-02-01

    Instead of a conventional dam, a membrane of reinforced plastic (the 'water sail'), hermetically anchored to the bottom and sides of a bay, could harness power from tides. Such a membrane, constructed in sections, and estimated to be 20 to 30 times cheaper to construct than a conventional tidal project, could operate in a tidal range of two meters, instead of the usual five meters. Moreover, it could be lowered or pulled aside to allow ship traffic to pass or to protect it during storms. The top of the barrier would be supported by a cable (fixed to floats) spanning the entrance to the bay, while the conversion of tidal energy would be accomplished using compressed air, with two tidal chambers connected to a large piston air motor, although the possible use of gas turbine engines will also be tested.

  5. Harnessing plant-microbe interactions for enhancing farm productivity

    PubMed Central

    Macdonald, Catriona; Singh, Brajesh

    2014-01-01

    Declining soil fertility and farm productivity is a major global concern in order to achieve food security for a burgeoning world population. It is reported that improving soil health alone can increase productivity by 10–15% and in combination with efficient plant traits, farm productivity can be increased up to 50–60%. In this article we explore the emerging microbial and bioengineering technologies, which can be employed to achieve the transformational increase in farm productivity and can simultaneously enhance environmental outcomes i.e., low green house gas (GHG) emissions. We argue that metagenomics, meta-transcriptomics and metabolomics have potential to provide fundamental knowledge on plant-microbes interactions necessary for new innovations to increase farm productivity. Further, these approaches provide tools to identify and select novel microbial/gene resources which can be harnessed in transgenic and designer plant technologies for enhanced resource use efficiencies. PMID:23799872

  6. STS-39 MS Harbaugh is suspended over JSC's WETF Bldg 29 pool via harness

    NASA Technical Reports Server (NTRS)

    1990-01-01

    STS-39 Mission Specialist (MS) Gregory J. Harbaugh, wearing launch and entry suit (LES) and launch and entry helmet (LEH), is suspended above JSC's Weightless Environment Training Facility (WETF) Bldg 29 pool via his parachute harness. Harbaugh will be dropped from the harness into the WETF's 25 ft deep pool to simulate an emergency egress bailout from the Space Shuttle into the ocean.

  7. STS-39 MS Bluford is suspended over JSC's WETF Bldg 29 pool via harness

    NASA Technical Reports Server (NTRS)

    1990-01-01

    STS-39 Mission Specialist (MS) Guion S. Bluford, Jr, wearing launch and entry suit (LES) and launch and entry helmet (LEH), is suspended above JSC's Weightless Environment Training Facility (WETF) Bldg 29 pool via his parachute harness. Bluford will be dropped from the harness into the WETF's 25 ft deep pool to simulate an emergency egress bailout from the Space Shuttle into the ocean.

  8. Harnessing the Power of Information Technology: Open Business Models in Higher Education

    ERIC Educational Resources Information Center

    Sheets, Robert G.; Crawford, Stephen

    2012-01-01

    Higher education is under enormous pressure to improve outcomes and reduce costs. Information technology can help achieve these goals, but only if it is properly harnessed. This article argues that one key to harnessing information technology is business model innovation that results in more "open" and "unbundled" operations in learning and…

  9. 14 CFR 121.311 - Seats, safety belts, and shoulder harnesses.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... 14 Aeronautics and Space 3 2011-01-01 2011-01-01 false Seats, safety belts, and shoulder harnesses... § 121.311 Seats, safety belts, and shoulder harnesses. (a) No person may operate an airplane unless... lounge or divan seat may share one approved safety belt during en route flight only. (b) Except...

  10. 14 CFR 121.311 - Seats, safety belts, and shoulder harnesses.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 14 Aeronautics and Space 3 2010-01-01 2010-01-01 false Seats, safety belts, and shoulder harnesses... § 121.311 Seats, safety belts, and shoulder harnesses. (a) No person may operate an airplane unless... lounge or divan seat may share one approved safety belt during en route flight only. (b) Except...

  11. 14 CFR 135.171 - Shoulder harness installation at flight crewmember stations.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 14 Aeronautics and Space 3 2010-01-01 2010-01-01 false Shoulder harness installation at flight... ON BOARD SUCH AIRCRAFT Aircraft and Equipment § 135.171 Shoulder harness installation at flight... configuration, excluding any pilot seat, of 10 seats or more unless it is equipped with an approved...

  12. 14 CFR 105.43 - Use of single-harness, dual-parachute systems.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... 14 Aeronautics and Space 2 2011-01-01 2011-01-01 false Use of single-harness, dual-parachute... TRANSPORTATION (CONTINUED) AIR TRAFFIC AND GENERAL OPERATING RULES PARACHUTE OPERATIONS Parachute Equipment and Packing § 105.43 Use of single-harness, dual-parachute systems. No person may conduct a parachute...

  13. 14 CFR 105.43 - Use of single-harness, dual-parachute systems.

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ... 14 Aeronautics and Space 2 2014-01-01 2014-01-01 false Use of single-harness, dual-parachute... TRANSPORTATION (CONTINUED) AIR TRAFFIC AND GENERAL OPERATING RULES PARACHUTE OPERATIONS Parachute Equipment and Packing § 105.43 Use of single-harness, dual-parachute systems. No person may conduct a parachute...

  14. 14 CFR 105.43 - Use of single-harness, dual-parachute systems.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... 14 Aeronautics and Space 2 2012-01-01 2012-01-01 false Use of single-harness, dual-parachute... TRANSPORTATION (CONTINUED) AIR TRAFFIC AND GENERAL OPERATING RULES PARACHUTE OPERATIONS Parachute Equipment and Packing § 105.43 Use of single-harness, dual-parachute systems. No person may conduct a parachute...

  15. 14 CFR 105.43 - Use of single-harness, dual-parachute systems.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... 14 Aeronautics and Space 2 2013-01-01 2013-01-01 false Use of single-harness, dual-parachute... TRANSPORTATION (CONTINUED) AIR TRAFFIC AND GENERAL OPERATING RULES PARACHUTE OPERATIONS Parachute Equipment and Packing § 105.43 Use of single-harness, dual-parachute systems. No person may conduct a parachute...

  16. Harnessing the Power of Information Technology: Open Business Models in Higher Education

    ERIC Educational Resources Information Center

    Sheets, Robert G.; Crawford, Stephen

    2012-01-01

    Higher education is under enormous pressure to improve outcomes and reduce costs. Information technology can help achieve these goals, but only if it is properly harnessed. This article argues that one key to harnessing information technology is business model innovation that results in more "open" and "unbundled" operations in learning and…

  17. STS-39 MS Bluford is suspended over JSC's WETF Bldg 29 pool via harness

    NASA Technical Reports Server (NTRS)

    1990-01-01

    STS-39 Mission Specialist (MS) Guion S. Bluford, Jr, wearing launch and entry suit (LES) and launch and entry helmet (LEH), is suspended above JSC's Weightless Environment Training Facility (WETF) Bldg 29 pool via his parachute harness. Bluford will be dropped from the harness into the WETF's 25 ft deep pool to simulate an emergency egress bailout from the Space Shuttle into the ocean.

  18. The effect of the use of full body harnesses on their protective properties.

    PubMed

    Baszczyński, Krzysztof; Jachowicz, Marcin

    2009-01-01

    A full body harness is a component of personal systems protecting against falls from a height. To ensure users' safety, the harness must retain its protective properties during its whole service period. All the elements of a harness (webbings, threads, metal buckles, etc.) are exposed to destructive factors. Harnesses stored and used for a few years were tested. The paper discusses the most frequent types of damage and their effect on the essential resistance parameters. The effect of atmospheric conditions, sunlight, mechanical damage and dust on the parameters of webbings was tested. Conclusions on the main causes of the loss of the protective properties of harnesses are drawn; periodic checks of the physical conditions and guidelines for estimating acceptable service time are recommended.

  19. Isomorphous crystal structures of chlorodi­acetyl­ene and iododi­acetyl­ene derivatives: simultaneous hydrogen and halogen bonds on carbon­yl

    PubMed Central

    Baillargeon, Pierre; Rahem, Tarik; Caron-Duval, Édouard; Tremblay, Jacob; Fortin, Cloé; Blais, Étienne; Fan, Victor; Fortin, Daniel; Dory, Yves L.

    2017-01-01

    The crystal structures of tert-butyl (5-chloro­penta-2,4-diyn-1-yl)carbamate, C10H12ClNO2 (II), and tert-butyl (5-iodo­penta-2,4-diyn-1-yl)carbamate, C10H12INO2 (IV), are isomorphous to previously reported structures and accordingly their mol­ecular and supra­molecular structures are similar. In the crystals of (II) and (IV), mol­ecules are linked into very similar two-dimensional wall organizations with anti­parallel carbamate groups involved in a combination of hydrogen and halogen bonds (bifurcated N—H⋯O=C and C≡C—X⋯O=C inter­actions on the same carbonyl group). There is no long-range parallel stacking of diynes, so the topochemical polymerization of di­acetyl­ene is prevented. A Cambridge Structural Database search revealed that C≡C—X⋯O=C contacts shorter than the sum of the van der Waals radii are scarce (only one structure for the C≡C—Cl⋯O=C inter­action and 13 structures for the similar C≡C—I⋯O=C inter­action). PMID:28932431

  20. Iron-Catalyzed Tandem Conia-Ene/Friedel-Crafts Reactions of o-Alkynyldihydrochalcones: Access to Benzo[b]fluorenes.

    PubMed

    Akbar, Sikkandarkani; Srinivasan, Kannupal

    2016-02-05

    o-Alkynyldihydrochalcones when treated with a catalytic amount of anhydrous FeCl3 in refluxing 1,2-dichloroethane underwent tandem Conia-ene and Friedel-Crafts reactions to yield benzo[b]fluorene derivatives in good yields.

  1. Light-driven nitrile imine-mediated tetrazole-ene cycloaddition as a versatile platform for fullerene conjugation.

    PubMed

    Sugawara, Yuuki; Jasinski, Nils; Kaupp, Michael; Welle, Alexander; Zydziak, Nicolas; Blasco, Eva; Barner-Kowollik, Christopher

    2015-08-21

    An efficient methodology for modular fullerene functionalization via the photo-induced nitrile imine-mediated tetrazole-ene cycloaddition (NITEC) is introduced. The versatility and platform character of the method is illustrated by the light-driven reaction of fullerenes with small molecule, polymeric and surface-immobilized tetrazoles. The efficient fullerene conjugation is evidenced via mass spectrometric techniques.

  2. Highly enantioselective and anti-diastereoselective catalytic intermolecular glyoxylate-ene reactions: effect of the geometrical isomers of alkenes.

    PubMed

    Zhang, Xiang; Wang, Min; Ding, Ran; Xu, Yun-He; Loh, Teck-Peng

    2015-06-05

    An efficient method for the synthesis of homoallylic alcohols with high enantioselectivities and anti-diastereoselectivities via an In(III)-catalyzed intermolecular glyoxylate-ene reaction has been developed. The geometrical isomers of alkenes were shown to have different reactivities. Only the isomers of the alkenes having a proton β-cis to the substituent reacted in this catalytic system.

  3. Analysis of Production Lead Time for Missile Repair Parts: Contracts Dealing with Cable Assemblies and Wiring Harnesses

    DTIC Science & Technology

    1975-04-01

    contracts dealing with cable assemblies and wiring harnesses . Techniques of regression analysis and graphical analysis were employed on the data observations from thirty cable assembly and wiring harness contracts.

  4. Fates of imine intermediates in radical cyclizations of N-sulfonylindoles and ene-sulfonamides.

    PubMed

    Zhang, Hanmo; Hay, E Ben; Geib, Stephen J; Curran, Dennis P

    2015-01-01

    Two new fates of imine intermediates formed on radical cyclizations of ene-sulfonamides have been identified, reduction and hydration/fragmentation. Tin hydride-mediated cyclizations of 2-halo-N-(3-methyl-N-sulfonylindole)anilines provide spiro[indoline-3,3'-indolones] or spiro-3,3'-biindolines (derived from imine reduction), depending on the indole C2 substituent. Cyclizations of 2-haloanilide derivatives of 3-carboxy-N-sulfonyl-2,3-dihydropyrroles also presumably form spiro-imines as primary products. However, the lactam carbonyl group facilitates the ring-opening of these cyclic imines by a new pathway of hydration and retro-Claisen-type reaction, providing rearranged 2-(2'-formamidoethyl)oxindoles.

  5. Fates of imine intermediates in radical cyclizations of N-sulfonylindoles and ene-sulfonamides

    PubMed Central

    Zhang, Hanmo; Hay, E Ben; Geib, Stephen J

    2015-01-01

    Summary Two new fates of imine intermediates formed on radical cyclizations of ene-sulfonamides have been identified, reduction and hydration/fragmentation. Tin hydride-mediated cyclizations of 2-halo-N-(3-methyl-N-sulfonylindole)anilines provide spiro[indoline-3,3'-indolones] or spiro-3,3'-biindolines (derived from imine reduction), depending on the indole C2 substituent. Cyclizations of 2-haloanilide derivatives of 3-carboxy-N-sulfonyl-2,3-dihydropyrroles also presumably form spiro-imines as primary products. However, the lactam carbonyl group facilitates the ring-opening of these cyclic imines by a new pathway of hydration and retro-Claisen-type reaction, providing rearranged 2-(2'-formamidoethyl)oxindoles. PMID:26664585

  6. A Thiol-Ene Coupling Approach to Native Peptide Stapling and Macrocyclization.

    PubMed

    Wang, Yuanxiang; Chou, Danny Hung-Chieh

    2015-09-07

    We report the discovery of a peptide stapling and macrocyclization method using thiol-ene reactions between two cysteine residues and an α,ω-diene in high yields. This new approach enabled us to selectively modify cysteine residues in native, unprotected peptides with a variety of stapling modifications for helix stabilization or general macrocyclization. We synthesized stapled Axin mimetic analogues and demonstrated increased alpha helicity upon peptide stapling. We then synthesized stapled p53 mimetic analogues using pure hydrocarbon linkers and demonstrated their abilities to block the p53-MDM2 interaction and selectively kill p53 wild-type colorectal carcinoma HCT-116 cells but not p53 null cells. In summary, we demonstrated a robust and versatile peptide stapling method that could be potentially applied to both synthetic and expressed peptides.

  7. Making Silicone Rubber Highly Resistant to Bacterial Attachment Using Thiol-ene Grafting

    PubMed Central

    2016-01-01

    Biomedical devices are indispensable in modern medicine yet offer surfaces that promote bacterial attachment and biofilm formation, resulting in acute and chronic healthcare-associated infections. We have developed a simple method to graft acrylates to silicone rubber, polydimethylsiloxane (PDMS), a commonly used device material that is often colonized by bacteria. We demonstrate a novel method whereby nontoxic bacteria attachment-resistant polymers can be readily grafted from and grafted to the surface using thiol-ene chemistry, substantially reducing bacterial colonization. With use of this approach, bacterial biofilm coverage can be reduced by 99% compared with standard PDMS in an in vitro assay. This grafting approach offers significant advantages over commonly used physisorbed coatings, especially in areas of high shear or mechanical stress. Furthermore, the approach is versatile such that the grafted material properties can be tailored for the desired final application. PMID:27775316

  8. Tailored Composite Polymer-Metal Nanoparticles by Miniemulsion Polymerization and Thiol-ene Functionalization

    PubMed Central

    van Berkel, Kim Y.

    2010-01-01

    A simple and modular synthetic approach, based on miniemulsion polymerization, has been developed for the fabrication of composite polymer-metal nanoparticle materials. The procedure produces well-defined composite structures consisting of gold, silver or MnFe2O4 nanoparticles (∼10 nm in diameter) encapsulated within larger spherical nanoparticles of poly(divinylbenzene) (∼100 nm in diameter). This methodology readily permits the incorporation of multiple metal domains into a single polymeric particle, while still preserving the useful optical and magnetic properties of the metal nanoparticles. The morphology of the composite particles is retained upon increasing the inorganic content, and also upon redispersion in organic solvents. Finally, the ability to tailor the surface chemistry of the composite nanoparticles and incorporate steric stabilizing groups using simple thiol-ene chemistry is demonstrated. PMID:20657708

  9. Flash photolysis and low temperature photochemistry of bovine rhodopsin with a fixed 11-ene.

    PubMed Central

    Mao, B; Tsuda, M; Ebrey, T G; Akita, H; Balogh-Nair, V; Nakanishi, K

    1981-01-01

    Nonbleachable rhodopsins containing retinal moieties with fixed 11-ene structures have been prepared. When the nonbleachable rhodopsin analogue corresponding to the natural pigment was flash-photolysed at 20.8 degrees C, no absorption changes occurred at the monitoring wavelengths of 380, 480, and 580 nm for the time range of 2 microseconds--10 s. This observation is in contrast to that of natural rhodopsin which showed the formation of metarhodopsin I and its decay to meta II. Irradiation of the artificial rhodopsin, 77 K, with light of 460 and 540 nm, also gave no spectral changes; in the case of natural rhodopsin, however, the irradiation leads to formation of the red-shifted intermediate bathorhodopsin. The absence of photochemistry in the artificial pigment shows that an 11-cis to trans photoisomerization of the retinal moiety is a crucial step in inducing the chain of events in te photolysis of rhodopsin. PMID:7272450

  10. Investigation of the stereochemical course of ene reductase-catalysed reactions by deuterium labelling.

    PubMed

    Brenna, Elisabetta; Fronza, Giovanni; Fuganti, Claudio; Parmeggiani, Fabio

    2015-01-01

    The stereoselective reduction of suitably substituted C═C bonds mediated by enzymes, called ene reductases, has received great attention in the last decade. Some successful applications of this biocatalysed procedure to the synthesis of chiral active pharmaceutical ingredients have been reported in the literature. The generation of suitable models to be used for predicting the stereochemical outcome of this kind of reductions is a challenging task. In the last years we have exploited deuterium labelling to investigate the stereochemical course of the enzyme-mediated reductions of a wide collection of substrates belonging to well-defined chemical classes. The results of this research have allowed us to draw conclusions on the relationship between the structural characteristics of the substrate and the binding mode it adopts in the enzyme active site. The collected data can be exploited to create an empirical model to rationalise and predict the stereoselectivity of old yellow enzyme (OYE)-catalysed reductions.

  11. Surface grafting of vinyl-functionalized poly(fluorene)s via thiol-ene click chemistry.

    PubMed

    Davis, Andrew R; Carter, Kenneth R

    2014-04-22

    Thiol-ene chemistry is used for the surface grafting of vinyl-functionalized poly(fluorene) derivatives onto substrates containing free surface thiol groups. The grafting reaction proceeds in a matter of minutes under UV irradiation without photoinitiator, and the resulting surface-bound, solvent-impervious conjugated polymers retain their characteristic optoelectronic properties. End-chain grafted poly(fluorene)s reach greater surface densities than their side-chain grafted counterparts and show less blue-shifting of photoluminescence upon grafting, suggesting that chain end-grafted conjugated polymers experience less disruption of their extended conjugation and adopt a more brush-like surface conformation. Surface grafted poly(fluorene)s showed facile photopatterning, and thin film transistors with semiconducting polymers directly grafted to the dielectric layer showed performances directly comparable to conventional self-assembled layers of performance-improving alkylsilanes.

  12. Inorganic-Organic Thiol-ene Coated Mesh for Oil/Water Separation.

    PubMed

    Chen, Qiyi; de Leon, Al; Advincula, Rigoberto C

    2015-08-26

    A highly efficient mesh for oil/water separation was fabricated by using a superhydrophobic and superoleophilic coating of thiol-ene hybrid, consisting of pentaerythritol tetra(3-mercaptopropionate) (PETMP), 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane (TMTVSi), and hydrophobic fumed silica nanoparticles, via a simple two-step fabrication process. Spray deposition and UV curing photopolymerization were sequentially performed, during which solvent evaporation provides microscale roughness while nanoparticle aggregation forms nanoscale roughness. The hierarchical morphologies were stabilized after UV curing photopolymerization. High contact angle (>150°) and low roll-off angle (<5°) were achieved due to the multiscale roughness structure of the hierarchical morphologies. These coatings also have excellent chemical resistance, as well as temperature and pH stability, after curing.

  13. Lumbar spine disc heights and curvature: upright posture vs. supine compression harness

    NASA Technical Reports Server (NTRS)

    Lee, Shi-Uk; Hargens, Alan R.; Fredericson, Michael; Lang, Philipp K.

    2003-01-01

    INTRODUCTION: Spinal lengthening in microgravity is thought to cause back pain in astronauts. A spinal compression harness can compress the spine to eliminate lengthening but the loading condition with harness is different than physiologic conditions. Our purpose was to compare the effect of spine compression with a harness in supine position on disk height and spinal curvature in the lumbar spine to that of upright position as measured using a vertically open magnetic resonance imaging system. METHODS: Fifteen healthy subjects volunteered. On day 1, each subject lay supine for an hour and a baseline scan of the lumbar spine was performed. After applying a load of fifty percent of body weight with the harness for thirty minutes, the lumbar spine was scanned again. On day 2, after a baseline scan, a follow up scan was performed after kneeling for thirty minutes within the gap between two vertically oriented magnetic coils. Anterior and posterior disk heights, posterior disk bulging, and spinal curvature were measured from the baseline and follow up scans. RESULTS: Anterior disk heights increased and posterior disk heights decreased compared with baseline scans both after spinal compression with harness and upright posture. The spinal curvature increased by both loading conditions of the spine. DISCUSSION: The spinal compression with specially designed harness has the same effect as the physiologic loading of the spine in the kneeling upright position. The harness shows some promise as a tool to increase the diagnostic capabilities of a conventional MR system.

  14. Application of a modified harness design for attachment of radio transmitters to shorebirds

    USGS Publications Warehouse

    Sanzenbacher, Peter; Haig, Susan M.; Oring, L.W.

    2000-01-01

    Radio transmitter attachment methodology is important to the design of radio telemetry studies. In 1998, we attached 5 transmitters to a captive population of Western Sandpipers(Calidris mauri) and 7 transmitters to wild Killdeer (Charadriusv ociferus) using a modified version of the Rappolea nd Tipton (1991) figure-8 leg-loop harness. Captive birds fitted with harnesses did not exhibit quantifiable differences in behavior relative to control birds. Based on initial success in using the leg-loop harnesses, we used harnesses to attach transmitters in the wild to 30 Killdeer and 49 Dunlin (Calidris alpina) during the winters of 1998-1999 and 1999-2000. This was part of a study on movements of wintering shorebirds in the Willamette Valley of Oregon,USA. Wild birds showed no adverse effects of the harnesses.Thus, the described harness is a practical method for attachment of transmitters to shorebirds. Advantages of this harness method include a reduction in handling time at capture, elimination of the need to clip feathers for attachment, and increased transmitter retention time.

  15. Lumbar spine disc heights and curvature: upright posture vs. supine compression harness

    NASA Technical Reports Server (NTRS)

    Lee, Shi-Uk; Hargens, Alan R.; Fredericson, Michael; Lang, Philipp K.

    2003-01-01

    INTRODUCTION: Spinal lengthening in microgravity is thought to cause back pain in astronauts. A spinal compression harness can compress the spine to eliminate lengthening but the loading condition with harness is different than physiologic conditions. Our purpose was to compare the effect of spine compression with a harness in supine position on disk height and spinal curvature in the lumbar spine to that of upright position as measured using a vertically open magnetic resonance imaging system. METHODS: Fifteen healthy subjects volunteered. On day 1, each subject lay supine for an hour and a baseline scan of the lumbar spine was performed. After applying a load of fifty percent of body weight with the harness for thirty minutes, the lumbar spine was scanned again. On day 2, after a baseline scan, a follow up scan was performed after kneeling for thirty minutes within the gap between two vertically oriented magnetic coils. Anterior and posterior disk heights, posterior disk bulging, and spinal curvature were measured from the baseline and follow up scans. RESULTS: Anterior disk heights increased and posterior disk heights decreased compared with baseline scans both after spinal compression with harness and upright posture. The spinal curvature increased by both loading conditions of the spine. DISCUSSION: The spinal compression with specially designed harness has the same effect as the physiologic loading of the spine in the kneeling upright position. The harness shows some promise as a tool to increase the diagnostic capabilities of a conventional MR system.

  16. Hydrophobic Coatings by Thiol-Ene Click Functionalization of Silsesquioxanes with Tunable Architecture

    PubMed Central

    Génois, Isabelle

    2017-01-01

    The hydrolysis-condensation of trialkoxysilanes under strictly controlled conditions allows the production of silsesquioxanes (SSQs) with tunable size and architecture ranging from ladder to cage-like structures. These nano-objects can serve as building blocks for the preparation of hybrid organic/inorganic materials with selected properties. The SSQs growth can be tuned by simply controlling the reaction duration in the in situ water production route (ISWP), where the kinetics of the esterification reaction between carboxylic acids and alcohols rules out the extent of organosilane hydrolysis-condensation. Tunable SSQs with thiol functionalities (SH-NBBs) are suitable for further modification by exploiting the simple thiol-ene click reaction, thus allowing for modifying the wettability properties of derived coatings. In this paper, coatings were prepared from SH-NBBs with different architecture onto cotton fabrics and paper, and further functionalized with long alkyl chains by means of initiator-free UV-induced thiol-ene coupling with 1-decene (C10) and 1-tetradecene (C14). The coatings appeared to homogeneously cover the natural fibers and imparted a multi-scale roughness that was not affected by the click functionalization step. The two-step functionalization of cotton and paper warrants a stable highly hydrophobic character to the surface of natural materials that, in perspective, suggests a possible application in filtration devices for oil-water separation. Furthermore, the purification of SH-NBBs from ISWP by-products was possible during the coating process, and this step allowed for the fast, initiator-free, click-coupling of purified NBBs with C10 and C14 in solution with a nearly quantitative yield. Therefore, this approach is an alternative route to get sol-gel-derived, ladder-like, and cage-like SSQs functionalized with long alkyl chains. PMID:28786939

  17. Hydrophobic Coatings by Thiol-Ene Click Functionalization of Silsesquioxanes with Tunable Architecture.

    PubMed

    Dirè, Sandra; Bottone, Davide; Callone, Emanuela; Maniglio, Devid; Génois, Isabelle; Ribot, François

    2017-08-08

    The hydrolysis-condensation of trialkoxysilanes under strictly controlled conditions allows the production of silsesquioxanes (SSQs) with tunable size and architecture ranging from ladder to cage-like structures. These nano-objects can serve as building blocks for the preparation of hybrid organic/inorganic materials with selected properties. The SSQs growth can be tuned by simply controlling the reaction duration in the in situ water production route (ISWP), where the kinetics of the esterification reaction between carboxylic acids and alcohols rules out the extent of organosilane hydrolysis-condensation. Tunable SSQs with thiol functionalities (SH-NBBs) are suitable for further modification by exploiting the simple thiol-ene click reaction, thus allowing for modifying the wettability properties of derived coatings. In this paper, coatings were prepared from SH-NBBs with different architecture onto cotton fabrics and paper, and further functionalized with long alkyl chains by means of initiator-free UV-induced thiol-ene coupling with 1-decene (C10) and 1-tetradecene (C14). The coatings appeared to homogeneously cover the natural fibers and imparted a multi-scale roughness that was not affected by the click functionalization step. The two-step functionalization of cotton and paper warrants a stable highly hydrophobic character to the surface of natural materials that, in perspective, suggests a possible application in filtration devices for oil-water separation. Furthermore, the purification of SH-NBBs from ISWP by-products was possible during the coating process, and this step allowed for the fast, initiator-free, click-coupling of purified NBBs with C10 and C14 in solution with a nearly quantitative yield. Therefore, this approach is an alternative route to get sol-gel-derived, ladder-like, and cage-like SSQs functionalized with long alkyl chains.

  18. Computational study of the carbonyl-ene reaction of encapsulated formaldehyde in Na-FAU zeolite

    NASA Astrophysics Data System (ADS)

    Sangthong, Winyoo; Probst, Michael; Limtrakul, Jumras

    2005-06-01

    Density-functional theory (B3LYP/6-31G(d,p)) and the ONIOM (Our-own-N-layer Integrated molecular Orbital+molecular Mechanics) approach utilizing two-layer ONIOM schemes (B3LYP/6-31G(d,p):UFF) have been employed to investigate structures of Na-exchanged zeolite-encapsulated formaldehyde (HCHO@Na-zeolite) and their interactions with propylene. The carbonyl-ene reaction of propylene and formaldehyde was studied on three model systems: (1) formaldehyde in Na-exchanged zeolite: HCHO@Na-zeolite/CH 3CH dbnd6 CH 2; (2) naked Na(I) as catalyst: Na(I)/HCHO/CH 3CH dbnd6 CH 2; (3) a bare model where only the reactants are present: HCHO/CH 3CH dbnd6 CH 2. It is found that inclusion of the extended zeolite framework has an effect on the structure and energetics of the adsorption complexes and leads to a lower energy barrier (25.1 kcal/mol) of the reaction as compared to the bare model system (34.4 kcal/mol). If the naked Na(I) interacts with the HCHO/CH 3CH dbnd6 CH 2 complex the energy barrier of the system is even lower than HCHO@Na-zeolite/CH 3CH dbnd6 CH 2, due to the large electrostatic field generated by the naked Na(I) cation (17.5 kcal/mol). The carbonyl-ene reaction of propylene using HCHO@Na-faujasite takes place in a single concerted reaction step.

  19. Support to Climate Data Dissemination in a Worldwide Data Federation by IS-ENES2

    NASA Astrophysics Data System (ADS)

    Rathmann, Torsten; Toussaint, Frank; Kindermann, Stephan; Lautenschlager, Michael

    2015-04-01

    Thousands of users accessed climate data produced as part of the Coupled Model Intercomparison Project Phase 5 (CMIP5). The data were created by about 30 different institutes and disseminated to a large variety of end users via a worldwide distributed infrastructure (Earth System Grid Federation, ESGF) consisting of data nodes and data portals. Part of the data was also used for the 5th Assessment Report of the Intergovernmental Panel on Climate Change and preserved in a long term archive. A support activity was funded within the IS-ENES2 FP7 project to support the various aspects of data dissemination for large intercomparison projects like CMIP5 and CORDEX. The activity was structured into the following parts: Support for data providers: • Development of basic data quality assurance tools, to be applied by data provider prior to making data accessible in the data federation • Support in installing and using the quality assurance tools • Agreements on best practices of data dissemination (e.g. search facets to be supported across sites etc.) Support for data users: Establishment of basic user support infrastructure components and services: • Askbot based internet forum for user support questions and answers • Support pages on central portals • Continuous maintenance of user support mailing lists Support for data centres and for fostering their collaboration: • Development of automatic consistency checking routines for data federation portals operated at different sites • Organization of data node installation and operation support events • Collection of distributed data usage statistic metrics • Development of Data Management Plans (DMP) • Activities towards common data access policies The experiences gained within the IS-ENES2 support activities will provide the basis of activities for improving the user support process in the future, especially in the context of upcoming large intercomparison projects like CMIP6, which will use the same

  20. Competition between dihydrogen bond and beryllium bond in complexes between HBeH and HArF: a huge blue shift of distant H-Ar stretch.

    PubMed

    Li, Qingzhong; Liu, Xiaofeng; Li, Ran; Cheng, Jianbo; Li, Wenzuo

    2012-05-01

    A novel interaction mechanism between HArF and BeH(2) has been validated and characterized with quantum chemical calculations at the MP2/aug-cc-pVQZ level. They can interact through beryllium bonding formed between the positively charged Be atom in BeH(2) and the negatively charged F atom in HArF, besides through dihydrogen bonding. The former (61.3 kcal/mol) is much stronger than the latter (5.9 kcal/mol). The red shift is found for the associated H-Ar stretch in the dihydrogen bonding, whereas the big blue shift is observed for the distant H-Ar stretch in the beryllium bonding. The blue shift of the distant H-Ar stretch is affected greatly by computational methods. It is calculated to be 712 cm(-1) at the CCSD(T)/6-311++G(3df,2p) level, which appears to be the largest blue shift validated for any weakly bound complex yet. The substitution effect on the beryllium bond is similar to that on hydrogen bonds. The Kr atom makes the beryllium bond weaken and the distant blue shift decrease. The nature and properties of beryllium bond have been analyzed with natural bond orbital (NBO), atoms in molecules (AIM), and energy decomposition. Copyright © 2012 Elsevier B.V. All rights reserved.

  1. Mic Flocks in the Cloud: Harnessing Mobile Ubiquitous Sensor Networks

    NASA Astrophysics Data System (ADS)

    Garces, M. A.; Christe, A.

    2015-12-01

    Smartphones provide a commercial, off-the-shelf solution to capture, store, analyze, and distribute infrasound using on-board or external microphones (mics) as well as on-board barometers. Free iOS infrasound apps can be readily downloaded from the Apple App Store, and Android versions are in progress. Infrasound propagates for great distances, has low sample rates, and provides a tractable pilot study scenario for open distributed sensor networks at regional and global scales using one of the most ubiquitous sensors on Earth - microphones. Data collection is no longer limited to selected vendors at exclusive prices: anybody on Earth can record and stream infrasound, and the diversity of recording systems and environments is rapidly expanding. Global deployment may be fast and easy (www.redvox.io), but comes with the cost of increasing data volume, velocity, variety, and complexity. Flocking - the collective motion of mobile agents - is a natural human response to threats or events of interest. Anticipating, modeling and harnessing flocking sensor topologies will be necessary for adaptive array and network processing. The increasing data quantity and complexity will exceed the processing capacity of human analysts and most research servers. We anticipate practical real-time applications will require the on-demand adaptive scalability and resources of the Cloud. Cloud architectures for such heterogeneous sensor networks will consider eventual integration into the Global Earth Observation System of Systems (GEOSS).

  2. Abasic pivot substitution harnesses target specificity of RNA interference.

    PubMed

    Lee, Hye-Sook; Seok, Heeyoung; Lee, Dong Ha; Ham, Juyoung; Lee, Wooje; Youm, Emilia Moonkyung; Yoo, Jin Seon; Lee, Yong-Seung; Jang, Eun-Sook; Chi, Sung Wook

    2015-12-18

    Gene silencing via RNA interference inadvertently represses hundreds of off-target transcripts. Because small interfering RNAs (siRNAs) can function as microRNAs, avoiding miRNA-like off-target repression is a major challenge. Functional miRNA-target interactions are known to pre-require transitional nucleation, base pairs from position 2 to the pivot (position 6). Here, by substituting nucleotide in pivot with abasic spacers, which prevent base pairing and alleviate steric hindrance, we eliminate miRNA-like off-target repression while preserving on-target activity at ∼ 80-100%. Specifically, miR-124 containing dSpacer pivot substitution (6pi) loses seed-mediated transcriptome-wide target interactions, repression activity and biological function, whereas other conventional modifications are ineffective. Application of 6pi allows PCSK9 siRNA to efficiently lower plasma cholesterol concentration in vivo, and abolish potentially deleterious off-target phenotypes. The smallest spacer, C3, also shows the same improvement in target specificity. Abasic pivot substitution serves as a general means to harness the specificity of siRNA experiments and therapeutic applications.

  3. Analytical Model of Shear of 4-harness Satin Weave Fabrics

    NASA Astrophysics Data System (ADS)

    Liu, Lu; Chen, Julie; Sherwood, James

    2004-06-01

    Trellis shear is the main deformation mode in the thermo-stamping process of woven fabric composites. To model the shear properties of woven fabrics analytically, the equilibrium equation of the unit cell of a 4-harness satin weave glass/polypropylene woven fabric is studied. Frictional resistance moment and lateral compaction resistance moment are then predicted by studying the geometry of the unit cell. Then the model is used to predict the load versus shear angle curves in the picture frame test to reduce or eliminate the test itself. A parametric study is carried out to determine the sensitivity of the friction coefficient. To validate the model, picture-frame experimental results are presented. A very close correlation is observed between the model predictions and the experimental results. Results of plain weave fabrics are included to show the analytical model's ability to predict the effect of weave pattern. Results from an international benchmark testing are also presented to help establish the test standards for experimental characterization of the shear properties of woven fabrics in the thermo-stamping process.

  4. Weakly supervised visual dictionary learning by harnessing image attributes.

    PubMed

    Gao, Yue; Ji, Rongrong; Liu, Wei; Dai, Qionghai; Hua, Gang

    2014-12-01

    Bag-of-features (BoFs) representation has been extensively applied to deal with various computer vision applications. To extract discriminative and descriptive BoF, one important step is to learn a good dictionary to minimize the quantization loss between local features and codewords. While most existing visual dictionary learning approaches are engaged with unsupervised feature quantization, the latest trend has turned to supervised learning by harnessing the semantic labels of images or regions. However, such labels are typically too expensive to acquire, which restricts the scalability of supervised dictionary learning approaches. In this paper, we propose to leverage image attributes to weakly supervise the dictionary learning procedure without requiring any actual labels. As a key contribution, our approach establishes a generative hidden Markov random field (HMRF), which models the quantized codewords as the observed states and the image attributes as the hidden states, respectively. Dictionary learning is then performed by supervised grouping the observed states, where the supervised information is stemmed from the hidden states of the HMRF. In such a way, the proposed dictionary learning approach incorporates the image attributes to learn a semantic-preserving BoF representation without any genuine supervision. Experiments in large-scale image retrieval and classification tasks corroborate that our approach significantly outperforms the state-of-the-art unsupervised dictionary learning approaches.

  5. Harnessing the Therapeutic Potential of Th17 Cells.

    PubMed

    Bystrom, Jonas; Taher, Taher E; Muhyaddin, M Sherwan; Clanchy, Felix I; Mangat, Pamela; Jawad, Ali S; Williams, Richard O; Mageed, Rizgar A

    2015-01-01

    Th17 cells provide protective immunity to infections by fungi and extracellular bacteria as well as cancer but are also involved in chronic inflammation. The cells were first identified by their ability to produce interleukin 17A (IL-17A) and, subsequently, associated with chronic inflammation and autoimmunity. Th17 cells have some gene profile similarity with stem cells and can remain dormant in mucosal tissues for long periods. Indeed, recent studies suggest that functionally distinct subsets of pro- and anti-inflammatory Th17 cells can interchange phenotype and functions. For development, Th17 cells require activation of the transcription factors STAT3 and RORγt while RUNX1, c-Maf, and Aiolos are involved in changes of phenotype/functions. Attempts to harness Th17 cells against pathogens and cancer using vaccination strategies are being explored. The cells gain protective abilities when induced to produce interferon γ (IFNγ). In addition, treatment with antibodies to IL-17 is effective in treating patients with psoriasis, psoriatic arthritis, and refectory rheumatoid arthritis. Moreover, since RORγt is a nuclear receptor, it is likely to be a potential future drug target for modulating Th17 functions. This review explores pathways through which Th17 subsets are induced, the molecular basis of their plasticity, and potential therapeutic strategies for their modulation in diseases.

  6. Abasic pivot substitution harnesses target specificity of RNA interference

    PubMed Central

    Lee, Hye-Sook; Seok, Heeyoung; Lee, Dong Ha; Ham, Juyoung; Lee, Wooje; Youm, Emilia Moonkyung; Yoo, Jin Seon; Lee, Yong-Seung; Jang, Eun-Sook; Chi, Sung Wook

    2015-01-01

    Gene silencing via RNA interference inadvertently represses hundreds of off-target transcripts. Because small interfering RNAs (siRNAs) can function as microRNAs, avoiding miRNA-like off-target repression is a major challenge. Functional miRNA–target interactions are known to pre-require transitional nucleation, base pairs from position 2 to the pivot (position 6). Here, by substituting nucleotide in pivot with abasic spacers, which prevent base pairing and alleviate steric hindrance, we eliminate miRNA-like off-target repression while preserving on-target activity at ∼80–100%. Specifically, miR-124 containing dSpacer pivot substitution (6pi) loses seed-mediated transcriptome-wide target interactions, repression activity and biological function, whereas other conventional modifications are ineffective. Application of 6pi allows PCSK9 siRNA to efficiently lower plasma cholesterol concentration in vivo, and abolish potentially deleterious off-target phenotypes. The smallest spacer, C3, also shows the same improvement in target specificity. Abasic pivot substitution serves as a general means to harness the specificity of siRNA experiments and therapeutic applications. PMID:26679372

  7. The globalization of health research: harnessing the scientific diaspora.

    PubMed

    Anand, Nalini P; Hofman, Karen J; Glass, Roger I

    2009-04-01

    The scientific diaspora is a unique resource for U.S. universities. By drawing on the expertise, experience, and catalytic potential of diaspora scientists, universities can capitalize more fully on their diverse intellectual resources to make lasting contributions to global health. This article examines the unique contributions of the diaspora in international research collaborations, advantages of harnessing the diaspora and benefits to U.S. universities of fostering these collaborations, challenges faced by scientists who want to work with their home countries, examples of scientists engaging with their home countries, and specific strategies U.S. universities and donors can implement to catalyze these collaborations. The contributions of the diaspora to the United States are immense: International students enrolled in academic year 2007-2008 contributed an estimated $15 billion to the U.S. economy. As scientific research becomes increasingly global, the percentage of scientific publications with authors from foreign countries has grown from 8% in 1988 to 20% in 2005. Diaspora scientists can help build trusting relationships with scientists abroad, and international collaborations may improve the health of underserved populations at home. Although opportunities for diaspora networks are increasing, most home countries often lack enabling policies, infrastructure, and resources to effectively utilize their diaspora communities abroad. This article examines how some governments have successfully mobilized their scientific diaspora to become increasingly engaged in their national research agendas. Recommendations include specific strategies, including those that encourage U.S. universities to promote mini-sabbaticals and provide seed funding and flexible time frames.

  8. Harnessing click detectors for the genuine characterization of light states

    PubMed Central

    Heilmann, René; Sperling, Jan; Perez-Leija, Armando; Gräfe, Markus; Heinrich, Matthias; Nolte, Stefan; Vogel, Werner; Szameit, Alexander

    2016-01-01

    The key requirement for harnessing the quantum properties of light is the capability to detect and count individual photons. Of particular interest are photon-number-resolving detectors, which allow one to determine whether a state of light is classical or genuinely quantum. Existing schemes for addressing this challenge rely on a proportional conversion of photons to electrons. As such, they are capable of correctly characterizing small photon fluxes, yet are limited by uncertainties in the conversion rate. In this work, we employ a divide-and-conquer approach to infallibly discerning non-classicality of states of light. This is achieved by transforming the incident fields into uniform spatial distributions that readily lend themselves for characterization by standard on-off detectors. Since the exact statistics of the light stream in multiplexed on-off detectors are click statistics, our technique is freely scalable to accommodate–in principle–arbitrarily large photon fluxes. Our experiments pave the way towards genuine integrated photon-number-resolving detection for advanced on-chip photonic quantum networks. PMID:26771053

  9. Harnessing high-dimensional hyperentanglement through a biphoton frequency comb

    NASA Astrophysics Data System (ADS)

    Xie, Zhenda; Zhong, Tian; Shrestha, Sajan; Xu, Xinan; Liang, Junlin; Gong, Yan-Xiao; Bienfang, Joshua C.; Restelli, Alessandro; Shapiro, Jeffrey H.; Wong, Franco N. C.; Wei Wong, Chee

    2015-08-01

    Quantum entanglement is a fundamental resource for secure information processing and communications, and hyperentanglement or high-dimensional entanglement has been separately proposed for its high data capacity and error resilience. The continuous-variable nature of the energy-time entanglement makes it an ideal candidate for efficient high-dimensional coding with minimal limitations. Here, we demonstrate the first simultaneous high-dimensional hyperentanglement using a biphoton frequency comb to harness the full potential in both the energy and time domain. Long-postulated Hong-Ou-Mandel quantum revival is exhibited, with up to 19 time-bins and 96.5% visibilities. We further witness the high-dimensional energy-time entanglement through Franson revivals, observed periodically at integer time-bins, with 97.8% visibility. This qudit state is observed to simultaneously violate the generalized Bell inequality by up to 10.95 standard deviations while observing recurrent Clauser-Horne-Shimony-Holt S-parameters up to 2.76. Our biphoton frequency comb provides a platform for photon-efficient quantum communications towards the ultimate channel capacity through energy-time-polarization high-dimensional encoding.

  10. Impact of Harness Attachment Point on Kinetics and Kinematics During Sled Towing.

    PubMed

    Bentley, Ian; Atkins, Steve J; Edmundson, Christopher J; Metcalfe, John; Sinclair, Jonathan K

    2016-03-01

    Resisted sprint training is performed in a horizontal direction and involves similar muscles, velocities, and ranges of motion (ROM) to those of normal sprinting. Generally, sleds are attached to the athletes through a lead (3 m) and harness; the most common attachment points are the shoulder or waist. At present, it is not known how the different harness point's impact on the kinematics and kinetics associated with sled towing (ST). The aim of the current investigation was to examine the kinetics and kinematics of shoulder and waist harness attachment points in relation to the acceleration phase of ST. Fourteen trained men completed normal and ST trials, loaded at 10% reduction of sprint velocity. Sagittal plane kinematics from the trunk, hip, knee, and ankle were measured, together with stance phase kinetics (third footstrike). Kinetic and kinematic parameters were compared between harness attachments using one-way repeated-measures analysis of variance. The results indicated that various kinetic differences were present between the normal and ST conditions. Significantly greater net horizontal mean force, net horizontal impulses, propulsive mean force, and propulsive impulses were measured (p < 0.05). Interestingly, the waist harness also led to greater net horizontal impulse when compared with the shoulder attachment (p < 0.001). In kinematic terms, ST conditions significantly increased peak flexion in hip, knee, and ankle joints compared with the normal trials (p < 0.05). Results highlighted that the shoulder harness had a greater impact on trunk and knee joint kinematics when compared with the waist harness (p < 0.05). In summary, waist harnesses seem to be the most suitable attachment point for the acceleration phase of sprinting. Sled towing with these attachments resulted in fewer kinematic alterations and greater net horizontal impulse when compared with the shoulder harness. Future research is necessary in order to explore the long-term adaptations of

  11. Harnessing optical loss for unique microlaser functionality (Conference Presentation)

    NASA Astrophysics Data System (ADS)

    Feng, Liang

    2017-05-01

    Lasers, as the key driving force in the field of optics and photonics over other photonic components, are now being significantly benefited from the studies of nanophotonics and metamaterials, broadening laser physics and device applications. The properties of light are much more beyond its simple intensity and temporal characteristics. The fruitful nature of light provides a great variety of freedoms in manipulating light for modern photonic applications, including spin (polarization), chirality, angular momentum, and spin-orbit coupling. Unfortunately, all these fundamental properties and functionalities of light have not been fully exploited in micro/nano-laser systems because the conventional principles of laser design in bulk optics cannot be easily scaled down to the micro/nano scale. The capability of creating microlasers with controlled spin/orbital information and chirality in their radiations is expected to revolutionize next generation of photonic systems for computing and communication. In this talk, I will focus on our recent effort in harnessing optical losses for unique microlaser functionalities, in particular, an orbital angular momentum (OAM) microlaser that structure and twist the lasing radiation at the microscale. The effective generation of OAM lasing, especially at a micro/nano-scale, could address the growing demand for information capacity. By exploiting the emerging non-Hermitian photonics design at an exceptional point, we demonstrate a microring laser producing a single-mode OAM vortex lasing with the ability to precisely define the topological charge of the OAM mode and its polarization state. Our OAM microlaser could find applications in the next generation of integrated optoelectronic devices for optical communications.

  12. Harnessing wound healing and regeneration for tissue engineering.

    PubMed

    Metcalfe, A D; Ferguson, M W J

    2005-04-01

    Biomedical science has made major advances in understanding how cells grow into functioning tissue and the signalling mechanisms used to achieve this are slowly being dissected. Tissue engineering is the application of that knowledge to the building or repairing of organs, including skin, the largest organ in the body. Generally, engineered tissue is a combination of living cells and a supporting matrix. Besides serving as burn coverings, engineered skin substitutes can help patients with diabetic foot ulcers. Today, most of these ulcers are treated with an approach that includes antibiotics, glucose control, special shoes and frequent cleaning and bandaging. The results of such treatments are often disappointing and ineffectual, and scarring remains a major problem, mechanically, cosmetically and psychologically. Within our group we are attempting to address this by investigating novel approaches to skin tissue engineering. We are identifying novel therapeutic manipulations to improve the degree of integration between a tissue engineered dermal construct and the host by both molecular manipulation of growth factors but also by understanding and harnessing mechanisms of regenerative biology. For the purpose of this summary, we will concentrate primarily on the latter of these two approaches in that we have identified a novel mouse mutant that completely and perfectly regenerates skin and cartilaginous components following ear injury. This experimental animal will allow us to characterize not only novel genes involved in the regeneration process but also to utilize cells from such animals in artificial skin equivalents to assess their behaviour compared with normal cells. This approach should allow us to create a tissue-engineered substitute, which more closely resembles the normal regional microanatomy and physiology of the skin, allowing better integration to the host with minimal or no scarring.

  13. Harnessing DNA-induced immune responses for improving cancer vaccines

    PubMed Central

    Herrada, Andrés A.; Rojas-Colonelli, Nicole; González-Figueroa, Paula; Roco, Jonathan; Oyarce, César; Ligtenberg, Maarten A.; Lladser, Alvaro

    2012-01-01

    DNA vaccines have emerged as an attractive strategy to promote protective cellular and humoral immunity against the encoded antigen. DNA vaccines are easy to generate, inexpensive to produce and purify at large-scale, highly stable and safe. In addition, plasmids used for DNA vaccines act as powerful “danger signals” by stimulating several DNA-sensing innate immune receptors that promote the induction of protective adaptive immunity. The induction of tumor-specific immune responses represents a major challenge for DNA vaccines because most of tumor-associated antigens are normal non-mutated self-antigens. As a consequence, induction of potentially self-reactive T cell responses against such poorly immunogenic antigens is controlled by mechanisms of central and peripheral tolerance as well as tumor-induced immunosuppression. Although several DNA vaccines against cancer have reached clinical testing, disappointing results have been observed. Therefore, the development of new adjuvants that strongly stimulate the induction of antitumor T cell immunity and counteract immune-suppressive regulation is an attractive approach to enhance the potency of DNA vaccines and overcome tumor-associated tolerance. Understanding the DNA-sensing signaling pathways of innate immunity that mediate the induction of T cell responses elicited by DNA vaccines represents a unique opportunity to develop novel adjuvants that enhance vaccine potency. The advance of DNA adjuvants needs to be complemented with the development of potent delivery systems, in order to step toward successful clinical application. Here, we briefly discuss recent evidence showing how to harness DNA-induced immune response to improve the potency of cancer vaccines and counteract tumor-associated tolerance. PMID:23111166

  14. Cancer vaccines: harnessing the potential of anti-tumor immunity.

    PubMed

    Suckow, Mark A

    2013-10-01

    Although the presence of cancer suggests failure of the immune system to protect against development of tumors, the possibility that immunity can be redirected and focused to generate an anti-tumor response offers great translational possibility. The key to this is identifying antigens likely to be present in any given tumor and functionally critical to tumor survival and growth. Such tumor-associated antigens (TAAs) are varied and optimally should be absent from normal tissue. Of particular interest are TAAs associated with the tumor stroma, as immunity directed against the stroma may restrict the ability of the tumor to grow and metastasize. Important to directing the immune system toward an effect anti-tumor response is the understanding of how TAAs are processed and how the tumor is able to evade immune elimination. The process of immunoediting happens in response to the selective pressure that the immune system places upon tumor cell populations and allows for emergence of tumor cells capable of escaping immune destruction. Efforts to harness the immune system for clinical application has been aided by vaccines based on purified recombinant protein or nucleic acid TAAs. For example, a vaccine for canine melanoma has been developed and approved based on immunization with DNA components of tyrosinase, a glycoprotein essential to melanin synthesis. The performance of cancer vaccines has been aided in some cases when supplemented with immunostimulatory molecules such as interleukin 2 or a novel extracellular matrix vaccine adjuvant. Vaccines with the broadest menu of antigenic targets may be those most likely to succeed against cancer. For this reason, tissue vaccines produced from harvested tumor material may offer significant benefit. With several cancer vaccines on the veterinary and human markets, efforts to understand basic tumor immunology are soon to yield great dividends.

  15. Innovation in the Harnessing and Transfer of Technology: The Gran Mariscal de Ayacucho Foundation

    ERIC Educational Resources Information Center

    Lerner de Almea, Ruth

    1977-01-01

    Discusses the background, organization, success, problems, and functions of the Gran Mariscal de Ayacucho Foundation, Caracas, Venezuela, for producing human resources for the harnessing of scientific technology. The fellowship program supports study by students both at home and abroad. (SL)

  16. Innovation in the Harnessing and Transfer of Technology: The Gran Mariscal de Ayacucho Foundation

    ERIC Educational Resources Information Center

    Lerner de Almea, Ruth

    1977-01-01

    Discusses the background, organization, success, problems, and functions of the Gran Mariscal de Ayacucho Foundation, Caracas, Venezuela, for producing human resources for the harnessing of scientific technology. The fellowship program supports study by students both at home and abroad. (SL)

  17. STS-39 MS Hieb is suspended over JSC's WETF Bldg 29 pool via harness

    NASA Technical Reports Server (NTRS)

    1990-01-01

    STS-39 Mission Specialist (MS) Richard J. Hieb, wearing launch and entry suit (LES) and launch and entry helmet (LEH), is hoisted above JSC's Weightless Environment Training Facility (WETF) Bldg 29 pool via his parachute harness. Hieb will be dropped from the harness into the WETF's 25 ft deep pool to simulate an emergency egress bailout from the Space Shuttle into the ocean. Divers in the pool will ensure Hieb's safety during the exercise.

  18. STS-39 MS Bluford is suspended over JSC's WETF Bldg 29 pool via harness

    NASA Image and Video Library

    1990-12-07

    S90-54755 (13 Dec 1990) --- Astronaut Guion S. Bluford, Jr., STS-39 Mission Specialist wearing launch and entry suit (LES) and launch and entry helmet (LEH), is suspended above JSC's Weightless Environment Training Facility (WETF) Bldg 29 pool via his parachute harness. Bluford will be dropped from the harness into the WETF's 25 ft deep pool to simulate an emergency egress bailout from the Space Shuttle into the ocean.

  19. Monocatenary, branched, double-headed, and bolaform surface active carbohydrate esters via photochemical thiol-ene/-yne reactions.

    PubMed

    Boyère, Cédric; Broze, Guy; Blecker, Christophe; Jérôme, Christine; Debuigne, Antoine

    2013-10-18

    An original and versatile method for the synthesis of a range of novel mannose-based surfactants was developed via metal-free photo-induced thiol-ene/-yne 'click' reactions. This light-mediated hydrothiolation reaction involving a thiolated mannose was successfully applied to terminal and internal alkenes, dienes, and alkynes, leading to monocatenary, branched, double-headed, and bolaform amphiphilic carbohydrate esters, respectively. A surface activity study showed that these new compounds possess valuable properties and display specific behavior at the air-water interface. It also demonstrated the greater flexibility of the thioether moiety in the spacer of the surfactants produced via a thiol-ene reaction in comparison with the triazole heterocyclic rings in similar glucose-based surfactants synthesized elsewhere by the alkyne-azide 1,3-dipolar addition.

  20. Biocatalyst mediated production of 6β,11α-dihydroxy derivatives of 4-ene-3-one steroids.

    PubMed

    Kolet, Swati P; Niloferjahan, Siddiqui; Haldar, Saikat; Gonnade, Rajesh; Thulasiram, Hirekodathakallu V

    2013-11-01

    Biotransformation of steroids with 4-ene-3-one functionality such as progesterone (I), testosterone (II), 17α-methyltestosterone (III), 4-androstene-3,17-dione (IV) and 19-nortestosterone (V) were studied by using a fungal system belonging to the genera of Mucor (M881). The fungal system efficiently and quantitatively converted these steroids in regio- and stereo-selective manner into corresponding 6β,11α-dihydroxy compounds. Time course experiments suggested that the transformation was initiated by hydroxylation at 6β- or 11α-(10β-hydroxy in case of V) to form monohydroxy derivatives which upon prolonged incubation were converted into corresponding 6β,11α-dihydroxy derivatives. The fermentation studies carried out using 5L table-top fermentor with substrates (I and II) clearly indicates that 6β,11α-dihydroxy derivatives of steroids with 4-ene-3-one functionality can be produced in large scale by using M881.

  1. Facile thiol-ene thermal crosslinking reaction facilitated hole-transporting layer for highly efficient and stable perovskite solar cells

    DOE PAGES

    Li, Zhong'an; Zhu, Zonglong; Chueh, Chu -Chen; ...

    2016-08-08

    A crosslinked organic hole-transporting layer (HTL) is developed to realize highly efficient and stable perovskite solar cells via a facile thiol-ene thermal reaction. This crosslinked HTL not only facilitates hole extraction from perovskites, but also functions as an effective protective barrier. Lastly, a high-performance (power conversion efficiency: 18.3%) device is demonstrated to show respectable photo and thermal stability without encapsulation.

  2. Catalytic hetero-ene reactions of 5-methyleneoxazolines: highly enantioselective synthesis of 2,5-disubstituted oxazole derivatives.

    PubMed

    Luo, Weiwei; Zhao, Jiannan; Yin, Chengkai; Liu, Xiaohua; Lin, Lili; Feng, Xiaoming

    2014-07-18

    An efficient catalytic asymmetric hetero-ene reaction of 5-methyleneoxazolines with 1,2-dicarbonyl compounds (including α-ketoesters and glyoxal derivatives) was realized using Ni(II)-N,N'-dioxide complexes as the catalysts. It provides a rapid, high yielding (up to 99%) route for the preparation of 2,5-disubstituted oxazole derivatives in a highly enantioenriched form (up to >99% ee) under mild conditions.

  3. 3,3'-Di-n-propyl-1,1'-[p-phenyl-enebis(methyl-ene)]diimidazolium dibromide.

    PubMed

    Haque, Rosenani A; Nasri, S Fatimah; Hemamalini, Madhukar; Fun, Hoong-Kun

    2011-08-01

    The asymmetric unit of the title compound, C(20)H(28)N(4) (2+)·2Br(-), consists of half a 3,3'-di-n-propyl-1,1'-[p-phenyl-enenis(methyl-ene)]diimidazolium cation and a bromide anion. The cation is located on an inversion center and adopts an ⋯AAA⋯ trans conformation. In the crystal, the cation is linked to the anions via weak C-H⋯Br hydrogen bonds.

  4. Oxa-ene reaction of enols of amides with 4-phenyl-1,2,4-triazoline-3,5-dione.

    PubMed

    Basheer, Ahmad; Rappoport, Zvi

    2008-01-04

    The reaction of 16 enols of amides with 4-phenyl-1,2,4-triazoline-1,3-dione gave open chain adducts rather than the [2 + 2] cycloadducts with a hemiaminal moiety, both in solid state and in solution. This assignment is based on X-ray crystallography, (1)H and (13)C NMR data, and IR spectra. The suggested mechanism involves hydroxyl proton loss in a formal oxa-ene reaction. Mechanistic details and a possible alternative are discussed.

  5. Facile thiol-ene thermal crosslinking reaction facilitated hole-transporting layer for highly efficient and stable perovskite solar cells

    SciTech Connect

    Li, Zhong'an; Zhu, Zonglong; Chueh, Chu -Chen; Luo, Jingdong; Jen, Alex K. -Y.

    2016-08-08

    A crosslinked organic hole-transporting layer (HTL) is developed to realize highly efficient and stable perovskite solar cells via a facile thiol-ene thermal reaction. This crosslinked HTL not only facilitates hole extraction from perovskites, but also functions as an effective protective barrier. Lastly, a high-performance (power conversion efficiency: 18.3%) device is demonstrated to show respectable photo and thermal stability without encapsulation.

  6. Highly regio- and stereocontrolled formation of functionalized tricyclo[4.2.1.0(2,8)]non-3-enes.

    PubMed

    Toselli, Nicolas; Martin, David; Achard, Mathieu; Tenaglia, Alphonse; Buono, Gérard

    2009-05-15

    The electrophilic activations of bicyclo[4.2.1]nonatrienes by 4-isopropyl-1,2,4-triazolinedione, N-iodosuccinimide, or an epoxidation/acidic ring-opening sequence is reported. The subsequent in situ trappings by water, alcohols, or benzoic acids led to original tricyclo[4.2.1.0(2,8)]non-3-enes with high regio- and stereoselectivities. The synthetic potentiality of these synthons is illustrated by the straightforward access to a fused cyclopropane featuring six consecutive controlled stereocenters.

  7. Asymmetric Electrophilic α-Amination of Silyl Enol Ether Derivatives via the Nitrosocarbonyl Hetero-ene Reaction.

    PubMed

    Sandoval, David; Samoshin, Andrey V; Read de Alaniz, Javier

    2015-09-18

    The first example of a general asymmetric nitrosocarbonyl hetero-ene reaction is described. The procedure uses a copper-catalyzed aerobic oxidation of a commercially available chiral nitrosocarbonyl precursor (EleNOr) and is operationally simple. The transformation is both high yielding and highly diastereoselective for a range of silyl enol ether derivatives. A variety of synthetically useful postfunctionalization reactions are presented along with a mechanistic rationale that can be used as a predictive model for future asymmetric reactions with nitrosocarbonyl intermediates.

  8. Hello, world: Harnessing social media for the Rosetta mission

    NASA Astrophysics Data System (ADS)

    Baldwin, Emily; Mignone, Claudia; O'Flaherty, Karen; Homfeld, Anne-Mareike; Bauer, Markus; McCaughrean, Mark

    2015-04-01

    The European Space Agency's (ESA) comet-chasing Rosetta mission was launched in 2004, before social media became a popular tool for mainstream communication. By harnessing a range of platforms for communicating the key messages of this unprecedented mission as it reached its destination ten years later, new audiences were reached and a global impact was achieved. Rosetta-specific social media accounts - @ESA_Rosetta on Twitter, the Rosetta Mission Facebook page and the rosettamission Instagram account - were developed during 2013/14 and used alongside the traditional reporting line of the main ESA website and the Rosetta blog to build awareness about the mission. Coordinated with ESA's existing social media channels (Flickr, YouTube, G+, Twitter, Facebook and Livestream) and with the support of ESA's country desks and Rosetta partner agency accounts (including @philae2014), information could be shared in a number of European languages, ensuring a wide reach across Europe - and the world. We discuss the roles of the various social media accounts in supporting and promoting the competitions and social media campaigns that were built around the key mission milestones of 2014: waking up from deep space hibernation (January), arriving at Comet 67P/Churyumov-Gerasimenko (August) and naming the landing site for Philae ahead of the landing event in November. We discuss the different approach to each channel, such as the first person twitter accounts, the dialogue with and between blog users, and the discussions held live via G+ Hangouts with leading scientists and spacecraft operators. We compare and contrast the audiences, the interaction we had with them and how challenges were overcome. We also use the science-fiction-meets-science-fact Ambition short movie, and its "undercover" dissemination on social media, as an example of how the profile of the Rosetta mission was raised in a unique way. By using a variety of social media platforms to target different audiences with

  9. Epithelial-to-Mesenchymal Plasticity Harnesses Endocytic Circuitries.

    PubMed

    Corallino, Salvatore; Malabarba, Maria Grazia; Zobel, Martina; Di Fiore, Pier Paolo; Scita, Giorgio

    2015-01-01

    execution of different biological processes, with a primary role in the control of polarized functions. Thus, they may be relevant for controlling EMT or certain aspects of it. Here, by discussing a few paradigmatic cases, we will outline how endocytosis may be harnessed by the EMT process to promote dynamic changes in cellular identity, and to increase cellular flexibility and adaptation to micro-environmental cues, ultimately impacting on physiological and pathological processes, first and foremost cancer progression.

  10. ENED-GEM: A Conceptual Framework Model for Psychological Enjoyment Factors and Learning Mechanisms in Educational Games about the Environment

    PubMed Central

    Fjællingsdal, Kristoffer S.; Klöckner, Christian A.

    2017-01-01

    Based on a thorough review of psychological literature, this article seeks to develop a model of game enjoyment and environmental learning (ENvironmental EDucational Game Enjoyment Model, ENED-GEM) and delineate psychological processes that might facilitate learning and inspire behavioral change from educational games about the environment. A critically acclaimed digital educational game about environmental issues (Fate of the World by Red Redemption/Soothsayer Games) was used as a case study. Two hundred forty-nine reviews of the game from the popular gaming and reviewing platform known as Steam were analyzed by means of a thematic content analysis in order to identify key player enjoyment factors believed to be relevant to the process of learning from games, as well as to gain an understanding of positive and negative impressions about the game’s general content. The end results of the thematic analysis were measured up to the suggested ENED-GEM framework. Initial results generally support the main elements of the ENED-GEM, and future research into the importance of these individual core factors is outlined. PMID:28701988

  11. Enhanced mechanical properties of photo-clickable thiol-ene PEG hydrogels through repeated photopolymerization of in-swollen macromer.

    PubMed

    Fiedler, C I; Aisenbrey, E A; Wahlquist, J A; Heveran, C M; Ferguson, V L; Bryant, S J; McLeod, R R

    2016-11-09

    Current hydrogels used for tissue engineering are limited to a single range of mechanical properties within the replicated tissue construct. We show that repeated in-swelling by a single hydrogel pre-cursor solution into an existing polymerized hydrogel followed by photo-exposure increases hydrogel mechanical properties. The process is demonstrated with a photo-clickable thiol-ene hydrogel using a biocompatible precursor solution of poly(ethylene glycol) dithiol and 8-arm poly(ethylene glycol) functionalized with norbornene. The polymer fraction in the precursor solution was varied by 5, 10, and 20 percent by weight and an off-stoichiometric ratio of thiol : ene was used, leaving free enes available for subsequent reaction. Multiple swelling and exposure cycles for the same precursor solution were performed. The compressive modulus increased by a factor between three and ten (formulation dependent), while volume swelling ratio decreased by a factor of two, consistent with increased crosslink density. The modified hydrogels also demonstrate increased toughness by fracturing at compressive forces five times greater than the initial hydrogel. We attribute the increased toughness to subsequent increases in crosslink density created by the repeated photopolymerization of in-swollen macromer. This technique demonstrates the ability to significantly modify hydrogel network properties by exploiting swelling and polymerization processes that can be applied to traditional three-dimensional printing systems to spatially control local mechanical properties.

  12. ENED-GEM: A Conceptual Framework Model for Psychological Enjoyment Factors and Learning Mechanisms in Educational Games about the Environment.

    PubMed

    Fjællingsdal, Kristoffer S; Klöckner, Christian A

    2017-01-01

    Based on a thorough review of psychological literature, this article seeks to develop a model of game enjoyment and environmental learning (ENvironmental EDucational Game Enjoyment Model, ENED-GEM) and delineate psychological processes that might facilitate learning and inspire behavioral change from educational games about the environment. A critically acclaimed digital educational game about environmental issues (Fate of the World by Red Redemption/Soothsayer Games) was used as a case study. Two hundred forty-nine reviews of the game from the popular gaming and reviewing platform known as Steam were analyzed by means of a thematic content analysis in order to identify key player enjoyment factors believed to be relevant to the process of learning from games, as well as to gain an understanding of positive and negative impressions about the game's general content. The end results of the thematic analysis were measured up to the suggested ENED-GEM framework. Initial results generally support the main elements of the ENED-GEM, and future research into the importance of these individual core factors is outlined.

  13. Aptamer-based organic-silica hybrid affinity monolith prepared via "thiol-ene" click reaction for extraction of thrombin.

    PubMed

    Wang, Zheng; Zhao, Jin-cheng; Lian, Hong-zhen; Chen, Hong-yuan

    2015-06-01

    A novel strategy for preparing aptamer-based organic-silica hybrid monolithic column was developed via "thiol-ene" click chemistry. Due to the large specific surface area of the hybrid matrix and the simplicity, rapidness and high efficiency of "thiol-ene" click reaction, the average coverage density of aptamer on the organic-silica hybrid monolith reached 420 pmol μL(-1). Human α-thrombin can be captured on the prepared affinity monolithic column with high specificity and eluted by NaClO4 solution. N-p-tosyl-Gly-Pro-Arg p-nitroanilide acetate was used as the sensitive chromogenic substrate of thrombin. The thrombin enriched by this affinity column was detected with a detection of limit of 0.01 μM by spectrophotometry. Furthermore, the extraction recovery of thrombin at 0.15 μM in human serum was 91.8% with a relative standard deviation of 4.0%. These results indicated that "thiol-ene" click chemistry provided a promising technique to immobilize aptamer on organic-inorganic hybrid monolith and the easily-assembled affinity monolithic material could be used to realize highly selective recognition of trace proteins.

  14. Skill Acquisition and Retention Following Simulation-Based Training in Pavlik Harness Application

    PubMed Central

    Moktar, Joel; Bradley, Catharine S.; Maxwell, Alexandra; Wedge, John H.; Kelley, Simon P.; Murnaghan, M. Lucas

    2016-01-01

    Background: Simulation-based learning is increasingly prevalent in many surgical training programs, as medical education moves toward competency-based curricula. In orthopaedic surgery, developmental dysplasia of the hip is a commonly treated condition, where the standard of care for patients less than six months of age is an orthotic device such as the Pavlik harness. However, despite widespread use of the Pavlik harness and the potential complications that may arise from inappropriate application, we know of no previously described formal training curriculum for Pavlik harness application. Methods: We developed a video and model-based simulation learning module for Pavlik harness application. Two novice groups (residents and allied health professionals) were exposed to the module and, at pre-intervention, post-intervention, and retention testing, were evaluated on their ability to apply a Pavlik harness to the model. Evaluations were completed using a previously validated Objective Structured Assessment of Technical Skills (OSATS) and a global rating scale (GRS) specific to Pavlik harness application. A control group that did not undergo the module was also evaluated at two time points to determine if exposure to the Pavlik harness alone would affect skill acquisition. All groups were compared with a group of clinical experts, whose scores were used as a competency benchmark. Statistical analysis of skill acquisition and retention was conducted using t tests and analysis of variance (ANOVA). Results: Exposure to the learning module improved resident and allied health professionals’ competency in applying a Pavlik harness (p < 0.05) to the level of the expert clinicians, and this level of competency was retained one month after exposure to the module. Control subjects who were not exposed to the module did not improve, nor did they achieve competency. Conclusions: The simulation-based learning module was shown to be an effective tool for teaching the application

  15. Photogenerated Lectin Sensors Produced by Thiol-Ene/Yne Photo-Click Chemistry in Aqueous Solution

    PubMed Central

    Norberg, Oscar; Lee, Irene H.; Aastrup, Teodor; Yan, Mingdi; Ramström, Olof

    2012-01-01

    The photoinitiated radical reactions between thiols and alkenes/alkynes (thiol-ene and thiol-yne chemistry) have been applied to a functionalization methodology to produce carbohydrate-presenting surfaces for analyses of biomolecular interactions. Polymer-coated quartz surfaces were functionalized with alkenes or alkynes in a straightforward photochemical procedure utilizing perfluorophenylazide (PFPA) chemistry. The alkene/alkyne surfaces were subsequently allowed to react with carbohydrate thiols in water under UV-irradiation. The reaction can be carried out in a drop of water directly on the surface without photoinitiator and any disulfide side products were easily washed away after the functionalization process. The resulting carbohydrate-presenting surfaces were evaluated in real-time studies of protein-carbohydrate interactions using a quartz crystal microbalance flow-through system with recurring injections of selected lectins with intermediate regeneration steps using low pH buffer. The resulting methodology proved fast, efficient and scalable to high-throughput analysis formats, and the produced surfaces showed significant protein binding with expected selectivities of the lectins used in the study. PMID:22341757

  16. Preparation and properties of cyclic acetal based biodegradable gel by thiol-ene photopolymerization.

    PubMed

    Wang, Kemin; Lu, Jian; Yin, Ruixue; Chen, Lu; Du, Shuang; Jiang, Yan; Yu, Qiang

    2013-04-01

    Synthetic, hydrolytically degradable biomaterials have been widely developed for biomedical use; however, most of them will form acidic products upon degradation of polymer backbone. In order to address this concern, we proposed to fabricate a biodegradable gel based on the crosslinking of a cyclic acetal monomer with reactable diallyl group and multifunctional thiols by thiol-ene photopolymerization. This gel produces diols and carbonyl end groups upon hydrolytic degradation and could be entirely devoid of acidic by-products. Real time infrared spectroscopy was employed to investigate the effect of different light intensities and concentrations of photoinitiator on the polymerization kinetics. With the increase of the concentration of photoinitiator and light intensity, both the rate of polymerization and final double bond conversion increased. Degradation of cyclic acetal based networks was investigated in PBS medium so as to simulate physiological conditions. The remaining mass of the materials after 25 days incubation was 84%. TGA analysis showed that the gels exhibited a typical weight loss (97.2%) at around 378 °C. In vitro cytotoxicity showed that the cyclic acetal based gels had non-toxicity to cell L-929 and had good biocompatibility.

  17. Superhydrophobic and Slippery Lubricant-Infused Flexible Transparent Nanocellulose Films by Photoinduced Thiol-Ene Functionalization.

    PubMed

    Guo, Jiaqi; Fang, Wenwen; Welle, Alexander; Feng, Wenqian; Filpponen, Ilari; Rojas, Orlando J; Levkin, Pavel A

    2016-12-14

    Films comprising nanofibrillated cellulose (NFC) are suitable substrates for flexible devices in analytical, sensor, diagnostic, and display technologies. However, some major challenges in such developments include their high moisture sensitivity and the complexity of current methods available for functionalization and patterning. In this work, we present a facile process for tailoring the surface wettability and functionality of NFC films by a fast and versatile approach. First, the NFC films were coated with a layer of reactive nanoporous silicone nanofilament by polycondensation of trichlorovinylsilane (TCVS). The TCVS afforded reactive vinyl groups, thereby enabling simple UV-induced functionalization of NFC films with various thiol-containing molecules via the photo "click" thiol-ene reaction. Modification with perfluoroalkyl thiols resulted in robust superhydrophobic surfaces, which could then be further transformed into transparent slippery lubricant-infused NFC films that displayed repellency against both aqueous and organic liquids with surface tensions as low as 18 mN·m(-1). Finally, transparent and flexible NFC films incorporated hydrophilic micropatterns by modification with OH, NH2, or COOH surface groups, enabling space-resolved superhydrophobic-hydrophilic domains. Flexibility, transparency, patternability, and perfect superhydrophobicity of the produced nanocellulose substrates warrants their application in biosensing, display protection, and biomedical and diagnostics devices.

  18. An ene reductase from Clavispora lusitaniae for asymmetric reduction of activated alkenes.

    PubMed

    Ni, Yan; Yu, Hui-Lei; Lin, Guo-Qiang; Xu, Jian-He

    2014-03-05

    A putative ene reductase gene from Clavispora lusitaniae was heterologously overexpressed in Escherichia coli, and the encoded protein (ClER) was purified and characterized for its biocatalytic properties. This NADPH-dependent flavoprotein was identified with reduction activities toward a diverse range of activated alkenes including conjugated enones, enals, maleimide derivative and α,β-unsaturated carboxylic esters. The purified ClER exhibited a relatively high activity of 7.3 U mg(prot)⁻¹ for ketoisophorone while a remarkable catalytic efficiency (k(cat)/K(m)=810 s⁻¹ mM⁻¹) was obtained for 2-methyl-cinnamaldehyde due to the high affinity. A series of prochiral activated alkenes were stereoselectively reduced by ClER furnishing the corresponding saturated products in up to 99% ee. The practical applicability of ClER was further evaluated for the production of (R)-levodione, a valuable chiral compound, from ketoisophorone. Using the crude enzyme of ClER and glucose dehydrogenase (GDH), 500 mM of ketoisophorone was efficiently converted to (R)-levodione with excellent stereoselectivity (98% ee) within 1h. All these positive features demonstrate a high synthetic potential of ClER in the asymmetric reduction of activated alkenes.

  19. Biostability enhancement of oil core - polysaccharide multilayer shell via photoinitiator free thiol-ene 'click' reaction.

    PubMed

    Calcagno, Vincenzo; Vecchione, Raffaele; Sagliano, Angela; Carella, Antonio; Guarnieri, Daniela; Belli, Valentina; Raiola, Luca; Roviello, Antonio; Netti, Paolo A

    2016-06-01

    Layer-by-layer of polyelectrolytes has emerged as one of the easiest and most controlled techniques to deposit ultrathin polymer layers mainly driven by electrostatic interactions. However, this kind of interaction results to be weak and easily breakable in physiological environment. Here we report on the preparation of nanocapsules completely made of natural biomaterials: a lipophilic core (soybean oil and egg lecithin as surfactant) as nanometric template and a polysaccharide-based multilayer shell (glycol chitosan and heparin) covalently cross-linked. We first modified glycol chitosan with a thiol moiety and heparin with an alkene moiety, respectively, and then we built a polymer multilayer film with a covalent cross-linkage among layers, exploiting the light initiated thiol-ene reaction, known as click chemistry. We showed the possibility to perform the covalent cross-linkage without any photoinitiator or metal catalyst, thus avoiding cytotoxic effects and further purification steps. The so realized nanocapsules resulted to be stable and completely biocompatible and, therefore, of interest for the biotechnology fields, mainly for drug delivery. Copyright © 2016 Elsevier B.V. All rights reserved.

  20. Functionalization of hybrid monolithic columns via thiol-ene click reaction for proteomics analysis.

    PubMed

    Liu, Zhongshan; Liu, Jing; Liu, Zheyi; Wang, Hongwei; Ou, Junjie; Ye, Mingliang; Zou, Hanfa

    2017-05-19

    The vinyl-functionalized hybrid monolithic columns (75 and 150μm i.d.) were prepared via sol-gel chemistry of tetramethoxysilane (TMOS) and vinyltrimethoxysilane (VTMS). The content of accessible vinyl groups was further improved after the monolithic column was post-treated with vinyldimethylethoxysilane (VDMES). The surface properties of monolithic columns were tailored via thiol-ene click reaction by using 1-octadecanethiol, sodium 3-mercapto-1-propanesulfonate and 2,2'-(ethylenedioxy)diethanethiol/vinylphosphonic acid, respectively. The preparing octadecyl-functionalized monolithic columns were adopted for proteomics analysis in cLC-MS/MS. A 37-cm-long×75-μm-i.d. monolithic column could identify 3918 unique peptides and 1067 unique proteins in the tryptic digest of proteins from HeLa cells. When a 90-cm-long×75-μm-i.d. monolithic column was used, the numbers of unique peptides and proteins were increased by 82% and 32%, respectively. Furthermore, strong cation exchange (SCX) monolithic columns (4cm in length×150μm i.d.) were also prepared and coupled with the 37-cm-long×75-μm-i.d. octadecyl-functionalized monolithic column for two-dimensional SCX-RPLC-MS/MS analysis, which could identify 17114 unique peptides and 3211 unique proteins. Copyright © 2017 Elsevier B.V. All rights reserved.

  1. Polysiloxane-based luminescent elastomers prepared by thiol-ene "click" chemistry.

    PubMed

    Zuo, Yujing; Lu, Haifeng; Xue, Lei; Wang, Xianming; Wu, Lianfeng; Feng, Shengyu

    2014-09-26

    Side-chain vinyl poly(dimethylsiloxane) has been modified with mercaptopropionic acid, methyl 3-mercaptopropionate, and mercaptosuccinic acid. Coordinative bonding of Eu(III) to the functionalized polysiloxanes was then carried out and crosslinked silicone elastomers were prepared by thiol-ene curing reactions of these composites. All these europium complexes could be cast to form transparent, uniform, thin elastomers with good flexibility and thermal stability. The networks were characterized by FTIR, NMR, UV/Vis, and luminescence spectroscopy as well as by scanning electron microscopy, thermogravimetric analysis, and X-ray photoelectron spectroscopy. The europium elastomer luminophores exhibited intense red light at 617 nm under UV excitation at room temperature due to the (5)D0 →(7)F2 transition in Eu(III) ions. The newly synthesized luminescent materials offer many advantages, including the desired mechanical flexibility. They cannot be dissolved or fused, and so they have potential for use in optical and electronic applications. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Occurrence of dammar-13(17)-enes in sediments: Indications for a yet unrecognized microbial constituent?

    NASA Astrophysics Data System (ADS)

    Meunier-Christmann, C.; Albrecht, P.; Brassell, S. C.; Ten Haven, H. L.; Van Der Linden, B.; Rullkötter, J.; Trendel, J. M.

    1991-11-01

    A pair of isomeric dammarenes has been identified in numerous Pleistocene to Jurassic sediment samples, most of them from continental margins. Their structures have been determined to be (20 R)- and (20 S)-dammar-13(17)-ene based on comparison of mass spectra and Chromatographic data with those of synthetic standards. Their saturated counterparts have also been found in a few samples. Based on rigorous nuclear magnetic resonance (NMR) studies with one synthetic standard and molecular mechanics calculations, it is suggested that geologically occurring dammaranes possess 13β,17α(H) stereochemistry. Compounds with a dammarane skeleton are well known natural products of several families of land plants, but the widespread occurrence of dammarenes in marine sediments suggests an alternative origin, supported by their carbon isotopic signature. Dammarenes can be envisaged as direct proton-induced cyclisation products from squalene and may represent a contribution from microorganisms. Although we are in favour of this hypothesis, an origin from geologically induced rearrangements of other compounds cannot, at present, be excluded.

  3. Use of thiol-ene click chemistry to modify mechanical and thermal properties of polyhydroxyalkanoates (PHAs).

    PubMed

    Levine, Alex C; Heberlig, Graham W; Nomura, Christopher T

    2016-02-01

    In order to diversify the number of applications for poly[(R)-3-hydroxyalkanoates] (PHAs), methods must be developed to alter their physical properties so they are not limited to aliphatic polyesters. Recently we developed Escherichia coli LSBJ as a living biocatalyst with the ability to control the repeating unit composition of PHA polymers, including the ability to incorporate unsaturated repeating units into the PHA polymer at specific ratios. The incorporation of repeating units with terminal alkenes in the side chain of the polymer allowed for the production of random PHA copolymers with defined repeating unit ratios that can be chemically modified for the purpose of tailoring the physical properties of these materials beyond what are available in current PHAs. In this study, unsaturated PHA copolymers were chemically modified via thiol-ene click chemistry to contain an assortment of new functional groups, and the mechanical and thermal properties of these materials were measured. Results showed that cross-linking the copolymer resulted in a unique combination of improved strength and pliability and that the addition of polar functional groups increased the tensile strength, Young's modulus, and hydrophilic profile of the materials. This work demonstrates that unsaturated PHAs can be chemically modified to extend their physical properties to distinguish them from currently available PHA polymers. Copyright © 2015 Elsevier B.V. All rights reserved.

  4. Inspection and monitoring plan, contaminated groundwater seeps 317/319/ENE Area, Argonne National Laboratory

    SciTech Connect

    1996-10-11

    During the course of completing the Resource Conservation and Recovery Act (RCRA) Facility Investigation (RFI) in the 317/319/East-Northeast (ENE) Area of Argonne National Laboratory-East (ANL-E), groundwater was discovered moving to the surface through a series of groundwater seeps. The seeps are located in a ravine approximately 600 ft south of the ANL-E fence line in Waterfall Glen Forest Preserve. Samples of the seep water were collected and analyzed for selected parameters. Two of the five seeps sampled were found to contain detectable levels of organic contaminants. Three chemical species were identified: chloroform (14--25 {micro}g/L), carbon tetrachloride (56--340 {micro}g/L), and tetrachloroethylene (3--6 {micro}g/L). The other seeps did not contain detectable levels of volatile organics. The nature of the contaminants in the seeps will also be monitored on a regular basis. Samples of surface water flowing through the bottom of the ravine and groundwater emanating from the seeps will be collected and analyzed for chemical and radioactive constituents. The results of the routine sampling will be compared with the concentrations used in the risk assessment. If the concentrations exceed those used in the risk assessment, the risk calculations will be revised by using the higher numbers. This revised analysis will determine if additional actions are warranted.

  5. Simple thiol-ene click chemistry modification of SBA-15 silica pores with carboxylic acids.

    PubMed

    Bordoni, Andrea V; Lombardo, M Verónica; Regazzoni, Alberto E; Soler-Illia, Galo J A A; Wolosiuk, Alejandro

    2015-07-15

    A straightforward approach for anchoring tailored carboxylic groups in mesoporous SiO2 colloidal materials is presented. The thiol-ene photochemical reaction between vinyltrimethoxysilane precursors and various thiocarboxylic acids which has, click chemistry features (i.e. high conversion yields, insensitivity to oxygen, mild reaction conditions), results in carboxylated silane precursors that can be readily used as surface modifiers. The carboxylic groups of acetic, undecanoic and succinic acid were immobilized on the silica mesopore walls of SBA-15 powders employing the synthesized silane precursors. Post-grafting has been confirmed through infrared spectrometry (FTIR), energy dispersive X-ray spectroscopy (EDS), elemental analysis (EA) and zeta potential measurements. Detailed field-emission gun scanning electron microscopy (FESEM) images and small angle X-ray scattering (SAXS) data revealed parallel mesopores and ordered mesostructures. It is shown that the immobilized COOH groups are chemically accessible for acid-base reactions as well as copper adsorption. Immobilization of easily synthesized tailored carboxylic modified alkoxide precursors within mesoporous systems provides a unique chemical nanoenvironment within these ordered frameworks.

  6. Iron complexes of tetramine ligands catalyse allylic hydroxyamination via a nitroso–ene mechanism

    PubMed Central

    Porter, David; Poon, Belinda M-L

    2015-01-01

    Summary Iron(II) complexes of the tetradentate amines tris(2-pyridylmethyl)amine (TPA) and N,N′-bis(2-pyridylmethyl)-N,N′-dimethylethane-1,2-diamine (BPMEN) are established catalysts of C–O bond formation, oxidising hydrocarbon substrates via hydroxylation, epoxidation and dihydroxylation pathways. Herein we report the capacity of these catalysts to promote C–N bond formation, via allylic amination of alkenes. The combination of N-Boc-hydroxylamine with either FeTPA (1 mol %) or FeBPMEN (10 mol %) converts cyclohexene to the allylic hydroxylamine (tert-butyl cyclohex-2-en-1-yl(hydroxy)carbamate) in moderate yields. Spectroscopic studies and trapping experiments suggest the reaction proceeds via a nitroso–ene mechanism, with involvement of a free N-Boc-nitroso intermediate. Asymmetric induction is not observed using the chiral tetramine ligand (+)-(2R,2′R)-1,1′-bis(2-pyridylmethyl)-2,2′-bipyrrolidine ((R,R′)-PDP). PMID:26734101

  7. Modular modification of xylan with UV-initiated thiol-ene reaction.

    PubMed

    Nurmi, Leena; Salminen, Reeta; Setälä, Harri

    2015-03-02

    Birch xylan was functionalized with various thiols through UV initiated radical thiol-ene reaction under mild conditions. Xylan was allylated through etherification with allyl glycidyl ether under alkaline conditions. The allylated xylan was then reacted with thiols containing varying functional groups: trimethylbenzyl mercaptan, dodecanethiol, thioglycolic acid, L-cysteine and cysteamine hydrochloride. The reactions were conducted under homogeneous conditions at room temperature, either in water (hydrophilic thiols) or in DMF (hydrophobic thiols). The effect of reaction parameters to the functionalization efficiency was studied, including, for example, thiol excess, thiol character, initiator amount and reaction mixture concentration. The reactions were fast and 100% conversion of allyl groups was reached in most cases, sometimes already within 10 min. Water as solvent resulted generally in faster reactions when compared to DMF, and it was possible to conduct the aqueous reaction even without added UV initiator. It was also possible to incorporate two functionalities simultaneously during one reaction into the xylan structure. Copyright © 2014 Elsevier Ltd. All rights reserved.

  8. Versatile ene-thiol photoclick reaction for preparation of multimodal monolithic silica capillary columns.

    PubMed

    Marechal, A; Laaniste, A; El-Debs, R; Dugas, V; Demesmay, C

    2014-10-24

    This paper presents a photografting process of monolithic silica capillary columns based on the ene-thiol click chemistry. This study is performed on a "generic" vinyl-functionalized silica monolith (Hmin 6±1μm). The photoclick reaction is investigated using different thiol monomers (octadecanethiol, cysteine and sodium mercaptoethanesulfonate) to prepare capillary columns dedicated to various chromatographic modes (reversed-phase, HILIC and strong cation exchange). Whatever the monomer used, the photografting reaction is achieved in less than 5min with a relatively high thiol monomer content. This allows preparing highly retentive and efficient monolithic columns while avoiding polymerization and/or column clogging. In addition to the aforementioned properties (duration, versatility, efficiency), this photo-triggered chemical reaction allows addressing several appropriate surface functionalizations inside a single monolithic column in order to prepare nanovolume multimodal capillary columns. A multimodal biphasic monolithic column with a 1cm length cation-exchange segment followed by a 9cm length reversed-phase segment (SCX-RP) is prepared through two successive photografting reactions using a UV-mask to localize the reactions. This multimodal biphasic column is investigated using a model sample for the selective fractionation and separation of cationic and neutral compounds and is applied to the on-line preconcentration and separation of β-blockers. Copyright © 2014 Elsevier B.V. All rights reserved.

  9. An examination of shoulder kinematics and kinetics when using a commercial trunk harness while sheep shearing.

    PubMed

    Gregory, Diane E; Milosavljevic, Stephan; Pal, Poonam; Callaghan, Jack P

    2008-01-01

    Sheep shearing is a very physically demanding occupation, especially on the low back, such that many commercial harnesses have been developed to help reduce the load on the back. Such harnesses have been shown to significantly reduce peak and cumulative low back loads; however, the effect that these harnesses have on the shoulders, which are also highly involved during sheep shearing, has not been previously examined. The purpose of this study was to examine the shoulder postures and cumulative shoulder moments of 12 New Zealand sheep shearers. The use of the trunk harness reduced the percentage of time spent in shoulder flexion greater than 90 degrees and the time spent in shoulder abduction greater than 45 degrees as well as reduced the cumulative net joint flexor, abductor, and adductor shoulder moments by a minimum of 21%, 14%, and 42%, respectively. Therefore, the use of a commercial trunk harness to reduce low back injury may also help to reduce the risk of shoulder injury while sheep shearing.

  10. Photo-initiated thiol-ene click reactions as a potential strategy for incorporation of [M(I)(CO)3]+ (M = Re, (99m)Tc) complexes.

    PubMed

    Hayes, Thomas R; Lyon, Patrice A; Silva-Lopez, Elsa; Twamley, Brendan; Benny, Paul D

    2013-03-18

    Click reactions offer a rapid technique to covalently assemble two molecules. In radiopharmaceutical construction, these reactions can be utilized to combine a radioactive metal complex with a biological targeting molecule to yield a potent tool for imaging or therapy applications. The photo-initiated radical thiol-ene click reaction between a thiol and an alkene was examined for the incorporation of [M(I)(CO)3](+) (M = Re, (99m)Tc) systems for conjugating biologically active targeting molecules containing a thiol. In this strategy, a potent chelate system, 2,2'-dipicolylamine (DPA), for [M(I)(CO)3](+) was functionalized at the central amine with a terminal alkene linker that was explored with two synthetic approaches, click then chelate and chelate then click, to determine the flexibility and applicability of the thiol-ene click reaction to specifically incorporate ligand systems and metal complexes with a thiol containing molecule. In the click then chelate approach, the thiol-ene click reaction was carried out with the DPA chelate followed by complexation with [M(I)(CO)3](+). In the chelate then click approach, the alkene functionalized DPA chelate was first complexed with [M(I)(CO)3](+) followed by the conduction of the thiol-ene click reaction. Initial studies utilized benzyl mercaptan as a model thiol for both strategies to generate the identical product from either route to provide information on reactivity and product formation. DPA ligands functionalized with two unique linker systems (allyl and propyl allyl ether) were prepared to examine the effect of the proximity of the chelate or complex on the thiol-ene click reaction. Both the thiol-ene click and coordination reactions with Re, (99m)Tc were performed in moderate to high yields demonstrating the potential of the thiol-ene click reaction for [M(I)(CO)3](+) incorporation into thiol containing biomolecules.

  11. Comparison of Pavlik harness application and immediate spica casting for femur fractures in infants.

    PubMed

    Podeszwa, David A; Mooney, James F; Cramer, Kathryn E; Mendelow, Michael J

    2004-01-01

    This retrospective study compares Pavlik harness application versus spica casting for the treatment of children under 1 year of age with a femoral shaft fracture. The clinical and radiographic outcomes of 24 patients treated in a Pavlik harness were compared with 16 patients treated in a spica cast. The average age and weight of the two groups were significantly different, but there were no differences in radiographic outcomes between the Pavlik and spica cast groups. Approximately one third of all spica patients had a skin complication that added an additional risk to the patient. There were no similar complications in the Pavlik group. There were no differences in the outcome of the fractures in the two groups. The authors believe that all children under 1 year of age with a femoral shaft fracture are candidates for treatment with a Pavlik harness.

  12. Thiol–ene-based biological/synthetic hybrid biomatrix for 3-D living cell culture

    PubMed Central

    Xu, Kedi; Fu, Yao; Chung, WeiJu; Zheng, Xiaoxiang; Cui, Yujia; Hsu, Ian C.; Kao, Weiyuan John

    2013-01-01

    Although various cell encapsulation materials are available commercially for a wide range of potential therapeutic cells, their combined clinical impact remains inconsistent. Synthetic materials such as poly(ethylene glycol) (PEG) hydrogels are mechanically robust and have been extensively explored but lack natural biofunctionality. Naturally derived materials including collagen, fibrin and alginate-chitosan are often labile and mechanically weak. In this paper we report the development of a hybrid biomatrix based on the thiol-ene reaction of PEG diacrylate (PEGdA) and cysteine/PEG-modified gelatin (gel-PEG-Cys). We hypothesized that covalent crosslinking decreases gelatin dissolution thus increasing gelatin resident time within the matrix and the duration of its biofunctionality; at the same time the relative ratio of PEGdA to gel-PEG-Cys in the matrix formulation directly affects hydrogel bulk and local microenvironment properties. Bulk viscoelastic properties were highly dependent on PEGdA concentration and total water content, while gel-PEG-Cys concentration was more critical to swelling profiles. Microviscoelastic properties were related to polymer concentration. The covalently crosslinked gel-PEG-Cys with PEGdA decreased gelatin dissolution out of the matrix and collagenase-mediated degradation. Fibroblasts and keratinocyte increased adhesion density and formed intercellular connections on stiffer hydrogel surfaces, while cells exhibited more cytoplasmic spreading and proliferation when entrapped within softer hydrogels. Hence, this material system contains multiparametric factors that can easily be controlled to modulate the chemical, physical and biological properties of the biomatrix for soft tissue scaffolding and cell presentation to reconstruct lost tissue architecture and physical functionality. PMID:22484717

  13. Spectroscopic characterization of structural isomers of naphthalene: 1-Phenyl-1-butyn-3-ene

    NASA Astrophysics Data System (ADS)

    Sebree, Joshua A.; Plusquellic, David F.; Zwier, Timothy S.

    2011-12-01

    Laser induced fluorescence (LIF), single vibronic level dispersed fluorescence (DFL) spectra, and high resolution rotationally resolved scans of the S 0-S 1 transition of the C 10H 8 isomer 1-phenyl-1-butyn-3-ene have been recorded under jet-cooled conditions. The S 0-S 1 origin of PAV at 34 922 cm -1 is very weak. A vibronic band located 464.0 above the origin, assigned as 30 10, dominates the LIF excitation spectrum, with intensity arising from vibronic coupling with the S 2 state. High resolution scans of the S 0-S 1 origin and 30 10 vibronic bands determine that the former is a 65:35 a: b hybrid band, while 30 10 is a pure a-type band, confirming the role for vibronic coupling and identifying the coupled state as the S 2 state. DFL spectra of all vibronic bands in the first 800 cm -1 of the spectrum were recorded. A near-complete assignment of the vibronic structure in both S 0 and S 1 states is obtained. Herzberg-Teller vibronic coupling is carried by two vibrations, ν28 and ν30, involving in-plane deformations of the vinylacetylene side chain, leading to Duschinsky mixing evident in the intensities of transitions in excitation and DFL spectra. Extensive Duschinsky mixing is also present among the lowest five out-of-plane vibrational modes, involving motion of the side chain. Comparison with the results of DFT B3LYP and TDDFT calculations with a 6-311+G(d,p) basis set confirm and strengthen the assignments.

  14. Stress relaxation via addition-fragmentation chain transfer in a thiol-ene photopolymerization

    PubMed Central

    Kloxin, Christopher J.; Scott, Timothy F.; Bowman, Christopher N.

    2009-01-01

    Allyl sulfide addition-fragmentation chain transfer was employed concurrently with the radical-mediated formation of a thiol-ene network to enable network adaptation and mitigation of polymerization-induced shrinkage stress. This result represents the first demonstration of simultaneous polymerization and network adaptation in covalently crosslinked networks with significant implications for the fabrication of low stress polymer networks. For comparison, analogous networks incorporating propyl sulfide moieties, incapable of addition-fragmentation, were synthesized and evaluated in parallel. At the highest irradiation intensity, the allyl sulfide-containing material demonstrated a more than 75% reduction in the final stress when compared with the propyl sulfide-containing material. Analysis of the conversion evolution revealed that allyl sulfide addition-fragmentation decreased the polymerization rate owing to thiyl radical sequestration. Slow consumption of the allyl sulfide functional group suggests that intramolecular homolytic substitution occurs by a step-wise, rather than concerted, mechanism. Simultaneous stress and conversion measurements demonstrated that the initial stress evolution was identical for both the allyl and propyl sulfide-containing materials but diverged after gelation. While addition-fragmentation chain transfer was found to occur throughout the polymerization, its effect on the stress evolution was concentrated towards the end of polymerization when network rearrangement becomes the dominant mechanism for stress relaxation. Even after the polymerization reaction was completed, the polymerization-induced shrinkage stress in the allyl sulfide-containing material continued to decrease, exhibiting a maximum in the stress evolution and demonstrating the potential for continuing, longer term stress relaxation. PMID:20160931

  15. Polymers of sodium-N-undec-10-ene-1-oyl taurate and sodium-N-undec-10-ene-1-oyl aminoethyl-2-phosphonate as pseudostationary phases for electrokinetic chromatography.

    PubMed

    Tellman, K T; Palmer, C P

    1999-01-01

    The use of micelle polymers, a class of polysoaps with a polymerized hydrophobic interior and a charged hydrophillic exterior, as pseudostationary phases in electrokinetic chromatography has generated significant interest. Their stable structure has been shown to provide significant advantages over conventional micelles when used as pseudostationary phases. In previous studies, micelle polymers have had carboxylate and sulfate head groups. These chemistries have limitations: carboxylate micelle polymers precipitate out of solution at pH less than seven or eight and sulfate head groups are not stable to hydrolysis and are hydrolyzed during polymerization. Additionally, while the chemical selectivity of conventional micelles varies with head group chemistry, no significant differences in chemical selectivity were observed between analogous polymers with sulfate and carboxylate groups. To overcome the limitations of carboxylate and sulfate head groups, and to further investigate the chemical selectivity of micelle polymers, poly(sodium-N-undec-10-ene-1-oyl-taurate) and poly(sodium-N-undec-10-ene-1-oyl-ethyl-2-phosphonate) micellar polymers have been synthesized and characterized as pseudostationary phases. These polymers have amide functionality and stable, strongly acidic sulfonate and phosphonate head groups. These polymers did provide improved solubility at low pH, and are stable under the conditions studied. The chromatographic performance and chemical selectivity of the polymers has been studied by several methods, including linear solvation energy relationships. Poly(sodiumN-undec-10-ene-1-oyl-taurate) has greater electrophoretic mobility than other polymers of this type, and can be used for the separation of hydrophobic compounds. The polymers do exhibit unique selectivity, but the differences in selectivity are not significant for the majority of compounds studied.

  16. Effectiveness of Mom-made Pavlik harness for maintaining reduction of the hip in DDH.

    PubMed

    Lewsirirat, Supphamard; Piyapromdee, Urawit; Sathompanich, Suphasak

    2015-01-01

    Co-operation of the parent is a major factor for successful treatment of developmental dysplasia of the hip (DDH). The commercial Pavlik harness is too expensive and the parent may not understand or refuse its use. Regarding the function of the Pavlik harness and awareness of complications, a Mom-made Pavlik harness was developed. To evaluate the effectiveness of Mom-made Pavlik harness in maintaining the reduction ofDDH MATERIAL AND METHOD: Infants with Ortolani positive DDH, ages up to five months, treated at Maharat Nakhon Ratchasima Hospital between October 2003 and September 2012, were analyzed, retrospectively. Irreducible DDH, neuromuscular DDH and hyperlaxity syndrome were excluded. A Mom-made Pavlik harness was used to maintain reduction after the initial two weeks of a hip spica cast. The success of treatment was evaluated by ultrasound of the hip. The center edge (CE) angle was measured from AP film at age one and four years. There were 24 infants, 35 hips with 11 bilateral, seven left and six right sides DDH. Thirty-two hips were successfully reduced (91.4%). Three hips had recurrent dislocation. Two of these were further managed by adductor tenotomy and closed reduction under general anesthesia and hip spica cast, followed by hip abduction brace. Another was treated by open reduction and Salter's innominate osteotomy. The average CE angle at age one and four years was 16.5 and 25.9 degree, respectively. Treatment of the infants with DDH requires a long period of care not only in hospital but also at home. Therefore, it needs the diligence, intention and regularity by their parents to achieve a successful outcome. The Mom-made Pavlik harness represents the spirit of this resolution.

  17. C27-C30 neohop-13(18)-enes and their saturated and aromatic derivatives in sediments: Indicators for diagenesis and water column stratification

    NASA Astrophysics Data System (ADS)

    Sinninghe Damsté, Jaap S.; Schouten, Stefan; Volkman, John K.

    2014-05-01

    A limited suite of C27, C29 and C30 rearranged hopenes identified as neohop-13(18)-enes have been reported in immature Recent and ancient marine/lacustrine sediments and their presence has been explained by dehydration and isomerisation of ubiquitous hopanols or hopenes. Here we investigated the source and fate of neohop-13(18)-enes in a range of Recent and ancient sediments. The analysis of δ13C values of hop-17(21)-ene and neohop-13(18)-ene in Arabian Sea surface sediments, in the Monterey Formation and in immature Cenomanian black shales show that they differ by 2-3‰, suggesting that the C30 neohop-13(18)-ene has a source different from those of the non-rearranged C30 hopenes. A new member of the family of neohop-13(18)-enes, the C28 hopene 28,30-dinorhop-13(18)-ene, was identified based on comparison of its mass spectral data with that of other members of the family of neohopenes. Its occurrence explains the formation of a series of orphan aromatic hopanoids bearing an ethyl group at C-21, known to occur in high concentrations in some organic-rich ancient sediments. Circumstantial evidence for this formation pathway is provided by identical δ13C values for the C28 28,30-dinorhop-13(18)-ene and two aromatic hopanoids in two Cretaceous black shales. Relatively abundant C28 28,30-dinorhopene and related aromatic derivatives were present in ancient sediments where the distribution of other biomarkers (i.e. isorenieratene derivatives) indicated a stratified palaeo water column. Therefore, it is suggested that these compounds are derived from bacteria dwelling at or below the chemocline and may be used as indicators of stratified water bodies in the past. 28,30-Dinorhop-13(18)-ene may also be a precursor of the unusual C28 desmethylhopane 28,30-dinorhopane found in high concentrations in anoxic sediments and a limited suite of crude oils, which is consistent with the proposal that it too ultimately derives from bacteria living at the oxic-anoxic interface.

  18. Subject Load-Harness Interaction During Zero-Gravity Treadmill Exercise

    NASA Technical Reports Server (NTRS)

    McCrory, Jean L.; Baron, Heidi A.; Derr, Janice A.; Davis, Brian L.; Cavanagh, Peter R.

    1996-01-01

    When astronauts exercise on orbit, a subject load device (SLD) must be used to return the subject back to the supporting surface. The load in the SLD needs to be transferred the body by a harness which typically distributes this load between the pelvis and We shoulders. Through the use of a zero-gravity simulator, this research compared subject comfort and ground reaction forces during treadmill running at three levels of subject load (60%,80%, and 100% of body weight) in two harness designs ("shoulder only" and "waist "and shoulder ").

  19. Aqueous and non-aqueous microchip electrophoresis with on-chip electrospray ionization mass spectrometry on replica-molded thiol-ene microfluidic devices.

    PubMed

    Tähkä, Sari M; Bonabi, Ashkan; Jokinen, Ville P; Sikanen, Tiina M

    2017-05-05

    This work describes aqueous and non-aqueous capillary electrophoresis on thiol-ene-based microfluidic separation devices that feature fully integrated and sharp electrospray ionization (ESI) emitters. The chip fabrication is based on simple and low-cost replica-molding of thiol-ene polymers under standard laboratory conditions. The mechanical rigidity and the stability of the materials against organic solvents, acids and bases could be tuned by adjusting the respective stoichiometric ratio of the thiol and allyl ("ene") monomers, which allowed us to carry out electrophoresis separation in both aqueous and non-aqueous (methanol- and ethanol-based) background electrolytes. The stability of the ESI signal was generally ≤10% RSD for all emitters. The respective migration time repeatabilities in aqueous and non-aqueous background electrolytes were below 3 and 14% RSD (n=4-6, with internal standard). The analytical performance of the developed thiol-ene microdevices was shown in mass spectrometry (MS) based analysis of peptides, proteins, and small molecules. The theoretical plate numbers were the highest (1.2-2.4×10(4)m(-1)) in ethanol-based background electrolytes. The ionization efficiency also increased under non-aqueous conditions compared to aqueous background electrolytes. The results show that replica-molding of thiol-enes is a feasible approach for producing ESI microdevices that perform in a stable manner in both aqueous and non-aqueous electrophoresis. Copyright © 2017 Elsevier B.V. All rights reserved.

  20. Ene-diene transmissive cycloaddition reactions with singlet oxygen: the vinylogous gem effect and its use for polyoxyfunctionalization of dienes.

    PubMed

    Eske, Angelika; Goldfuss, Bernd; Griesbeck, Axel G; de Kiff, Alan; Kleczka, Margarethe; Leven, Matthias; Neudörfl, Jörg-M; Vollmer, Moritz

    2014-02-21

    The singlet oxygen reactivities and regioselectivities of the model compounds 1b-d were compared with those of the geminal (gem) selectivity model ethyl tiglate (1a). The kinetic cis effect is k(E)/k(Z) = 5.2 for the tiglate/angelate system 1a/1a' without a change in the high gem regioselectivity. Further conjugation to vinyl groups enabled mode-selective processes, namely, [4 + 2] cycloadditions versus ene reactions. The site-specific effects of methylation on the mode selectivity and the regioselectivity of the ene reaction were studied for dienes 1e-g. A vinylogous gem effect was observed for the γ,δ-dimethylated and α,γ,δ-trimethylated substrates 1h and 1i, respectively. The corresponding phenylated substrates 1j-l showed similar mode selectivity, as monomethylated 1j exhibited exclusively [4 + 2] reactivity while the tandem products 12 and 14 were isolated from the di- and trimethylated substrates 1k and 1l, respectively. The vinylogous gem effect favors the formation of 1,3-dienes from the substrates, and thus, secondary singlet oxygen addition was observed to give hydroperoxy-1,2-dioxenes 19 and 20 in an ene-diene transmissive cycloaddition sequence. These products were reduced to give alcohols (16, 17, and 18) or furans (24 and 25), respectively, or treated with titanium(IV) alkoxides to give the epoxy alcohols 26 and 27. The vinylogous gem effect is rationalized by DFT calculations showing that biradicals are the low-energy intermediates and that no reaction path bifurcations compete.

  1. Efficient Synthesis of Polycyclic γ-Lactams by Catalytic Carbonylation of Ene-Imines via Nickelacycle Intermediates.

    PubMed

    Hoshimoto, Yoichi; Ashida, Keita; Sasaoka, Yukari; Kumar, Ravindra; Kamikawa, Ken; Verdaguer, Xavier; Riera, Antoni; Ohashi, Masato; Ogoshi, Sensuke

    2017-07-03

    The nickel(0)-catalyzed carbonylative cycloaddition of 1,5- and 1,6-ene-imines with carbon monoxide (CO) is reported. Key to this reaction is the efficient regeneration of the catalytically active nickel(0) species from nickel carbonyl complexes such as [Ni(CO)3 L]. A variety of tri- and tetracyclic γ-lactams were thus prepared in excellent yields with 100 % atom efficiency. Preliminary results on asymmetric derivatives promise potential in the synthesis of enantioenriched polycyclic γ-lactams. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Radical cyclizations of cyclic ene sulfonamides occur with β-elimination of sulfonyl radicals to form polycyclic imines

    PubMed Central

    Zhang, Hanmo; Hay, E. Ben; Geib, Steven J.; Curran, Dennis P.

    2013-01-01

    Radical cyclizations of cyclic ene sulfonamides provide stable bicyclic and tricyclic aldimines and ketimines in good yields. Depending on the structure of the precursor, the cyclizations occur to provide fused and spirocyclic imines with five-, six-, and seven-membered rings. The initial radical cyclization produces an α-sulfonamidoyl radical that undergoes elimination to form the imine and a phenylsulfonyl radical. In a related method, 3,4-dihydroquinolines can also be produced by radical translocation reactions of N-(2-iodophenylsulfonyl)tetrahydroisoquinolines. In either case, very stable sulfonamides are cleaved to form imines (rather than amines) under mild reductive conditions. PMID:24111991

  3. Diastereoselective rhodium-catalyzed ene-cycloisomerization reactions of alkenylidenecyclopropanes: total synthesis of (-)-α-kainic acid.

    PubMed

    Evans, P Andrew; Inglesby, Phillip A

    2012-02-29

    The rhodium-catalyzed ene-cycloisomerization of alkenylidenecyclopropanes provides an atom-economical approach to five-membered carbo- and heterocycles that contain two new stereogenic centers. A key and striking feature of this protocol is that the alkene geometry does not impact the efficiency and diastereocontrol, which provides excellent synthetic versatility. For instance, (E)- and (Z)-allylic alcohols furnish the corresponding aldehydes with similar efficiency and selectivity. This process facilitates the construction of a key intermediate in an eight-step total synthesis of (-)-α-kainic acid. © 2012 American Chemical Society

  4. Rh(I)-catalyzed Pauson-Khand-type cycloaddition reaction of ene-vinylidenecyclopropanes with carbon monoxide (CO).

    PubMed

    Yuan, Wei; Dong, Xiang; Shi, Min; McDowell, Patrick; Li, Guigen

    2012-11-02

    An intramolecular Pauson-Khand type cycloaddition reaction of ene-vinylidenecyclopropanes with carbon monoxide has been established by using [Rh(COD)Cl](2) as the catalyst. The reaction was found to be highly efficient in solvents of 1,2-dichloroethane and 1,1,2,2-tetrachloroethane to give excellent yields of 90-99%. The reaction provides easy access to a series of fused 6,5-ring structures containing spiro-cyclopropane units that are useful for drug design and development. A mechanism of this cycloaddition process has been proposed accounting for structures of resulting products that were unambiguously assigned by X-ray diffractional analysis.

  5. Gas phase thermal reactions of exo-8-cyclopropyl-bicyclo[4.2.0]oct-2-ene (1-exo).

    PubMed

    Leber, Phyllis A; Nocket, Anthony J; Hancock-Cerutti, William; Bemis, Christopher Y; Khine, Wint Khant; Mohrbacher Iii, Joseph A; Baldwin, John E

    2014-01-27

    The title compound 1-exo (with minor amounts of its C8 epimer 1-endo) was prepared by Wolff-Kishner reduction of the cycloadduct of 1,3-cyclohexadiene and cyclopropylketene. The [1,3]-migration product 2-endo was synthesized by efficient selective cyclopropanation of endo-5-vinylbicyclo[2.2.2]oct-2-ene at the exocyclic π-bond. Gas phase thermal reactions of 1-exo afforded C8 epimerization to 1-endo, [1,3]- migrations to 2-exo and 2-endo, direct fragmentation to cyclohexadiene and vinylcyclopropane, and CPC rearrangement in the following relative kinetic order: kep > k13 > kf > kCPC.

  6. The Phenol-Ene Reaction: Biaryl Synthesis via Trapping Reactions between HDDA-Generated Benzynes and Phenolics.

    PubMed

    Zhang, Juntian; Niu, Dawen; Brinker, Vincent A; Hoye, Thomas R

    2016-11-04

    Benzynes produced thermally by the cycloisomerization of triyne-containing precursors [i.e., by the hexadehydro-Diels-Alder (HDDA) reaction] react with phenols at the carbon ortho to the hydroxyl in an enelike fashion. Following tautomerization of the intermediate cyclohexadienones, this produces biaryl derivatives. DFT calculations of model reactions support this mechanistic interpretation. Substituted, unsymmetrical phenols and bis-phenols react in a fashion that can be explained by engagement of the most readily available (non-hydrogen-bonded) hydroxyl in the phenol-ene process.

  7. Chemoenzymatic asymmetric synthesis of pregabalin precursors via asymmetric bioreduction of β-cyanoacrylate esters using ene-reductases.

    PubMed

    Winkler, Christoph K; Clay, Dorina; Davies, Simon; O'Neill, Pat; McDaid, Paul; Debarge, Sebastien; Steflik, Jeremy; Karmilowicz, Mike; Wong, John W; Faber, Kurt

    2013-02-15

    The asymmetric bioreduction of a library of β-cyanoacrylate esters using ene-reductases was studied with the aim to provide a biocatalytic route to precursors for GABA analogues, such as pregabalin. The stereochemical outcome could be controlled by substrate-engineering through size-variation of the ester moiety and by employing stereochemically pure (E)- or (Z)-isomers, which allowed to access both enantiomers of each product in up to quantitative conversion in enantiomerically pure form. In addition, stereoselectivities and conversions could be improved by mutant variants of OPR1, and the utility of the system was demonstrated by preparative-scale applications.

  8. Chemoenzymatic Asymmetric Synthesis of Pregabalin Precursors via Asymmetric Bioreduction of β-Cyanoacrylate Esters Using Ene-Reductases

    PubMed Central

    2013-01-01

    The asymmetric bioreduction of a library of β-cyanoacrylate esters using ene-reductases was studied with the aim to provide a biocatalytic route to precursors for GABA analogues, such as pregabalin. The stereochemical outcome could be controlled by substrate-engineering through size-variation of the ester moiety and by employing stereochemically pure (E)- or (Z)-isomers, which allowed to access both enantiomers of each product in up to quantitative conversion in enantiomerically pure form. In addition, stereoselectivities and conversions could be improved by mutant variants of OPR1, and the utility of the system was demonstrated by preparative-scale applications. PMID:23316696

  9. Radical cyclizations of cyclic ene sulfonamides occur with β-elimination of sulfonyl radicals to form polycyclic imines.

    PubMed

    Zhang, Hanmo; Hay, E Ben; Geib, Steven J; Curran, Dennis P

    2013-11-06

    Radical cyclizations of cyclic ene sulfonamides provide stable bicyclic and tricyclic aldimines and ketimines in good yields. Depending on the structure of the precursor, the cyclizations occur to provide fused and spirocyclic imines with five-, six-, and seven-membered rings. The initial radical cyclization produces an α-sulfonamidoyl radical that undergoes elimination to form the imine and a phenylsulfonyl radical. In a related method, 3,4-dihydroquinolines can also be produced by radical translocation reactions of N-(2-iodophenylsulfonyl)tetrahydroiso-quinolines. In either case, very stable sulfonamides are cleaved to form imines (rather than amines) under mild reductive conditions.

  10. Reliability and Validity of the Zephyr[TM] BioHarness[TM] to Measure Respiratory Responses to Exercise

    ERIC Educational Resources Information Center

    Hailstone, Jono; Kilding, Andrew E.

    2011-01-01

    The Zephyr[TM] BioHarness[TM] (Zephyr Technology, Auckland, New Zealand) is a wireless physiological monitoring system that has the ability to measure respiratory rate unobtrusively. However, the ability of the BioHarness[TM] to accurately and reproducibly determine respiratory rate across a range of intensities is currently unknown. The aim of…

  11. Reliability and Validity of the Zephyr[TM] BioHarness[TM] to Measure Respiratory Responses to Exercise

    ERIC Educational Resources Information Center

    Hailstone, Jono; Kilding, Andrew E.

    2011-01-01

    The Zephyr[TM] BioHarness[TM] (Zephyr Technology, Auckland, New Zealand) is a wireless physiological monitoring system that has the ability to measure respiratory rate unobtrusively. However, the ability of the BioHarness[TM] to accurately and reproducibly determine respiratory rate across a range of intensities is currently unknown. The aim of…

  12. Harnessing the power of big data: infusing the scientific method with machine learning to transform ecology

    USDA-ARS?s Scientific Manuscript database

    Most efforts to harness the power of big data for ecology and environmental sciences focus on data and metadata sharing, standardization, and accuracy. However, many scientists have not accepted the data deluge as an integral part of their research because the current scientific method is not scalab...

  13. Language Teaching in a Globalised World: Harnessing Linguistic Super-Diversity in the Classroom

    ERIC Educational Resources Information Center

    Bruen, Jennifer; Kelly, Niamh

    2016-01-01

    The student body is becoming increasingly diverse in terms of language, nationality and cultural background. This study explores ways in which such linguistic diversity can be harnessed in the language classroom to enhance the language learning process. This paper describes a series of activities which were designed and implemented in four higher…

  14. Early failure of Pavlik harness treatment for developmental hip dysplasia: clinical and ultrasound predictors.

    PubMed

    Lerman, J A; Emans, J B; Millis, M B; Share, J; Zurakowski, D; Kasser, J R

    2001-01-01

    A cohort of 93 patients with developmental dysplasia of the hip (DDH) treated with a Pavlik harness were evaluated to determine predictors of treatment failure. Failure was defined as failure to achieve or maintain hip reduction in the Pavlik harness. Of 93 patients (137 hips), 17 (26 hips) failed Pavlik harness treatment. Univariate risk factors for failure included bilaterality, initial clinical exam, and initial ultrasound (US) percent coverage. Clinical exam and initial percent coverage were multivariate risk factors for failure. Among initially clinically dislocatable hips, a low initial US alpha angle correlated with an increased likelihood of failure. All (6/6) patients with an initially irreducible hip and an initial coverage of <20% by US eventually failed treatment. Gender, side of pathology, and age at diagnosis and initiation of treatment did not correlate with failure. Irreducibility by physical exam combined with US coverage of <20% identified a patient group that uniformly failed Pavlik harness treatment. These patients may be candidates for alternative bracing, traction, or closed or open reduction.

  15. 14 CFR 105.43 - Use of single-harness, dual-parachute systems.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 14 Aeronautics and Space 2 2010-01-01 2010-01-01 false Use of single-harness, dual-parachute... TRANSPORTATION (CONTINUED) AIR TRAFFIC AND GENERAL OPERATING RULES PARACHUTE OPERATIONS Parachute Equipment and... been packed within 180 days before the date of its use by a certificated parachute rigger, the...

  16. Pressure distribution under three different types of harnesses used for guide dogs.

    PubMed

    Peham, C; Limbeck, S; Galla, K; Bockstahler, B

    2013-12-01

    The aim of this study was to evaluate the pressure distribution under three different types of harnesses used for guide dogs (designated H1, H2 and H3). The dogs (n = 8) led a trainer through a course including a range of exercises (straight line, curve left, curve right, upstairs and downstairs). All dogs were clinically sound and showed no sign of lameness. The pressures beneath the harnesses were determined by sensor strips and related to the gait. In all harnesses, the highest pressures were found in the right sternal region (H1 2.02 ± 0.6N/cm(2); H2 1.76 ± 0.4N/cm(2); H3 1.14 ± 0.5 N/cm(2)). In all other regions, the pressures were in the range of 0-1.32 N/cm(2). The right and left sternal regions were almost constantly loaded. Contrary to previous assumptions, the back regions had minimal loading. This investigation demonstrated that there were significant differences among the harnesses.

  17. Kinematic assessment of treadmill running using different body-weight support harnesses.

    PubMed

    Millslagle, Duane; Levy, Morris; Matack, Nicholas

    2006-10-01

    10 male collegiate runners (M age = 21.4, SD = 1.5 yr.) ran on a treadmill with no body-weight support (BWS), 20% BWS, and 40% BWS conditions. In addition, they wore three different commercially available harnesses at the 20% and 40% BWS conditions. The aim was to run on the treadmill at a fast speed while maintaining an adequate step length. The purpose was to investigate how each harness changed running gait, and the differences in running gait between the harnesses with various body-weight support. Analysis of variance indicated significant restriction of upper body torso rotation between the harnesses at the 40% BWS conditions. Body-weight support resulted in a longer stride, decreased cadence, less vertical displacement of the center of mass, and diminished hip and ankle joint excursions. These changes indicated that increased body-weight support results in longer steps with the foot contacting the belt for a shorter period of time with less leg angular changes throughout the running cycling.

  18. STS-42 Payload Specialist Bondar suspended from parachute harness in JSC WETF

    NASA Technical Reports Server (NTRS)

    1991-01-01

    STS-42 Discovery, Orbiter Vehicle (OV) 103, Payload Specialist Roberta L. Bondar, wearing launch and entry suit (LES) and launch and entry helmet (LEH), is suspended from her parachute harness over JSC's Weightless Environment Training Facility (WETF) Bldg 29 pool during launch emergency egress exercises. Bondar is representing Canada during the International Microgravity Laboratory 1 (IML-1) mission aboard OV-103.

  19. 42 CFR 84.73 - Harnesses; installation and construction; minimum requirements.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... 42 Public Health 1 2012-10-01 2012-10-01 false Harnesses; installation and construction; minimum requirements. 84.73 Section 84.73 Public Health PUBLIC HEALTH SERVICE, DEPARTMENT OF HEALTH AND HUMAN SERVICES OCCUPATIONAL SAFETY AND HEALTH RESEARCH AND RELATED ACTIVITIES APPROVAL OF RESPIRATORY PROTECTIVE DEVICES...

  20. 42 CFR 84.116 - Harnesses; installation and construction; minimum requirements.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... 42 Public Health 1 2012-10-01 2012-10-01 false Harnesses; installation and construction; minimum requirements. 84.116 Section 84.116 Public Health PUBLIC HEALTH SERVICE, DEPARTMENT OF HEALTH AND HUMAN SERVICES OCCUPATIONAL SAFETY AND HEALTH RESEARCH AND RELATED ACTIVITIES APPROVAL OF RESPIRATORY...

  1. 42 CFR 84.73 - Harnesses; installation and construction; minimum requirements.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... 42 Public Health 1 2013-10-01 2013-10-01 false Harnesses; installation and construction; minimum requirements. 84.73 Section 84.73 Public Health PUBLIC HEALTH SERVICE, DEPARTMENT OF HEALTH AND HUMAN SERVICES OCCUPATIONAL SAFETY AND HEALTH RESEARCH AND RELATED ACTIVITIES APPROVAL OF RESPIRATORY PROTECTIVE DEVICES...

  2. 42 CFR 84.73 - Harnesses; installation and construction; minimum requirements.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... 42 Public Health 1 2011-10-01 2011-10-01 false Harnesses; installation and construction; minimum requirements. 84.73 Section 84.73 Public Health PUBLIC HEALTH SERVICE, DEPARTMENT OF HEALTH AND HUMAN SERVICES OCCUPATIONAL SAFETY AND HEALTH RESEARCH AND RELATED ACTIVITIES APPROVAL OF RESPIRATORY PROTECTIVE DEVICES...

  3. 42 CFR 84.73 - Harnesses; installation and construction; minimum requirements.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... 42 Public Health 1 2014-10-01 2014-10-01 false Harnesses; installation and construction; minimum requirements. 84.73 Section 84.73 Public Health PUBLIC HEALTH SERVICE, DEPARTMENT OF HEALTH AND HUMAN SERVICES OCCUPATIONAL SAFETY AND HEALTH RESEARCH AND RELATED ACTIVITIES APPROVAL OF RESPIRATORY PROTECTIVE DEVICES...

  4. 42 CFR 84.116 - Harnesses; installation and construction; minimum requirements.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... 42 Public Health 1 2011-10-01 2011-10-01 false Harnesses; installation and construction; minimum requirements. 84.116 Section 84.116 Public Health PUBLIC HEALTH SERVICE, DEPARTMENT OF HEALTH AND HUMAN SERVICES OCCUPATIONAL SAFETY AND HEALTH RESEARCH AND RELATED ACTIVITIES APPROVAL OF RESPIRATORY...

  5. 42 CFR 84.116 - Harnesses; installation and construction; minimum requirements.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... 42 Public Health 1 2013-10-01 2013-10-01 false Harnesses; installation and construction; minimum requirements. 84.116 Section 84.116 Public Health PUBLIC HEALTH SERVICE, DEPARTMENT OF HEALTH AND HUMAN SERVICES OCCUPATIONAL SAFETY AND HEALTH RESEARCH AND RELATED ACTIVITIES APPROVAL OF RESPIRATORY...

  6. 42 CFR 84.116 - Harnesses; installation and construction; minimum requirements.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... 42 Public Health 1 2014-10-01 2014-10-01 false Harnesses; installation and construction; minimum requirements. 84.116 Section 84.116 Public Health PUBLIC HEALTH SERVICE, DEPARTMENT OF HEALTH AND HUMAN SERVICES OCCUPATIONAL SAFETY AND HEALTH RESEARCH AND RELATED ACTIVITIES APPROVAL OF RESPIRATORY...

  7. Harnessing Sparse and Low-Dimensional Structures for Robust Clustering of Imagery Data

    ERIC Educational Resources Information Center

    Rao, Shankar Ramamohan

    2009-01-01

    We propose a robust framework for clustering data. In practice, data obtained from real measurement devices can be incomplete, corrupted by gross errors, or not correspond to any assumed model. We show that, by properly harnessing the intrinsic low-dimensional structure of the data, these kinds of practical problems can be dealt with in a uniform…

  8. 14 CFR 27.785 - Seats, berths, litters, safety belts, and harnesses.

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ... about in the rotorcraft in normal flight must be padded. (f) Each seat and its supporting structure must..., the headrest and its supporting structure must be designed to resist the inertia forces specified in... structure; and (ii) Each safety belt or harness to the seat or structure. (g) When the safety belt...

  9. 14 CFR 29.785 - Seats, berths, litters, safety belts, and harnesses.

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ... in the rotorcraft in normal flight must be padded. (f) Each seat and its supporting structure must be..., the headrest and its supporting structure must be designed to resist the inertia forces specified in... structure; and (ii) Each safety belt or harness to the seat or structure. (g) When the safety belt...

  10. 14 CFR 29.785 - Seats, berths, litters, safety belts, and harnesses.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... in the rotorcraft in normal flight must be padded. (f) Each seat and its supporting structure must be..., the headrest and its supporting structure must be designed to resist the inertia forces specified in... structure; and (ii) Each safety belt or harness to the seat or structure. (g) When the safety belt...

  11. 14 CFR 23.785 - Seats, berths, litters, safety belts, and shoulder harnesses.

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ...: (a) Each seat/restraint system and the supporting structure must be designed to support occupants... and the attachment of— (1) Each seat to the structure; and (2) Each safety belt and shoulder harness to the seat or structure. (b) Each forward-facing or aft-facing seat/restraint system in...

  12. 14 CFR 29.785 - Seats, berths, litters, safety belts, and harnesses.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... in the rotorcraft in normal flight must be padded. (f) Each seat and its supporting structure must be..., the headrest and its supporting structure must be designed to resist the inertia forces specified in... structure; and (ii) Each safety belt or harness to the seat or structure. (g) When the safety belt...

  13. 14 CFR 23.785 - Seats, berths, litters, safety belts, and shoulder harnesses.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ...: (a) Each seat/restraint system and the supporting structure must be designed to support occupants... and the attachment of— (1) Each seat to the structure; and (2) Each safety belt and shoulder harness to the seat or structure. (b) Each forward-facing or aft-facing seat/restraint system in...

  14. 14 CFR 27.785 - Seats, berths, litters, safety belts, and harnesses.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... about in the rotorcraft in normal flight must be padded. (f) Each seat and its supporting structure must..., the headrest and its supporting structure must be designed to resist the inertia forces specified in... structure; and (ii) Each safety belt or harness to the seat or structure. (g) When the safety belt...

  15. 14 CFR 29.785 - Seats, berths, litters, safety belts, and harnesses.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... in the rotorcraft in normal flight must be padded. (f) Each seat and its supporting structure must be..., the headrest and its supporting structure must be designed to resist the inertia forces specified in... structure; and (ii) Each safety belt or harness to the seat or structure. (g) When the safety belt...

  16. 14 CFR 23.785 - Seats, berths, litters, safety belts, and shoulder harnesses.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ...: (a) Each seat/restraint system and the supporting structure must be designed to support occupants... and the attachment of— (1) Each seat to the structure; and (2) Each safety belt and shoulder harness to the seat or structure. (b) Each forward-facing or aft-facing seat/restraint system in...

  17. 14 CFR 27.785 - Seats, berths, litters, safety belts, and harnesses.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... about in the rotorcraft in normal flight must be padded. (f) Each seat and its supporting structure must..., the headrest and its supporting structure must be designed to resist the inertia forces specified in... structure; and (ii) Each safety belt or harness to the seat or structure. (g) When the safety belt...

  18. 14 CFR 29.785 - Seats, berths, litters, safety belts, and harnesses.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... in the rotorcraft in normal flight must be padded. (f) Each seat and its supporting structure must be..., the headrest and its supporting structure must be designed to resist the inertia forces specified in... structure; and (ii) Each safety belt or harness to the seat or structure. (g) When the safety belt...

  19. 14 CFR 27.785 - Seats, berths, litters, safety belts, and harnesses.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... about in the rotorcraft in normal flight must be padded. (f) Each seat and its supporting structure must..., the headrest and its supporting structure must be designed to resist the inertia forces specified in... structure; and (ii) Each safety belt or harness to the seat or structure. (g) When the safety belt...

  20. 14 CFR 23.785 - Seats, berths, litters, safety belts, and shoulder harnesses.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ...: (a) Each seat/restraint system and the supporting structure must be designed to support occupants... and the attachment of— (1) Each seat to the structure; and (2) Each safety belt and shoulder harness to the seat or structure. (b) Each forward-facing or aft-facing seat/restraint system in...

  1. 14 CFR 27.785 - Seats, berths, litters, safety belts, and harnesses.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... about in the rotorcraft in normal flight must be padded. (f) Each seat and its supporting structure must..., the headrest and its supporting structure must be designed to resist the inertia forces specified in... structure; and (ii) Each safety belt or harness to the seat or structure. (g) When the safety belt...

  2. Harnessing ICT Potential: The Adoption and Analysis of ICT Systems for Enhancing the Student Learning Experience

    ERIC Educational Resources Information Center

    Dawson, Shane; Heathcote, Liz; Poole, Gary

    2010-01-01

    Purpose: This paper aims to examine how effective higher education institutions have been in harnessing the data capture mechanisms from their student information systems, learning management systems and communication tools for improving the student learning experience and informing practitioners of the achievement of specific learning outcomes.…

  3. 42 CFR 84.73 - Harnesses; installation and construction; minimum requirements.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... 42 Public Health 1 2010-10-01 2010-10-01 false Harnesses; installation and construction; minimum requirements. 84.73 Section 84.73 Public Health PUBLIC HEALTH SERVICE, DEPARTMENT OF HEALTH AND HUMAN SERVICES OCCUPATIONAL SAFETY AND HEALTH RESEARCH AND RELATED ACTIVITIES APPROVAL OF RESPIRATORY PROTECTIVE DEVICES...

  4. 42 CFR 84.116 - Harnesses; installation and construction; minimum requirements.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... 42 Public Health 1 2010-10-01 2010-10-01 false Harnesses; installation and construction; minimum requirements. 84.116 Section 84.116 Public Health PUBLIC HEALTH SERVICE, DEPARTMENT OF HEALTH AND HUMAN SERVICES OCCUPATIONAL SAFETY AND HEALTH RESEARCH AND RELATED ACTIVITIES APPROVAL OF RESPIRATORY...

  5. After the electronic field: structure, bonding, and the first hyperpolarizability of HArF.

    PubMed

    Wu, Heng-Qing; Zhong, Rong-Lin; Kan, Yu-He; Sun, Shi-Ling; Zhang, Min; Xu, Hong-Liang; Su, Zhong-Min

    2013-04-30

    In this work, we add different strength of external electric field (E(ext)) along molecule axis (Z-axis) to investigate the electric field induced effect on HArF structure. The H-Ar bond is the shortest at E(ext) = -189 × 10(-4) and the Ar-F bond show shortest value at E(ext) = 185 × 10(-4) au. Furthermore, the wiberg bond index analyses show that with the variation of HArF structure, the covalent bond H-Ar shows downtrend (ranging from 0.79 to 0.69) and ionic bond Ar-F shows uptrend (ranging from 0.04 to 0.17). Interestingly, the natural bond orbital analyses show that the charges of F atom range from -0.961 to -0.771 and the charges of H atoms range from 0.402 to 0.246. Due to weakened charge transfer, the first hyperpolarizability (β(tot)) can be modulated from 4078 to 1087 au. On the other hand, make our results more useful to experimentalists, the frequency-dependent first hyperpolarizabilities were investigated by the coupled perturbed Hartree-Fork method. We hope that this work may offer a new idea for application of noble-gas hydrides.

  6. The Facebook-in-Action: Challenging, Harnessing and Enhancing Students Class Assignments and Projects

    ERIC Educational Resources Information Center

    Saifudin, Adam Mohd; Yacob, Aizan; Saad, Rohaizah

    2016-01-01

    Issues of universities students harnessing and capitalizing the usage of Facebook for their own learning capabilities and effective thinking is always the focus of education scholars, in assessing the quality class assignments and projects produced by them. Therefore, Facebook is now becoming unbearable influence since the internet activation in…

  7. Harnessing the Potential of Information Technologies in Education: Finding Innovation and Adaptability in Mali and Ghana.

    ERIC Educational Resources Information Center

    Breslar, Zoey L.

    This study is based on the premises that information technologies (IT) are essential to African development and that education systems are responsible for developing a countries' human capacity to maximize those technologies. The study examines the ability of education systems in Mali and Ghana to develop the capacity to harness the potential of…

  8. Language Teaching in a Globalised World: Harnessing Linguistic Super-Diversity in the Classroom

    ERIC Educational Resources Information Center

    Bruen, Jennifer; Kelly, Niamh

    2016-01-01

    The student body is becoming increasingly diverse in terms of language, nationality and cultural background. This study explores ways in which such linguistic diversity can be harnessed in the language classroom to enhance the language learning process. This paper describes a series of activities which were designed and implemented in four higher…

  9. Harnessing Sparse and Low-Dimensional Structures for Robust Clustering of Imagery Data

    ERIC Educational Resources Information Center

    Rao, Shankar Ramamohan

    2009-01-01

    We propose a robust framework for clustering data. In practice, data obtained from real measurement devices can be incomplete, corrupted by gross errors, or not correspond to any assumed model. We show that, by properly harnessing the intrinsic low-dimensional structure of the data, these kinds of practical problems can be dealt with in a uniform…

  10. Harnessing ICT Potential: The Adoption and Analysis of ICT Systems for Enhancing the Student Learning Experience

    ERIC Educational Resources Information Center

    Dawson, Shane; Heathcote, Liz; Poole, Gary

    2010-01-01

    Purpose: This paper aims to examine how effective higher education institutions have been in harnessing the data capture mechanisms from their student information systems, learning management systems and communication tools for improving the student learning experience and informing practitioners of the achievement of specific learning outcomes.…

  11. Improving Students' Educational Experience by Harnessing Digital Technology: elgg in the ODL Environment

    ERIC Educational Resources Information Center

    Tung, Lai Cheng

    2013-01-01

    Given the rising popularity of both open and distance learning (ODL) and social networking tools, it seems logical to merge and harness these two popular technologies with the goal of improving student educational experience. The integration seems to hold tremendous promise for the open and distance learning mode. To reduce the gap in the…

  12. 42 CFR 84.1133 - Harnesses; installation and construction; minimum requirements.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... 42 Public Health 1 2010-10-01 2010-10-01 false Harnesses; installation and construction; minimum requirements. 84.1133 Section 84.1133 Public Health PUBLIC HEALTH SERVICE, DEPARTMENT OF HEALTH AND HUMAN... DEVICES Dust, Fume, and Mist; Pesticide; Paint Spray; Powered Air-Purifying High Efficiency Respirators...

  13. Thiol-ene and photo-cleavage chemistry for controlled presentation of biomolecules in hydrogels.

    PubMed

    Grim, Joseph C; Marozas, Ian A; Anseth, Kristi S

    2015-12-10

    photochemical methods have led to important advances in the tissue regeneration community, namely the thiol-ene photo-click reaction for bioconjugation and photocleavage reactions that allow for the removal of protecting groups. Specific examples will be highlighted where these methodologies have been used to engineer hydrogels that control and direct cell function with the aim of inspiring their use in regenerative medicine. Copyright © 2015 Elsevier B.V. All rights reserved.

  14. A colorimetric detection of acrylamide in potato chips based on nucleophile-initiated thiol-ene Michael addition.

    PubMed

    Hu, Qinqin; Fu, Yingchun; Xu, Xiahong; Qiao, Zhaohui; Wang, Ronghui; Zhang, Ying; Li, Yanbin

    2016-02-07

    Acrylamide (AA), a neurotoxin and a potential carcinogen, has been found in various thermally processed foods such as potato chips, biscuits, and coffee. Simple, cost-effective, and sensitive methods for the rapid detection of AA are needed to ensure food safety. Herein, a novel colorimetric method was proposed for the visual detection of AA based on a nucleophile-initiated thiol-ene Michael addition reaction. Gold nanoparticles (AuNPs) were aggregated by glutathione (GSH) because of a ligand-replacement, accompanied by a color change from red to purple. In the presence of AA, after the thiol-ene Michael addition reaction between GSH and AA with the catalysis of a nucleophile, the sulfhydryl group of GSH was consumed by AA, which hindered the subsequent ligand-replacement and the aggregation of AuNPs. Therefore, the concentration of AA could be determined by the visible color change caused by dispersion/aggregation of AuNPs. This new method showed high sensitivity with a linear range from 0.1 μmol L(-1) to 80 μmol L(-1) and a detection limit of 28.6 nmol L(-1), and especially revealed better selectivity than the fluorescence sensing method reported previously. Moreover, this new method was used to detect AA in potato chips with a satisfactory result in comparison with the standard methods based on chromatography, which indicated that the colorimetric method can be expanded for the rapid detection of AA in thermally processed foods.

  15. A robust platform for functional microgels via thiol-ene achemistry with reactive polyether-based nanoparticles

    PubMed Central

    Fleischmann, Carolin; Gopez, Jeffrey; Lundberg, Pontus; Ritter, Helmut; Killops, Kato L.

    2015-01-01

    We herein report the development of crosslinked polyether particles as a reactive platform for the preparation of functional microgels. Thiol-ene crosslinking of poly(allyl glycidyl ether) in miniemulsion droplets - stabilized by a surface active, bio-compatible polyethylene glycol block copolymer - resulted in colloidal gels with a PEG corona and an inner polymeric network containing reactive allyl units. The stability of the allyl groups allows the microgels to be purified and stored before a second, subsequent thiol-ene functionalization step allows a wide variety of pH- and chemically-responsive groups to be introduced into the nanoparticles. The facile nature of this synthetic platform enables the preparation of microgel libraries that are responsive to different triggers but are characterized by the same size distribution, surface functionality, and crosslinking density. In addition, the utilization of a crosslinker containing cleavable ester groups renders the resulting hydrogel particles degradable at elevated pH or in the presence of esterase under physiological conditions. PMID:26005499

  16. Beyond PDMS: off-stoichiometry thiol-ene (OSTE) based soft lithography for rapid prototyping of microfluidic devices.

    PubMed

    Carlborg, Carl Fredrik; Haraldsson, Tommy; Öberg, Kim; Malkoch, Michael; van der Wijngaart, Wouter

    2011-09-21

    In this article we introduce a novel polymer platform based on off-stoichiometry thiol-enes (OSTEs), aiming to bridge the gap between research prototyping and commercial production of microfluidic devices. The polymers are based on the versatile UV-curable thiol-ene chemistry but takes advantage of off-stoichiometry ratios to enable important features for a prototyping system, such as one-step surface modifications, tuneable mechanical properties and leakage free sealing through direct UV-bonding. The platform exhibits many similarities with PDMS, such as rapid prototyping and uncomplicated processing but can at the same time mirror the mechanical and chemical properties of both PDMS as well as commercial grade thermoplastics. The OSTE-prepolymer can be cast using standard SU-8 on silicon masters and a table-top UV-lamp, the surface modifications are precisely grafted using a stencil mask and the bonding requires only a single UV-exposure. To illustrate the potential of the material we demonstrate key concepts important in microfluidic chip fabrication such as patterned surface modifications for hydrophobic stops, pneumatic valves using UV-lamination of stiff and rubbery materials as well as micromachining of chip-to-world connectors in the OSTE-materials. This journal is © The Royal Society of Chemistry 2011

  17. [Preparation of organic-inorganic hybrid boronate affinity monolith via thiol-ene click reaction for specific capture of glycoproteins].

    PubMed

    Yang, Fan; Mao, Jie; He, Xiwen; Chen, Langxing; Zhang, Yukui

    2013-06-01

    A novel strategy for the preparation of the organic-inorganic hybrid boronate affinity monolith was developed via the "thiol-ene" click reaction. A thiol group-modified silica monolith was first synthesized via the sol-gel process by the in situ co-condensation with tetramethoxysilane (TMOS) and 3-mercaptopropyltrimethoxysilane (MPTMS) as precursors. Then 3-acrylamidophenylboronic acid (AAPBA) was covalently immobilized on the hybrid monolith via the "thiol-ene" click reaction to form AAPBA-silica hybrid affinity monolith. The reaction conditions for the preparation of AAPBA-silica hybrid affinity monolith were optimized, including the ratio of TMOS to MPTMS, the contents of poly(ethylene glycol) (PEG) and methanol. The morphology and mechanical stability of the boronate affinity monolith were characterized and evaluated by scanning electron microscopy and Fourier-transform infrared spectroscopy. The obtained boronate affinity hybrid monolith exhibited excellent specificity toward the nucleosides containing cis-diols under neutral conditions. It was further applied to the specific capture of the glycoproteins ovalbumin and horseradish peroxidase. The method is novel and reliable, which has a great potential for the preparation of different kinds of the boronate affinity monoliths.

  18. Facile preparation of organic-silica hybrid monolith for capillary hydrophilic liquid chromatography based on "thiol-ene" click chemistry.

    PubMed

    Chen, Ming-Luan; Zhang, Jun; Zhang, Zheng; Yuan, Bi-Feng; Yu, Qiong-Wei; Feng, Yu-Qi

    2013-04-05

    In this work, a one-step approach to facile preparation of organic-inorganic hybrid monoliths was successfully developed. After vinyl-end organic monomers and azobisisobutyronitrile (AIBN) were mixed with hydrolyzed tetramethoxysilane (TMOS) and 3-mercaptopropyltrimethoxysilane (MPTMS), the homogeneous mixture was introduced into a fused-silica capillary for simultaneous polycondensation and "thiol-ene" click reaction to form the organic-silica hybrid monoliths. By employing this strategy, two types of organic-silica hybrid monoliths with positively charged quaternary ammonium and amide groups were prepared, respectively. The functional groups were successfully introduced onto the monoliths during the sol-gel process with "thiol-ene" click reaction, which was demonstrated by ζ-potential assessment, energy dispersive X-ray spectroscopy (EDX), and Fourier transform infrared (FT-IR) spectroscopy. The porous structure of the prepared monolithic columns was examined by scanning electron microscopy (SEM), nitrogen adsorption-desorption measurement, and mercury intrusion porosimetry. These results indicate the prepared organic-silica hybrid monoliths possess homogeneous column bed, large specific surface area, good mechanical stability, and excellent permeability. The prepared monolithic columns were then applied for anion-exchange/hydrophilic interaction liquid chromatography. Different types of analytes, including benzoic acids, inorganic ions, nucleosides, and nucleotides, were well separated with high column efficiency around 80,000-130,000 plates/m. Taken together, we present a facile and universal strategy to prepare organic-silica hybrid monoliths with a variety of organic monomers using one-step approach.

  19. Double bond in the side chain of 1alpha,25-dihydroxy-22-ene-vitamin D(3) is reduced during its metabolism: studies in chronic myeloid leukemia (RWLeu-4) cells and rat kidney.

    PubMed

    Sunita Rao, D; Balkundi, D; Uskokovic, M R; Tserng, K; Clark, J W; Horst, R L; Satyanarayana Reddy, G

    2001-08-01

    1alpha,25-Dihydroxyvitamin D(3) [1alpha,25(OH)(2)D(3)] is mainly metabolized via the C-24 oxidation pathway and undergoes several side chain modifications which include C-24 hydroxylation, C-24 ketonization, C-23 hydroxylation and side chain cleavage between C-23 and C-24 to form the final product, calcitroic acid. In a recent study we reported that 1alpha,25-dihydroxyvitamin D(2) [1alpha,25(OH)(2)D(2)] like 1alpha,25(OH)(2)D(3), is also converted into the same final product, calcitroic acid. This finding indicated that 1alpha,25(OH)(2)D(2) also undergoes side chain cleavage between C-23 and C-24. As the side chain of 1alpha,25(OH)(2)D(2) when compared to the side chain of 1alpha,25(OH)(2)D(3), has a double bond between C-22 and C-23 and an extra methyl group at C-24 position, it opens the possibility for both (a) double bond reduction and (b) demethylation to occur during the metabolism of 1alpha,25(OH)(2)D(2). We undertook the present study to establish firmly the possibility of double bond reduction in the metabolism of vitamin D(2) related compounds. We compared the metabolism of 1alpha,25-dihydroxy-22-ene-vitamin D(3) [1alpha,25(OH)(2)-22-ene-D(3)], a synthetic vitamin D analog whose side chain differs from that of 1alpha,25(OH)(2)D(3) only through a single modification namely the presence of a double bond between C-22 and C-23. Metabolism studies were performed in the chronic myeloid leukemic cell line (RWLeu-4) and in the isolated perfused rat kidney. Our results indicate that both 1alpha,25(OH)(2)-22-ene-D(3) and 1alpha,25(OH)(2)D(3) are converted into common metabolites namely, 1alpha,24(R),25-trihydroxyvitamin D(3) [1alpha,24(R),25(OH)(3)D(3)], 1alpha,25-dihydroxy-24-oxovitamin D(3) [1alpha,25(OH)(2)-24-oxo-D(3)], 1alpha,23(S),25-trihydroxy-24-oxovitamin D(3) and 1alpha,23-dihydroxy-24,25,26,27-tetranorvitamin D(3). This finding indicates that the double bond in the side chain of 1alpha,25(OH)(2)-22-ene-D(3) is reduced during its metabolism. Along with

  20. The influence of a back support harness on spinal forces during sheep shearing.

    PubMed

    Milosavljevic, Stephan; Carman, Allan B; Milburn, Peter D; Wilson, Barry D; Davidson, Peter L

    2004-09-15

    Previous research has classified the occupation of sheep shearing as heavy work where shearers flex their spine and hips for long periods of time, handle awkward loads and expend high amounts of energy. The aim of this research was to investigate the magnitude of spinal forces produced during the shearing phase of the work and to determine whether the use of a commercially available back support harness would reduce these forces. Following discussion on task complexity and risk of back injury with senior shearing instructors, three component tasks of the shearing phase were identified as posing high risk of injury and were prioritized for primary analysis. Although the dragging out of a sheep in preparation for shearing and an unexpected loss of animal control were also identified as being of high risk, technological and instrumentation difficulties precluded their analysis. Twelve experienced shearers were videotaped while shearing with and without the use of a back harness. Surface mounted retro-reflective markers placed on the trunk defined three linked segments: Pelvis, Lumbar and Head, Arms, and Upper Trunk (HAUT). A 3D, link segment, top down, inverse dynamics approach was used to describe the motion and to estimate forces involved during the identified tasks of shearing. The spinal force/time profiles of this sample of shearers demonstrated large compressive and shear forces for all three tasks that are close to the NIOSH and University of Waterloo action limits for compressive and shear forces respectively (McGill 1997, Yingling and McGill 1999, Marras 2000). The use of the back support harness reduced these forces by substantial and statistically significant amounts. This effect was consistent across all three tasks. The results of this study demonstrate the production of high levels of compressive and shear forces within the spine of shearers during the three shearing tasks studied and that the use of a back support harness can substantially reduce these

  1. Formal Alder-ene reaction of a bicyclo[1.1.0]butane in the synthesis of the tricyclic quaternary ammonium core of daphniglaucins

    PubMed Central

    Ueda, Masafumi; Walczak, Maciej A. A.; Wipf, Peter

    2008-01-01

    A tricyclic substructure of the tetracyclic nitrogen core of the daphniglaucins was formed by an oxidative activation of the allyl side chain of a bicyclo[1.1.0]butylmethylamine, a spontaneous intramolecular formal Alder-ene reaction, and a selective cyclization of a triol intermediate. PMID:19129907

  2. Inhibitory effect of some imidazole antifungal compounds on the synthesis of 16-ene-C19-steroid catalyzed by pig testicular microsomes.

    PubMed

    Nakajin, S; Takahashi, K; Shinoda, M

    1991-01-01

    The activity of the enzyme (16-ene-C19-steroid synthesizing enzyme) responsible for the conversion of C21-steroids to 16-ene-C19-steroids, which was localized on pig testicular microsomes, was inhibited by some typical imidazole antifungal compounds such as clotrimazole, econazole, miconazole and ketoconazole which are known to be universal inhibitors of cytochrome P-450-dependent enzymes. The 50% inhibitory concentrations of clotrimazole, econazole and miconazole were 0.29, 0.36 and 1.25 microM, respectively for 16-ene-C19-steroid synthesizing enzyme activity. Clotrimazole was the most powerful inhibitor of all the compounds examined, which shows the competitive inhibition for 16-ene-C19-steroid synthesizing enzyme activity. The Ki-value was 0.26 microM for its activity. The degree of the inhibition by these imidazole compounds was very similar to the inhibition of 17 alpha-hydroxylase and C17,20-lyase activities on pig testicular microsomes.

  3. Design, synthesis, and evaluation of novel 3-amino-4-hydrazine-cyclobut-3-ene-1,2-diones as potent and selective CXCR2 chemokine receptor antagonists.

    PubMed

    Liu, Shilan; Liu, Yinhui; Wang, Hongmei; Ding, Yili; Wu, Hao; Dong, Jingchao; Wong, Angela; Chen, Shu-Hui; Li, Ge; Chan, Manuel; Sawyer, Nicole; Gervais, Francois G; Henault, Martin; Kargman, Stacia; Bedard, Leanne L; Han, Yongxin; Friesen, Rick; Lobell, Robert B; Stout, David M

    2009-10-01

    We describe herein a novel series of 3-amino-4-hydrazine-cyclobut-3-ene-1,2-diones as potent and selective inhibitors against the CXCR2 chemokine receptor and IL-8-mediated chemotaxis of a CXCR2-expressing cell line. Furthermore, these alkyl-hydrazine series inhibitors such as 5b demonstrated acceptable metabolic stability when incubated in human and rat microsomes.

  4. Theoretical Study of Decomposition Pathways for HArF and HKrF

    NASA Technical Reports Server (NTRS)

    Chaban, Galina M.; Lundell, Jan; Gerber, R. Benny; Kwak, Donchan (Technical Monitor)

    2002-01-01

    To provide theoretical insights into the stability and dynamics of the new rare gas compounds HArF and HKrF, reaction paths for decomposition processes HRgF to Rg + HF and HRgF to H + Rg + F (Rg = Ar, Kr) are calculated using ab initio electronic structure methods. The bending channels, HRgF to Rg + HF, are described by single-configurational MP2 and CCSD(T) electronic structure methods, while the linear decomposition paths, HRgF to H + Rg + F, require the use of multi-configurational wave functions that include dynamic correlation and are size extensive. HArF and HKrF molecules are found to be energetically stable with respect to atomic dissociation products (H + Rg + F) and separated by substantial energy barriers from Rg + HF products, which ensure their kinetic stability. The results are compatible with experimental data on these systems.

  5. Therapeutic strategies for harnessing human eosinophils in allergic inflammation, hypereosinophilic disorders, and cancer.

    PubMed

    Amini-Vaughan, Zhaleh J; Martinez-Moczygemba, Margarita; Huston, David P

    2012-10-01

    The eosinophil is a multifunctional granulocyte best known for providing host defense against parasites. Paradoxically, eosinophils are also implicated in the pathogenesis of allergic inflammation, asthma, and hypereosinophilic syndromes. Emerging evidence also supports the potential for harnessing the cytotoxic power of eosinophils and redirecting it to kill solid tumors. Central to eosinophil physiology is interleukin-5 (IL-5) and its receptor (IL-5R) which is composed of a ligand-specific alpha chain (IL-5Rα) and the common beta chain (βc). Eosinophil activation can lead to their degranulation, resulting in rapid release of an arsenal of tissue-destructive proinflammatory mediators and cytotoxic proteins that can be both beneficial and detrimental to the host. This review discusses eosinophil immunobiology and therapeutic strategies for targeting of IL-5 and IL-5R, as well as the potential for harnessing eosinophil cytotoxicity as a tumoricide.

  6. 'Soft' harness for external attachment of large radio transmitters to northern pike (Esox lucius)

    USGS Publications Warehouse

    Herke, S.W.; Moring, J.R.

    1999-01-01

    We developed a 'soft' harness for dorsally attaching large, external radio transmitters to northern pike (Esox lucius). The key harness component was a soft, flexible, thick-walled tubing that prevented tissue abrasion by the attachment lines which passed through the tubing. Six field-tagged fish (1.5-7.5 kg) were monitored for 45-115 days before tracking was terminated. Tracking patterns of fish indicated no apparent effect of these large, external transmitters on movement behavior; further, the transmitters did not appear to entangle the fish in vegetation. One fish with its transmitter still secure was recaptured after 54 days, and there was minimal tissue erosion under the transmitter. With minor improvements for the attachment lines and the transmitter saddle, the method is suitable for externally attaching large telemetry transmitters to fish.

  7. Failed Pavlik harness treatment for DDH as a risk factor for avascular necrosis.

    PubMed

    Tiruveedhula, Madhu; Reading, Isabel C; Clarke, Nicholas M P

    2015-03-01

    Avascular necrosis (AVN) of the femoral head is an irreversible complication seen in the treatment of developmental dysplasia of hip (DDH) with the Pavlik harness. Its incidence is reported to be low after successful reduction of the hip but high if the hip is not concentrically relocated. We aim to investigate its incidence after failed Pavlik harness treatment. We prospectively followed up a group of children who failed Pavlik harness treatment for DDH treated at our institution by the senior author between 1988 and 2001 and compared their rates of AVN with a group of children who presented late and hence were treated surgically. AVN was graded as described by Kalamchi and MacEwen and only grade 2 to 4 AVN was considered significant and included in the analysis. Thirty-seven hips were included in the failed Pavlik group (group 1) and 86 hips in the no Pavlik group (group 2). Ten hips in group 1 developed AVN (27%), whereas only 7 hips in group 2 (8%) developed AVN; the odds of developing AVN after failed Pavlik treatment was 4.7 (95% confidence interval, 1.3-14.1) (P=0.009) with a relative risk of 3.32 (range, 1.37 to 8.05). There was no statistically significant association observed with duration of splintage and severity of AVN (Spearman's correlation, -0.46; P=0.18). However, there was a positive correlation noted with age at presentation and severity of AVN. Therefore, we advise close monitoring of hips in the Pavlik harness and discontinue its use if the hips are not reduced within 3 weeks. Level III.

  8. Harnessing Localized Ridges for High-Aspect-Ratio Hierarchical Patterns with Dynamic Tunability and Multifunctionality

    PubMed Central

    Cao, Changyong; Chan, Hon Fai; Zang, Jianfeng; Leong, Kam W.; Zhao, Xuanhe

    2014-01-01

    We invent a simple method for fabricating high-aspect-ratio, hierarchical and dynamically tunable surface patterns by harnessing localized-ridge instabilities in gold nanofilms coated on elastomer substrates (a); develop a theoretical model to calculate the critical parameters (e.g. wavelength and amplitude) for designing the new patterns (b); and demonstrate novel applications of the patterns as super-hydrophobic coatings (c) and biomimetic cell-culture substrates (d) capable of on-demand tunability. PMID:24339233

  9. The relevance of netnography to the harness of Romanian health care electronic word-of-mouth

    PubMed Central

    Bratucu, R; Gheorghe, IR; Radu, A; Purcarea, VL

    2014-01-01

    Abstract Nowadays, consumers use the computer mediated communication to make purchase decisions on a large variety of products and services. Since health care services are archetypal by nature, consumers in this field are one of the most encountered users of electronic word-of-mouth. The objective of this paper is to explain and support the necessity of adopting a different qualitative method when electronic word of mouth is harnessed on health care dedicated forums, that is, netnography. PMID:25408755

  10. STS-32 Pilot Wetherbee wearing LES is suspended by harness over WETF pool

    NASA Technical Reports Server (NTRS)

    1989-01-01

    STS-32 Pilot James D. Wetherbee, wearing a launch and entry suit (LES) and lauch and entry helmet (LEH), is suspended by his parachute harness over JSC's Weightless Environment Training Facility (WETF) Bldg 29 25 ft deep pool. During the exercises the crew practiced the procedures to follow in the event of an emergency aboard the Space Shuttle and familiarized themselves with post-Challenger pole system of emergency egress.

  11. Inadequate harnesses as a cause of death in two light aircraft accidents.

    PubMed

    Hill, I R

    1980-09-01

    In the two accidents described, both fatalities occurred because the victims were wearing only lap belts. One of the victims was piloting an aircraft. These were survivable aircraft accidents and illustrate the inadequacy of this type of harness. Recently promulgated legislation in the United Kingdom should mean that front seat incidents of this nature will become a rarity. The dangers will still exist for those in rear passenger seats, however, because they are not covered by the new laws.

  12. The relevance of netnography to the harness of Romanian health care electronic word-of-mouth.

    PubMed

    Bratucu, R; Gheorghe, I R; Radu, A; Purcarea, V L

    2014-09-15

    Nowadays, consumers use the computer mediated communication to make purchase decisions on a large variety of products and services. Since health care services are archetypal by nature, consumers in this field are one of the most encountered users of electronic word-of-mouth. The objective of this paper is to explain and support the necessity of adopting a different qualitative method when electronic word of mouth is harnessed on health care dedicated forums, that is, netnography.

  13. Toxic but Drank: Gustatory Aversive Compounds Induce Post-ingestional Malaise in Harnessed Honeybees

    PubMed Central

    Ayestaran, Ainara

    2010-01-01

    Background Deterrent substances produced by plants are relevant due to their potential toxicity. The fact that most of these substances have an unpalatable taste for humans and other mammals contrasts with the fact that honeybees do not reject them in the range of concentrations in which these compounds are present in flower nectars. Here we asked whether honeybees detect and ingest deterrent substances and whether these substances are really toxic to them. Results We show that pairing aversive substances with an odor retards learning of this odor when it is subsequently paired with sucrose. Harnessed honeybees in the laboratory ingest without reluctance a considerable volume (20 µl) of various aversive substances, even if some of them induce significant post-ingestional mortality. These substances do not seem, therefore, to be unpalatable to harnessed bees but induce a malaise-like state that in some cases results in death. Consistently with this finding, bees learning that one odor is associated with sugar, and experiencing in a subsequent phase that the sugar was paired with 20 µl of an aversive substance (devaluation phase), respond less than control bees to the odor and the sugar. Such stimulus devaluation can be accounted for by the malaise-like state induced by the aversive substances. Conclusion Our results indicate that substances that taste bitter to humans as well as concentrated saline solutions base their aversive effect on the physiological consequences that their ingestion generates in harnessed bees rather than on an unpalatable taste. This conclusion is only valid for harnessed bees in the laboratory as freely-moving bees might react differently to aversive compounds could actively reject aversive substances. Our results open a new possibility to study conditioned taste aversion based on post-ingestional malaise and thus broaden the spectrum of aversive learning protocols available in honeybees. PMID:21060877

  14. World Bank: harnessing civil society expertise in undertaking and disseminating research findings.

    PubMed

    Simms, Ben

    2013-01-01

    The UK Consortium on AIDS and International Development was an essential partner to the evaluation leaders in harnessing the contribution and expertise of civil society. This article describes what the partnership entailed, the additional value it brought and how civil society might use the evaluation findings both as a tool for advocacy and a means for improving its own engagement with the individuals directly affected by HIV and with those who care for them.

  15. Numerical Simulation Research on Relationship between the Strong Earthquakes around the Bayan Har Block

    NASA Astrophysics Data System (ADS)

    En, Li Ping

    2017-04-01

    Considering the difference of regional geological structure, active block division, the main active fault zone, irregular topography and layered lithosphere structure, the 3-D viscoelastic finite element model of the Tibetan Plateau including the Bayan Har block is constructed by introducing the latest deep inversion results. Using the observed values of GPS and direction of the maximum principal compressive stress as constrain condition, the present tectonic background stress field of the Tibetan Plateau is reconstructed. Based on it, the 14 strong earthquakes with M≥7 around the Bayan Har block since 1900 are simulated successively. From the viewpoint of Coulomb failure stress, the effective stress and stress field evolution, the relationship between the strong earthquakes around Bayan Har block is discussed. The calculation result shows that considering both the influence of coseismic effect and secular tectonic stress loading, there are 11 earthquakes located in positive value region of total stress change; and while there are 8 earthquakes if only considering the influence of coseismic effect. Before the 2013 Lushan Ms7.0 earthquake, the southern part of Longmenshan fault zone is in a state of high stress. The coseismic Coulomb failure stress of the location of Lushan earthquake caused by Wenchuan earthquake is about 0.016MPa, which indicated that the Lushan earthquake is triggered by Wenchuan earthquake from the viewpoint of Coulomb failure stress. After the strong earthquake sequence since 1900, the stress has been released in most areas of Bayan Har block, and only small areas still in the state of high stress.

  16. Loss of function mutations in HARS cause a spectrum of inherited peripheral neuropathies.

    PubMed

    Safka Brozkova, Dana; Deconinck, Tine; Griffin, Laurie Beth; Ferbert, Andreas; Haberlova, Jana; Mazanec, Radim; Lassuthova, Petra; Roth, Christian; Pilunthanakul, Thanita; Rautenstrauss, Bernd; Janecke, Andreas R; Zavadakova, Petra; Chrast, Roman; Rivolta, Carlo; Zuchner, Stephan; Antonellis, Anthony; Beg, Asim A; De Jonghe, Peter; Senderek, Jan; Seeman, Pavel; Baets, Jonathan

    2015-08-01

    Inherited peripheral neuropathies are a genetically heterogeneous group of disorders characterized by distal muscle weakness and sensory loss. Mutations in genes encoding aminoacyl-tRNA synthetases have been implicated in peripheral neuropathies, suggesting that these tRNA charging enzymes are uniquely important for the peripheral nerve. Recently, a mutation in histidyl-tRNA synthetase (HARS) was identified in a single patient with a late-onset, sensory-predominant peripheral neuropathy; however, the genetic evidence was lacking, making the significance of the finding unclear. Here, we present clinical, genetic, and functional data that implicate HARS mutations in inherited peripheral neuropathies. The associated phenotypic spectrum is broad and encompasses axonal and demyelinating motor and sensory neuropathies, including four young patients presenting with pure motor axonal neuropathy. Genome-wide linkage studies in combination with whole-exome and conventional sequencing revealed four distinct and previously unreported heterozygous HARS mutations segregating with autosomal dominant peripheral neuropathy in four unrelated families (p.Thr132Ile, p.Pro134His, p.Asp175Glu and p.Asp364Tyr). All mutations cause a loss of function in yeast complementation assays, and p.Asp364Tyr is dominantly neurotoxic in a Caenorhabditis elegans model. This study demonstrates the role of HARS mutations in peripheral neuropathy and expands the genetic and clinical spectrum of aminoacyl-tRNA synthetase-related human disease. © The Author (2015). Published by Oxford University Press on behalf of the Guarantors of Brain. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

  17. Mapping the Sea Floor of the Historic Area Remediation Site (HARS) Offshore of New York City

    USGS Publications Warehouse

    Butman, Bradford

    2002-01-01

    The area offshore of New York City has been used for the disposal of dredged material for over a century. The area has also been used for the disposal of other materials such as acid waste, industrial waste, municipal sewage sludge, cellar dirt, and wood. Between 1976 and 1995, the New York Bight Dredged Material Disposal Site, also known as the Mud Dump Site (MDS), received on average about 6 million cubic yards of dredged material annually. In September 1997 the MDS was closed as a disposal site, and it and the surrounding area were designated as the Historic Area Remediation Site (HARS). The sea floor of the HARS, approximately 9 square nautical miles in area, currently is being remediated by placing a minimum 1-m-thick cap of clean dredged material on top of the surficial sediments that are contaminated from previous disposal of dredged and other materials. The U.S. Geological Survey (USGS) is working cooperatively with the U.S. Army Corps of Engineers (USACE) to map the sea floor geology of the HARS and changes in the characteristics of the surficial sediments over time.

  18. Effects of harness-attached transmitters on premigration and reproduction of Brant

    USGS Publications Warehouse

    Ward, David H.; Flint, Paul L.

    1995-01-01

    Radio transmitters are an important tool in waterfowl ecology studies, but little is known about their effects on free-ranging geese. We attached transmitters to female brant (Branta bernicla nigricans) to investigate migration schedules at a fall staging area, return rates to nesting grounds, and nesting rates of returning females in subsequent breeding seasons. Radio-tagged females (n = 62) carried either 35-g back-mounted transmitters attached with ribbon harnesses, or 26- or 32-g back-mounted transmitters affixed with plastic-coated wire harnesses (Dwyer 1972). Arrival and departure schedules at Izembek Lagoon, Alaska, did not differ (P > 0.05) between radio-tagged females and the entire population in 1987-89. Color-banded females with transmitters returned to the breeding colony in subsequent nesting seasons (1988-92) at a lower (P ≤ 0.003) rate (≤4%) than color-banded females without transmitters (57-83%). The 1 returning color-banded female with a transmitter did not breed, while an average 90% of the returning color-banded females without transmitters nested in subsequent breeding seasons (P = 0.005). Back-mounted, harness-attached transmitters may bias data in studies of waterfowl behavior, productivity, and survival.

  19. Root-derived CLE glycopeptides control nodulation by direct binding to HAR1 receptor kinase.

    PubMed

    Okamoto, Satoru; Shinohara, Hidefumi; Mori, Tomoko; Matsubayashi, Yoshikatsu; Kawaguchi, Masayoshi

    2013-01-01

    Leguminous plants establish a symbiosis with rhizobia to enable nitrogen fixation in root nodules under the control of the presumed root-to-shoot-to-root negative feedback called autoregulation of nodulation. In Lotus japonicus, autoregulation is mediated by CLE-RS genes that are specifically expressed in the root, and the receptor kinase HAR1 that functions in the shoot. However, the mature functional structures of CLE-RS gene products and the molecular nature of CLE-RS/HAR1 signalling governed by these spatially distant components remain elusive. Here we show that CLE-RS2 is a post-translationally arabinosylated glycopeptide derived from the CLE domain. Chemically synthesized CLE-RS glycopeptides cause significant suppression of nodulation and directly bind to HAR1 in an arabinose-chain and sequence-dependent manner. In addition, CLE-RS2 glycopeptide specifically produced in the root is found in xylem sap collected from the shoot. We propose that CLE-RS glycopeptides are the long sought mobile signals responsible for the initial step of autoregulation of nodulation.

  20. Accelerations and Passenger Harness Loads Measured in Full-Scale Light-Airplane Crashes

    NASA Technical Reports Server (NTRS)

    Eiband, A. Martin; Simpkinson, Scott H.; Black, Dugald O.

    1953-01-01

    Full-scale light-airplane crashes simulating stall-spin accidents were conducted to determine the decelerations to which occupants are exposed and the resulting harness forces encountered in this type of accident. Crashes at impact speeds from 42 to 60 miles per hour were studied. The airplanes used were of the familiar steel-tube, fabric-covered, tandem, two-seat type. In crashes up to an impact speed of 60 miles per hour, crumpling of the forward fuselage structure prevented the maximum deceleration at the rear-seat location from exceeding 26 to 33g. This maximum g value appeared independent of the impact speed. Restraining forces in the seatbelt - shoulder-harness combination reached 5800 pounds. The rear-seat occupant can survive crashes of the type studied at impact speeds up to 60 miles per hour, if body movement is restrained by an adequate seatbelt-shoulder-harness combination so as to prevent injurious contact with obstacles normally present in the cabin. Inwardly collapsing cabin structure, however, is a potential hazard in the higher-speed crashes.

  1. Molecular mapping of a sunflower rust resistance gene from HAR6

    PubMed Central

    Bulos, Mariano; Ramos, María L.; Altieri, Emiliano; Sala, Carlos A.

    2013-01-01

    Sunflower rust, caused by Puccinia helianthi Schw., can result in significant yield losses in cultivated sunflower (Helianthus annuus L. var. macrocarpus Ckll.). HAR6 is a germplasm population resistant to most predominant rust races. The objectives of this study were to map the resistance factor present in HAR6 (RHAR6), and to provide and validate molecular tools for the identification of this gene for marker assisted selection purposes. Virulence reaction of seedlings for the F2 population and F2:3 families suggested that a single dominant gene confers rust resistance in HAR6-1, a selected rust resistance line from the original population. Genetic mapping with eight markers covered 97.4 cM of genetic distance on linkage group 13 of the sunflower consensus map. A co-dominant marker ZVG61 is the closest marker distal to RHAR6 at a genetic distance of 0.7 cM, while ORS581, a dominant marker linked in the coupling phase, is proximal to RHAR6 at a genetic distance of 1.5 cM. Validation of these markers was assessed by converting a susceptible line into a rust resistant isoline by means of marker assisted backcrossing. The application of these results to assist the breeding process and to design new strategies for rust control in sunflower is discussed. PMID:23641190

  2. Crystal structure of bis-(η(2)-ethyl-ene)(η(5)-penta-methyl-cyclo-penta-dien-yl)cobalt.

    PubMed

    Ramful, Chandika D; Robertson, Katherine N; Ylijoki, Kai E O

    2016-09-01

    The title compound, [Co(C10H15)(C2H4)2], was prepared by Na/Hg reduction of [Co2(C10H15)2(μ-Cl)2] in THF under an ethyl-ene atmosphere and crystallized from pentane at 193 K. The Co-C(olefin) bonds have an average length of 2.022 (2) Å, while the Co-C(penta-dien-yl) bonds average 2.103 (19) Å. The olefin C=C bonds are 1.410 (1) Å. The dihedral angle between the planes defined by the cyclo-penta-dienyl ligand and the two olefin ligands is 0.25 (12)°. In the crystal, mol-ecules are linked into chains by C-H⋯π inter-actions.

  3. Facile Synthesis of Prussian Blue Derivate-Modified Mesoporous Material via Photoinitiated Thiol-Ene Click Reaction for Cesium Adsorption.

    PubMed

    Qian, Jun; Ma, Jiaqi; He, Weiwei; Hua, Daoben

    2015-08-01

    A novel strategy to synthesize a functional mesoporous material for efficient removal of cesium is reported. Specifically, Prussian blue derivate-modified SBA-15 (SBA-15@FC) was prepared by photoinitiated thiol-ene reaction between thiol-modified SBA-15 and pentacyano(4-vinyl pyridine)ferrate complex. The effects of weight percentage of the Prussian blue derivate, pH, adsorbent dose, co-existing ions, and initial concentration were evaluated on the adsorption of cesium ions. The adsorption kinetically follows a pseudo-second-order model and reaches equilibrium within 2 h with a high adsorption capacity of about 13.90 mg Cs g(-1) , which indicates that SBA-15@FC is a promising adsorbent to effectively remove cesium from aqueous solutions.

  4. Preparation of a novel carboxyl stationary phase by "thiol-ene" click chemistry for hydrophilic interaction chromatography.

    PubMed

    Peng, Xi-Tian; Liu, Tao; Ji, Shu-Xian; Feng, Yu-Qi

    2013-08-01

    A novel carboxyl-bonded silica stationary phase was prepared by "thiol-ene" click chemistry. The resultant Thiol-Click-COOH phase was evaluated under hydrophilic interaction liquid chromatography (HILIC) mobile phase conditions. A comparison of the chromatographic performance of Thiol-Click-COOH and pure silica columns was performed according to the retention behaviors of analytes and the charged state of the stationary phases. The results indicated that the newly developed Thiol-Click-COOH column has a higher surface charge and stronger hydrophilicity than the pure silica column. Furthermore, the chromatographic behaviors of five nucleosides on the Thiol-Click-COOH phase were investigated in detail. Finally, a good separation of 13 nucleosides and bases, and four water-soluble vitamins was achieved.

  5. Synthesis of antibacterial amphiphilic elastomer based on polystyrene-block-polyisoprene-block-polystyrene via thiol-ene addition.

    PubMed

    Keleş, Elif; Hazer, Baki; Cömert, Füsun B

    2013-04-01

    A new type of amphiphilic antibacterial elastomer has been described. Thermoplastic elastomer, polystyrene-block-polyisoprene-block-polystyrene (PS-b-PI-b-PS) triblock copolymer was functionalized in toluene solution by free radical mercaptan addition in order to obtain an amphiphilic antibacterial elastomer. Thiol terminated PEG was grafted through the double bonds of PS-b-PI-b-PS via free radical thiol-ene coupling reaction. The antibacterial properties of the amphiphilic graft copolymers were observed. The original and the modified polymers were used to create microfibers in an electro-spinning process. Topology of the electrospun micro/nanofibers were studied by using scanning electron microscopy (SEM). The chemical structures of the amphiphilic comb type graft copolymers were elucidated by the combination of elemental analysis, (1)H NMR, (13)C NMR, GPC and FTIR.

  6. Color-Transformable Silicone Elastomers Prepared by Thiol-Ene Reaction with Potential Application in UV-LEDs.

    PubMed

    Zuo, Yujing; Gou, Zhiming; Zhang, Jie; Feng, Shengyu

    2016-04-01

    A series of high-efficiency, full-color fluorescent elastomers based on polysiloxane matrix prepared by an easy thiol-ene "click" reaction is reported here. It is found for the first time that the same elastomer can emit transformable colors by conveniently altering the excitation wavelength because of the effect of energy transfer and the "fluorescence switch" of lanthanide ions. A fluent change in emission colors can also be feasible and conveniently reproducible by varying the stoichiometric ratio of lanthanide ions and rhodamine-B in solution and in polymer elastomers. The obtained elastomers are further coated onto commercially available UV-LED cells from the solution medium followed by an in situ cross-linking step.

  7. Chiral bis(oxazoline) copper(II) complexes: versatile catalysts for enantioselective cycloaddition, Aldol, Michael, and carbonyl ene reactions.

    PubMed

    Johnson, J S; Evans, D A

    2000-06-01

    A bis(oxazoline) (box) copper(II) complex and its hydrated counterpart (1 and 2) function as enantioselective Lewis acid catalysts for carbocyclic and hetero Diels-Alder, aldol, Michael, ene, and amination reactions with substrates capable of chelation through six- and five-membered rings. X-ray crystallography of the chiral complexes reveals a propensity for the formation of distorted square planar or square pyramidal geometries. The sense of asymmetric induction is identical for all the processes catalyzed by [Cu((S,S)-t-Bu-box)](X)(2) complexes 1 and 2 (X = OTf and SbF) resulting from the intervention of a distorted square planar catalyst-substrate binary complex. These catalyzed processes exhibit excellent temperature-selectivity profiles. Reactions catalyzed by [Cu(S,S-Ph-pybox)](SbF(6))(2) and their derived chelation complexes are also discussed.

  8. Fabrication of Large-Area Two-Dimensional Microgel Colloidal Crystals via Interfacial Thiol-Ene Click Reaction.

    PubMed

    Li, Xiaoyun; Weng, Junying; Guan, Ying; Zhang, Yongjun

    2016-04-26

    A method for the fabrication of high quality, large area 2D colloidal crystals (CCs) using poly(N-isopropylacrylamide) (PNIPAM) microgel sphere, an extremely soft colloid, as building block was proposed. First the microgel spheres were assembled into 3D colloidal crystals. The first 111 plane of the 3D crystal close to the substrate was then fixed in situ onto the substrate. Highly efficient photoinitiated thiol-ene coupling was chosen for the fixing purpose. Thanks to the high quality of 3D microgel CCs, the resulting 2D CCs exhibit a high degree of ordering. Large area 2D CCs were fabricated because large area 3D microgel CCs can be facilely fabricated. Besides planar substrates, the method allows the fabrication of 2D CCs on curved surface, too. In addition, the interpartical distance in the 2D CCs can be tuned by the concentration of the microgel dispersion.

  9. Orthogonal dual thiol–chloroacetyl and thiol–ene couplings for the sequential one-pot assembly of heteroglycoclusters

    PubMed Central

    Fiore, Michele; Daskhan, Gour Chand; Thomas, Baptiste

    2014-01-01

    Summary We describe the first one-pot orthogonal strategy to prepare well-defined cyclopeptide-based heteroglycoclusters (hGCs) from glycosyl thiols. Both thiol–chloroactetyl coupling (TCC) and thiol–ene coupling (TEC) have been used to decorate cyclopeptides regioselectively with diverse combination of sugars. We demonstrate that the reaction sequence starting with TCC can be performed one-pot whereas the reverse sequence requires a purification step after the TEC reaction. The versatility of this orthogonal strategy has been demonstrated through the synthesis of diverse hGCs displaying alternating binary combinations of α-D-Man or β-D-GlcNAc, thus providing rapid access to attractive heteroglycosylated platforms for diverse biological applications. PMID:25161711

  10. Holographic polymer dispersed liquid crystal (HPDLC) transmission gratings formed by visible light initiated thiol-ene photopolymerization

    NASA Astrophysics Data System (ADS)

    Wofford, Jeremy M.; Natarajan, Lalgudi V.; Tondiglia, Vincent P.; Sutherland, Richard L.; Lloyd, Pamela F.; Siwecki, Stephen A.; Bunning, Timothy J.

    2006-08-01

    We report on the initial development of a visible initiator for thiol-ene photopolymerization using the 647 nm radiation from a Krypton ion laser. The photoinitiator system consists of the dye oxazine 170 perchlorate and the co-initiator benzoyl peroxide. Electron transfer occurs between the singlet excited state of the oxazine dye and benzoyl peroxide with subsequent decomposition of the peroxide yielding benzoyl oxy radicals capable of free radical initiation. We demonstrate that this photoinitiation system enables holographic patterning of HPDLC gratings as initial Bragg transmission gratings with a periodicity less than one micron using 647 nm radiation. These gratings were electrically switchable between a diffractive and transmissive state. Morphology studies using bright field transmission electron microscopy (BFTEM) indicate the phase separation of nearly spherical shaped nematic liquid crystal droplets of several hundred nanometers in diameter. This demonstration suggests that reflection gratings can be written using this photoinitiator system and 647 nm radiation which have switchable notch wavelengths approaching 2 microns.

  11. Modifying surface resistivity and liquid moisture management property of keratin fibers through thiol-ene click reactions.

    PubMed

    Yu, Dan; Cai, Jackie Y; Church, Jeffrey S; Wang, Lijing

    2014-01-22

    This paper reports on a new method for improving the antistatic and liquid moisture management properties of keratinous materials. The method involves the generation of thiols by controlled reduction of cystine disulfide bonds in keratin with tris(2-carboxyethyl) phosphine hydrochloride and subsequent grafting of hydrophilic groups onto the reduced keratin by reaction with an acrylate sulfonate or acrylamide sulfonate through thiol-ene click chemistry. The modified substrates were characterized with Raman spectroscopy and scanning electron microscopy and evaluated for their performance changes in liquid moisture management, surface resistivity, and wet burst strength. The results have revealed that the thiol-acrylate reaction is more efficient than the thiol-acrylamide reaction, and the keratinous substrate modified with an acrylate sulfonate salt exhibits significantly improved antistatic and liquid moisture management properties.

  12. Surface modification of model hydrogel contact lenses with hyaluronic acid via thiol-ene "click" chemistry for enhancing surface characteristics.

    PubMed

    Korogiannaki, Myrto; Zhang, Jianfeng; Sheardown, Heather

    2017-10-01

    Discontinuation of contact lens wear as a result of ocular dryness and discomfort is extremely common; as many as 26% of contact lens wearers discontinue use within the first year. While patients are generally satisfied with conventional hydrogel lenses, improving on-eye comfort continues to remain a goal. Surface modification with a biomimetic, ocular friendly hydrophilic layer of a wetting agent is hypothesized to improve the interfacial interactions of the contact lens with the ocular surface. In this work, the synthesis and characterization of poly(2-hydroxyethyl methacrylate) surfaces grafted with a hydrophilic layer of hyaluronic acid are described. The immobilization reaction involved the covalent attachment of thiolated hyaluronic acid (20 kDa) on acrylated poly(2-hydroxyethyl methacrylate) via nucleophile-initiated Michael addition thiol-ene "click" chemistry. The surface chemistry of the modified surfaces was analyzed by Fourier transform infrared spectroscopy-attenuated total reflectance and X-ray photoelectron spectroscopy. The appearance of N (1s) and S (2p) peaks on the low resolution X-ray photoelectron spectroscopy spectra confirmed successful immobilization of hyaluronic acid. Grafting hyaluronic acid to the poly(2-hydroxyethyl methacrylate) surfaces decreased the contact angle, the dehydration rate, and the amount of nonspecific sorption of lysozyme and albumin in comparison to pristine hydrogel materials, suggesting the development of more wettable surfaces with improved water-retentive and antifouling properties, while maintaining optical transparency (>92%). In vitro testing also showed excellent viability of human corneal epithelial cells with the hyaluronic acid-grafted poly(2-hydroxyethyl methacrylate) surfaces. Hence, surface modification with hyaluronic acid via thiol-ene "click" chemistry could be useful in improving contact lens surface properties, potentially alleviating symptoms of contact lens related dryness and discomfort during

  13. The Belem Framework for Action: Harnessing the Power and Potential of Adult Learning and Education for a Viable Future

    ERIC Educational Resources Information Center

    Adult Learning, 2012

    2012-01-01

    This article presents the Belem Framework for Action. This framework focuses on harnessing the power and potential of adult learning and education for a viable future. This framework begins with a preamble on adult education and towards lifelong learning.

  14. The Belem Framework for Action: Harnessing the Power and Potential of Adult Learning and Education for a Viable Future

    ERIC Educational Resources Information Center

    Adult Learning, 2012

    2012-01-01

    This article presents the Belem Framework for Action. This framework focuses on harnessing the power and potential of adult learning and education for a viable future. This framework begins with a preamble on adult education and towards lifelong learning.

  15. Corticosteroidogenesis in the toad Bufo arenarum H: evidence for a precursor role for an aldosterone 3 beta-hydroxy-5-ene analogue (3 beta, 11 beta, 21-trihydroxy-20-oxo-5-pregnen-18-al).

    PubMed Central

    Ceballos, N R; Shackleton, C H; Harnik, M; Cozza, E N; Gros, E G; Lantos, C P

    1993-01-01

    A material isolated following pregnenolone incubations with toad (Bufo arenarum) inter-renal tissue at 28 degrees C has been identified as a 3 beta-hydroxy-5-ene analogue of aldosterone (3 beta, 11 beta, 21-trihydroxy-20-oxo-5-pregnen-18-al). The initial identification was made by enzymic and m.s. methods, and structural confirmation was achieved through comparison with chemically synthesized authentic material. The relative efficacy of corticosterone, 18-hydroxycorticosterone and the 3 beta-hydroxy-5-ene aldosterone analogue as aldosterone precursors was evaluated. In the in vitro situation studied, the 3 beta-hydroxy-5-ene steroid was by far the best precursor. PMID:8503841

  16. Development of an alternative five-point restraint harness to accommodate children with special healthcare needs in child safety seats.

    PubMed

    Brinkey, Lori; Manary, Miriam; Santioni, Daniel

    2011-01-01

    Commercial automotive child restraint systems (CRSs) do not accommodate all children with special healthcare needs. This study developed an alternative harness for a commercial CRS to meet the needs of children for whom a five-point harness cannot be positioned over medically involved areas and/or children whose conditions require the harness belts to be threaded through medical devices. After initial design work and a series of frontal sled-impact tests, one of two prototype designs was chosen for fit testing on children with and without healthcare conditions. After a minor modification, additional sled-impact testing was conducted to determine compliance of the system to federal standards. The CRS with alternate harness provides good fit to children with a variety of healthcare needs and complies with all performance criteria of FMVSS 213, with the exception of peak forward head excursion using the Hybrid III 6-year-old crash-test dummy. It is expected that all performance criteria will be met using the newly-issued federal allowance to conduct CRS frontal-impact tests using an earlier version of the dummy. The new harness shows promise as a low-cost solution for achieving a safer level of transportation for children who may otherwise travel unrestrained or with a severely misused CRS harness.

  17. Protective level of safety harnesses combined with some racing car seats in frontal impacts--a laboratory study.

    PubMed

    Ottoson, A L; Lövsund, P

    1986-12-01

    As a basis for a prospective modification of the present seat-belt regulation in Sweden, the protective level of safety harnesses compared with three-point belts has been studied. Biomechanical tests were carried out with different combinations of belts and seats. The results showed that a three-point belt on a conventional seat offered the best protection in frontal impacts. The geometry of the safety harness (inverted Y-harness and four-point belt) induces the lap belt to slide over the iliac crest and the restraining force will be on the abdomen (submarining). This may be prevented by the use of a six-point belt, where two crotch straps keep the lap belt in position. The safety harness induces strong rebounds on the head, owing to the fact that the shoulder straps stop the forward motion of the torso too fast. High accelerations and HIC-values were registered for the head. The shoulder straps of the safety harnesses also expose the wearer's shoulders and spine to high stresses in frontal impacts, which may induce injuries to the shoulders and compression injuries to the spine. Various solutions which may result in an increase of the protective level of the system safety harness and racing-car seat in frontal impacts are discussed.

  18. Different DMRT3 Genotypes Are Best Adapted for Harness Racing and Riding in Finnhorses.

    PubMed

    Jäderkvist Fegraeus, Kim; Johansson, Lisa; Mäenpää, Minna; Mykkänen, Anna; Andersson, Lisa S; Velie, Brandon D; Andersson, Leif; Árnason, Thorvaldur; Lindgren, Gabriella

    2015-01-01

    Previous studies showed a positive effect of the DMRT3 "gait keeper" mutation on harness racing performance in Standardbreds, French-, and Nordic trotters. The mutation has also been shown to influence riding traits in multiple breeds. This study investigated the effect of the DMRT3 mutation on harness racing performance and riding traits in Finnhorses. Finnhorses used for harness racing (n = 180) and for riding (n = 59) were genotyped for the DMRT3 mutation. For the trotters the genotypes were evaluated for association with racing performance (number of starts, victories, placings, earnings, and race times). At 3-6 years of age the AA genotype was superior compared with the CA and CC genotypes. The AA horses had a significantly higher proportion of victories (P = 1.4×10(-6)) and placings (P = 4.1×10(-7)), better race times (P = 0.01), and earned more money (P = 0.009) compared with C-horses. For the Finnhorses used for riding the owners answered a questionnaire to score how well the horse performed the gaits walk, trot, and canter on a scale from 1 to 6. These scores were tested for association with the DMRT3 genotypes. Although AA horses were more successful as racehorses, the CC and CA horses appear more adapted for classical riding disciplines. The AA horses received significantly lower gait scores compared with C-horses for the majority of gaits. Except for rhythm in extended canter (P = 0.05), there were no significant differences between CA and CC horses. This study shows that there are different optimal genotypes for different disciplines and the DMRT3 mutation clearly influences gaits and performance in Finnhorses.

  19. Characterization of the metabolic pathway of 1,25-dihydroxy-16-ene vitamin D3 in rat kidney by on-line high performance liquid chromatography-electrospray tandem mass spectrometry.

    PubMed

    Yeung, B; Vouros, P; Siu-Caldera, M L; Reddy, G S

    1995-04-18

    1,25-Dihydroxy-16-ene vitamin D3 is a synthetic analog of 1,25-dihydroxyvitamin D3, the most physiologically active metabolite of vitamin D3. The renal metabolism of 1,25-dihydroxy-16-ene vitamin D3 had been studied previously using a perfused rat kidney system [Reddy et al., Bioorg Med Chem Lett 3: 1879-1884, 1993], and its C-24 oxidative metabolic pathway had been found to be different from that of 1,25-dihydroxyvitamin D3 by HPLC. To further delineate the differences between the C-24 oxidative metabolic pathways of 1,25-dihydroxyvitamin D3 and 1,25-dihydroxy-16-ene vitamin D3 in this present study we investigated the C-24 oxidation pathway of 1,25-dihydroxy-16-ene vitamin D3 using a novel detection approach based on on-line capillary liquid chromatography coupled to electrospray tandem mass spectrometry. Two types of tandem mass spectrometric detection were employed to characterize the metabolites in the kidney perfusate: (a) the preliminary screening of metabolites by parent scan, which led to the tentative discovery of the production of 1,23,25-trihydroxy-24-oxo-16-ene vitamin D3, a new metabolite of 1,25-dihydroxy-16-ene vitamin D3, and (b) the pharmacokinetic studies of the substrate, 1,25-dihydroxy-16-ene vitamin D3 and its metabolites by multiple reaction monitoring. In the latter, the mass spectrometric sensitivity for quantification was found to be about 20-fold better than UV detection. The current work concluded that the C-24 oxidative metabolic pathway of 1,25-dihydroxy-16-ene vitamin D3 closely mimicked that of its natural counterpart. Furthermore, the use of mass spectrometry permitted the clearance rate of the starting substrate to be studied at a more physiological level (ng/mL or submicromolar level), which had not been possible previously by HPLC-UV detection.

  20. Wearing a safety harness during treadmill walking influences lower extremity kinematics mainly through changes in ankle regularity and local stability

    PubMed Central

    2012-01-01

    Background Wearing a harness during treadmill walking ensures the subject's safety and is common practice in biomedical engineering research. However, the extent to which such practice influences gait is unknown. This study investigated harness-related changes in gait patterns, as evaluated from lower extremity kinematics during treadmill walking. Findings Healthy subjects (n = 10) walked on a treadmill at their preferred speed for 3 minutes with and without wearing a harness (LiteGait®, Mobility Research, Inc.). In the former condition, no weight support was provided to the subjects. Lower extremity kinematics was assessed in the sagittal plane from the mean (meanRoM), standard deviation (SDRoM) and coefficient of variation (CoVRoM) of the hip, knee, and ankle ranges of motion (RoM), as well as from the sample entropy (SampEn) and the largest Lyapunov exponent (LyE) of the joints' angles. Wearing the harness increased the meanRoM of the hip, the SDRoM and the CoVRoM of the knee, and the SampEn and the LyE of the ankle. In particular, the harness effect sizes for both the SampEn and the LyE of the ankle were large, likely reflecting a meaningful decline in the neuromuscular stabilizing control of this joint. Conclusions Wearing a harness during treadmill walking marginally influences lower extremity kinematics, resulting in more or less subtle changes in certain kinematic variables. However, in cases where differences in gait patterns would be expressed through modifications in these variables, having subjects walk with a harness may mask or reinforce such differences. PMID:22305105

  1. New Dimensions in Microarchitecture Harnessing 3D Integration Technologies (BRIEFING CHARTS)

    DTIC Science & Technology

    2007-03-06

    New Dimensions in Microarchitecture Harnessing 3D Integration Technologies Kerry Bernstein IBM T.J. Watson Research Center Yorktown Heights, NY...e m o r y H i e r a r c h y L1 Size limited by Cycle time Components of Processor Performance From ISCA ’06 Keynote address by Phil Emma , IBM Delay...From ISCA ’06 Keynote address by Phil Emma , IBM 6 March, 2007 New Dimensions in Microarchitecture 8 What Is Bandwidth Used For? Miss Penalty

  2. Harnessing collaborative technology to accelerate achievement of chronic disease management objectives for Canada.

    PubMed

    Thompson, Leslee J; Healey, Lindsay; Falk, Will

    2007-01-01

    Morgan and colleagues put forth a call to action for the transformation of the Canadian healthcare system through the adoption of a national chronic disease prevention and management (CDPM) strategy. They offer examples of best practices and national solutions including investment in clinical information technologies to help support improved care and outcomes. Although we acknowledge that the authors propose CDPM solutions that are headed in the right direction, more rapid deployment of solutions that harness the potential of advanced collaborative technologies is required. We provide examples of how technologies that exist today can help to accelerate the achievement of some key CDPM objectives.

  3. Deaf Workers in Restaurant, Retail, and Hospitality Sector Employment: Harnessing Research to Promote Advocacy.

    PubMed

    Stokar, Hayley

    2017-09-06

    A quarter century after the passage of the Americans with Disabilities Act (ADA) (1990), workplace accommodation is still a struggle for deaf employees and their managers. Many challenges are the result of communication barriers that can be overcome through much needed-though often absent-advocacy and training. The current article highlights the literature on the employment of deaf individuals in the United States service industries of food service, retail, and hospitality conducted from 2000-2016. Exploring dimensions of both hiring and active workplace accommodation, suggestions are made for how social work advocates can harness information and strengthen their approaches for educating managers and supporting workers.

  4. Biology and Applications of CRISPR Systems: Harnessing Nature's Toolbox for Genome Engineering.

    PubMed

    Wright, Addison V; Nuñez, James K; Doudna, Jennifer A

    2016-01-14

    Bacteria and archaea possess a range of defense mechanisms to combat plasmids and viral infections. Unique among these are the CRISPR-Cas (clustered regularly interspaced short palindromic repeats-CRISPR associated) systems, which provide adaptive immunity against foreign nucleic acids. CRISPR systems function by acquiring genetic records of invaders to facilitate robust interference upon reinfection. In this Review, we discuss recent advances in understanding the diverse mechanisms by which Cas proteins respond to foreign nucleic acids and how these systems have been harnessed for precision genome manipulation in a wide array of organisms.

  5. Classical conditioning of proboscis extension in harnessed Africanized honey bee queens (Apis mellifera L.).

    PubMed

    Aquino, Italo S; Abramson, Charles I; Soares, Ademilson E E; Fernandes, Andrea Cardoso; Benbassat, Danny

    2004-06-01

    Experiments are reported on learning in virgin Africanized honey bee queens (Apis mellifera L.). Queens restrained in a "Pavlovian harness" received a pairing of hexanal odor with a 1.8-M feeding of sucrose solution. Compared to explicitly unpaired controls, acquisition was rapid in reaching about 90%. Acquisition was also rapid in queens receiving an unconditioned stimulus of "bee candy" or an unconditioned stimulus administered by worker bees. During extinction the conditioned response declines. The steepest decline was observed in queens receiving an unconditioned stimulus of bee candy. These findings extend previous work on learning of Afrianized honey bee workers to a population of queen bees.

  6. The IS-ENES climate4impact portal: bridging the CMIP5 and CORDEX data to impact users

    NASA Astrophysics Data System (ADS)

    Som de Cerff, Wim; Plieger, Maarten; Page, Christian; Tatarinova, Natalia; Hutjes, Ronald; de Jong, Fokke; Bärring, Lars; Sjökvist, Elin; Vega Saldarriaga, Manuel; Santiago Cofiño Gonzalez, Antonio

    2015-04-01

    The aim of climate4impact (climate4impact.eu) is to enhance the use of Climate Research Data and to enhance the interaction with climate effect/impact communities. The portal is based on 17 impact use cases from 5 different European countries, and is evaluated by a user panel consisting of use case owners. It has been developed within the IS-ENES European project and is currently operated and further developed in the IS ENES2 project. As the climate impact community is very broad, the focus is mainly on the scientific impact community. Climate4impact is connected to the Earth System Grid Federation (ESGF) nodes containing global climate model data (GCM data) from the fifth phase of the Coupled Model Intercomparison Project (CMIP5) and regional climate model data (RCM) data from the Coordinated Regional Climate Downscaling Experiment (CORDEX). This global network of climate model data centers offers services for data description, discovery and download. The climate4impact portal connects to these services using OpenID, and offers a user interface for searching, visualizing and downloading global climate model data and more. A challenging task is to describe the available model data and how it can be used. The portal informs users about possible caveats when using climate model data. All impact use cases are described in the documentation section, using highlighted keywords pointing to detailed information in the glossary. Climate4impact currently has two main objectives. The first one is to work on a web interface which automatically generates a graphical user interface on WPS endpoints. The WPS calculates climate indices and subset data using OpenClimateGIS/icclim on data stored in ESGF data nodes. Data is then transmitted from ESGF nodes over secured OpenDAP and becomes available in a new, per user, secured OpenDAP server. The results can then be visualized again using ADAGUC WMS. Dedicated wizards for processing of climate indices will be developed in close

  7. Monooxime reactivators of acetylcholinesterase with (E)-but-2-ene linker: preparation and reactivation of tabun- and paraoxon-inhibited acetylcholinesterase.

    PubMed

    Musilek, Kamil; Holas, Ondrej; Jun, Daniel; Dohnal, Vlastimil; Gunn-Moore, Frank; Opletalova, Veronika; Dolezal, Martin; Kuca, Kamil

    2007-11-01

    Acetylcholinesterase reactivators are crucial antidotes for the treatment of organophosphate intoxication. Fifteen new monooxime reactivators of acetylcholinesterase with a (E)-but-2-ene linker were developed in an effort to extend the properties of K-oxime (E)-1-(4-carbamoylpyridinium)-4-(4-hydroxyiminomethylpyridinium)-but-2-ene dibromide (K203). The known reactivators (pralidoxime, HI-6, obidoxime, K075, K203) and the new compounds were tested in vitro on a model of tabun- and paraoxon-inhibited AChE. Monooxime reactivators were not able to exceed the best known compounds for tabun poisoning, but some of them did show reactivation comparable with known compounds for paraoxon poisoning. However, extensive differences were found by a SAR study for various substitutions on the non-oxime part of the reactivator molecule.

  8. First example of stepwise, zwitterionic mechanism for bicyclo[2.2.1]hept-5-ene (norbornene) formation process catalyzed by the 1-butyl-3-methylimidazolium cations.

    PubMed

    Jasiński, Radomir

    B3LYP/6-31++G(d) calculations indicated that the reaction of (2E)-3-phenyl-2-nitroprop-2-enenitrile with cyclopentadiene catalyzed by cations of 1,3-dialkylimidazolium ionic liquid shall not take place according to the classical scheme of one-step [2+4] Diels-Alder cycloaddition. Along the path finally leading to bicyclo[2.2.1]hept-5-ene (norbornene) with a nitro group in endo orientation, the process of bicarbocyclic skeleton formation shall take place according to the domino mechanism, via [2+4] heterocycloadduct. On the other hand, along the path leading finally to bicyclo[2.2.1]hept-5-ene with a nitro group in exo orientation, acyclic adduct with a zwitterionic nature is formed in the first reaction, which undergoes cyclisation next in the second step of the reaction.

  9. Preparation and Characterization of Polyhedral Oligomeric Silsesquioxane-Containing, Titania-Thiol-Ene Composite Photocatalytic Coatings, Emphasizing the Hydrophobic-Hydrophilic Transition.

    PubMed

    Jefferson, LaCrissia U; Netchaev, Anton D; Jefcoat, Jennifer A; Windham, Amber D; McFarland, Frederick M; Guo, Song; Buchanan, Randy K; Buchanan, J Paige

    2015-06-17

    Coatings prepared from titania-thiol-ene compositions were found to be both self-cleaning, as measured by changes in water contact angle, and photocatalytic toward the degradation of an organic dye. Stable titania-thiol-ene dispersions at approximately 2 wt % solids were prepared using a combination of high-shear mixing and sonication in acetone solvent from photocatalytic titania, trisilanol isobutyl polyhedral oligomeric silsesquioxane (POSS) dispersant, and select thiol-ene monomers, i.e., trimethylolpropane tris(3-mercaptopropionate) (TMPMP), pentaerythritol allyl ether (APE), and 1,3,5-triallyl-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (TTT). The dispersed particle compositions were characterized by DLS and TEM. The synthetic methods employed yield a strongly bound particle/POSS complex, supported by IR, 29Si NMR, and TGA. The factors of spray techniques, carrier solvent volatility, and particle size and size distributions, in combination, likely all contribute to the highly textured but uniform surfaces observed via SEM and AFM. Polymer composites possessed thermal transitions (e.g., Tg) consistent with composition. In general, the presence of polymer matrix provided mechanical integrity, without significantly compromising or prohibiting other critical performance characteristics, such as film processing, photocatalytic degradation of adsorbed contaminants, and the hydrophobic-hydrophilic transition. In all cases, coatings containing photocatalytic titania were converted from superhydrophobic to superhydrophilic, as defined by changes in the water contact angle. The superhydrophilic state of samples was considered persistent, since long time durations in complete darkness were required to observe any significant hydrophobic return. In a preliminary demonstration, the photocatalytic activity of prepared coatings was confirmed through the degradation of crystal violet dye. This work demonstrates that a scalable process can be found to prepare titania-thiol-ene

  10. Improved Performance of DNA Microarray Multiplex Hybridization Using Probes Anchored at Several Points by Thiol-Ene or Thiol-Yne Coupling Chemistry.

    PubMed

    Bañuls, Maria-Jose; Jiménez-Meneses, Pilar; Meyer, Albert; Vasseur, Jean-Jacques; Morvan, François; Escorihuela, Jorge; Puchades, Rosa; Maquieira, Ángel

    2017-02-15

    Nucleic acid microarray-based assay technology has shown lacks in reproducibility, reliability, and analytical sensitivity. Here, a new strategy of probe attachment modes for silicon-based materials is built up. Thus, hybridization ability is enhanced by combining thiol-ene or thiol-yne click chemistry reactions with a multipoint attachment of polythiolated probes. The viability and performance of this approach was demonstrated by specifically determining Salmonella PCR products up to a 20 pM sensitivity level.

  11. Total synthesis of (+)-asteriscanolide: further exploration of the rhodium(I)-catalyzed [(5+2)+1] reaction of ene-vinylcyclopropanes and CO.

    PubMed

    Liang, Yong; Jiang, Xing; Fu, Xu-Fei; Ye, Siyu; Wang, Tao; Yuan, Jie; Wang, Yuanyuan; Yu, Zhi-Xiang

    2012-03-05

    The total synthesis of (+)-asteriscanolide is reported. The synthetic route features two key reactions: 1) the rhodium(I)-catalyzed [(5+2)+1] cycloaddition of a chiral ene-vinylcyclopropane (ene-VCP) substrate to construct the [6.3.0] carbocyclic core with excellent asymmetric induction, and 2) an alkoxycarbonyl-radical cyclization that builds the bridging butyrolactone ring with high efficiency. Other features of this synthetic route include the catalytic asymmetric alkynylation of an aldehyde to synthesize the chiral ene-VCP substrate, a highly regioselective conversion of the [(5+2)+1] cycloadduct into its enol triflate, and the inversion of the inside-outside tricycle to the outside-outside structure by an ester-reduction/elimination to enol-ether/hydrogenation procedure. In addition, density functional theory (DFT) rationalization of the chiral induction of the [(5+2)+1] reaction and the diastereoselectivity of the radical annulation has been presented. Equally important is that we have also developed other routes to synthesize asteriscanolide using the rhodium(I)-catalyzed [(5+2)+1] cycloaddition as the key step. Even though these routes failed to achieve the total synthesis, these experiments gave further useful information about the scope of the [(5+2)+1] reaction and paved the way for its future application in synthesis. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Synthesis and Applications of Silyl 2-Methylprop-2-ene-1-sulfinates in Preparative Silylation and GC-Derivatization Reactions of Polyols and Carbohydrates.

    PubMed

    Marković, Dean; Tchawou, Wandji Augustin; Novosjolova, Irina; Laclef, Sylvain; Stepanovs, Dmitrijs; Turks, Māris; Vogel, Pierre

    2016-03-14

    Trimethylsilyl, triethylsilyl, tert-butyldimethylsilyl, and triisopropylsilyl 2-methylprop-2-ene-1-sulfinates were prepared through (CuOTf)2⋅C6H6-catalyzed sila-ene reactions of the corresponding methallylsilanes with SO2 at 50 °C. Sterically hindered, epimerizable, and base-sensitive alcohols gave the corresponding silyl ethers in high yields and purities at room temperature and under neutral conditions. As the byproducts of the silylation reaction (SO2 +isobutylene) are volatile, the workup was simplified to solvent evaporation. The developed method can be employed for the chemo- and regioselective semiprotection of polyols and glycosides and for the silylation of unstable aldols. The high reactivity of the developed reagents is shown by the synthesis of sterically hindered per-O-tert-butyldimethylsilyl-α-D-glucopyranose, the X-ray crystallographic analysis of which is the first for a per-O-silylated hexopyranose. The per-O-silylation of polyols, hydroxy carboxylic acids, and carbohydrates with trimethylsilyl 2-methylprop-2-ene-1-sulfinate was coupled with the GC analysis of nonvolatile polyhydroxy compounds both qualitatively and quantitatively.

  13. Biotransformation of ent-kaur-16-ene and ent-trachylobane 7β-acetoxy derivatives by the fungus Gibberella fujikuroi (Fusarium fujikuroi).

    PubMed

    Fraga, Braulio M; Bressa, Carlo; González-Vallejo, Victoria; González, Pedro; Guillermo, Ricardo

    2012-09-01

    Candol A (7β-hydroxy-ent-kaur-16-ene) (6) is efficiently transformed by Gibberella fujikuroi into the gibberellin plant hormones. In this work, the biotransformation of its acetate by this fungus has led to the formation of 7β-acetoxy-ent-kaur-16-en-19-oic acid (3), whose corresponding alcohol is a short-lived intermediate in the biosynthesis of gibberellins and seco-ring ent-kaurenoids in this fungus. Further biotransformation of this compound led to the hydroxylation of the 3β-positions to give 7β-acetoxy-3β-hydroxy-ent-kaur-16-en-19-oic acid (14), followed by a 2β- or 18-hydroxylation of this metabolite. The incubation of epicandicandiol 7β-monoacetate (7β-acetoxy-18-hydroxy-ent-kaur-16-ene) (10) produces also the 19-hydroxylation to form the 18,19 diol (20), which is oxidized to give the corresponding C-18 or C-19 acids. These results indicated that the presence of a 7β-acetoxy group does not inhibit the fungal oxidation of C-19 in 7β-acetoxy-ent-kaur-16-ene, but avoids the ring B contraction that leads to the gibberellins and the 6β-hydroxylation necessary for the formation of seco-ring B ent-kaurenoids. The biotransformation of 7β-acetoxy-ent-trachylobane (trachinol acetate) (27) only led to the formation of 7β-acetoxy-18-hydroxy-ent-trachylobane (33).

  14. New Padded Harness for Self-Acquisition of Resting 12-Lead ECGs

    NASA Technical Reports Server (NTRS)

    Schlegel, T. T.; Rood, A. T.

    2011-01-01

    We have developed a dry-electrode harness that permits easy, rapid, and unsupervised self-acquisition of resting 12-lead ECGs without the use of any disposables. Various other advantageous features of the harness include: 1) padded or inflatable cushions at the lateral sides of the torso that function to press the left arm (LA) and right arm (RA) dry electrodes mounted on cushions against sideward (as shown in the Figure below) or downward-rested arms of the subject; 2) sufficient distal placement of the arm electrodes with good abutment and without the need for adhesives, straps, bands, bracelets, or gloves on the arms; 3) padding over the sternum to avoid "tenting" in the V1 through V3 (and V3R, when present) electrode positions; 4) easy-to-don, one-piece design with an adjustable single point of connection and an adjustable shoulder strap; and 5) Lund or "modified Lund" placement of the dry electrodes, the results of which more effectively reproduce results from "standard" 12-lead ECG placements than do results from Mason-Likar lead placements.

  15. Plug-and-play design approach to smart harness for modular small satellites

    NASA Astrophysics Data System (ADS)

    Mughal, M. Rizwan; Ali, Anwar; Reyneri, Leonardo M.

    2014-02-01

    A typical satellite involves many different components that vary in bandwidth demand. Sensors that require a very low data rate may reside on a simple two- or three-wire interface such as I2C, SPI, etc. Complex sensors that require high data rate and bandwidth may reside on an optical interface. The AraMiS architecture is an enhanced capability architecture with different satellite configurations. Although keeping the low-cost and COTS approach of CubeSats, it extends the modularity concept as it also targets different satellite shapes and sizes. But modularity moves beyond the mechanical structure: the tiles also have thermo-mechanical, harness and signal-processing functionalities. Further modularizing the system, every tile can also host a variable number of small sensors, actuators or payloads, connected using a plug-and-play approach. Every subsystem is housed in a small daughter board and is supplied, by the main tile, with power and data distribution functions, power and data harness, mechanical support and is attached and interconnected with space-grade spring-loaded connectors. The tile software is also modular and allows a quick adaptation to specific subsystems. The basic software for the CPU is properly hardened to guarantee high level of radiation tolerance at very low cost.

  16. Potential of mixed microalgae to harness biodiesel from ecological water-bodies with simultaneous treatment.

    PubMed

    Mohan, S Venkata; Devi, M Prathima; Mohanakrishna, G; Amarnath, N; Babu, M Lenin; Sarma, P N

    2011-01-01

    Biodiesel as an eco-friendly fuel is gaining much acceptance in recent years. This communication provides an overview on the possibility of using mixed microalgae existing in ecological water-bodies for harnessing biodiesel. Microalgal cultures from five water-bodies are cultivated in domestic wastewater in open-ponds and the harvested algal-biomass was processed through acid-catalyzed transesterification. Experiments evidenced the potential of using mixed microalgae for harnessing biodiesel. Presence of palmitic acid (C16:0) in higher fraction and physical properties of algal oil correlated well with the biodiesel properties. Functional characteristics of water-bodies showed to influence both species diversity and lipid accumulation. Microalgae from stagnant water-bodies receiving domestic discharges documented higher lipid accumulation. Algal-oil showed to consist 33 types of saturated and unsaturated fatty acids having wide food and fuel characteristics. Simultaneous wastewater treatment was also noticed due to the syntrophic association in the water-body microenvironment. Diversity studies visualized the composition of algae species known to accumulate higher lipids.

  17. Water gate array for current flow or tidal movement pneumatic harnessing system

    DOEpatents

    Gorlov, Alexander M.

    1991-01-01

    The invention, which provides a system for harnessing power from current flow or tidal movement in a body of water, comprises first and second hydro-pneumatic chambers each having ingress and egress below the water surface near the river or ocean floor and water gates operative to open or seal the ports to the passage of water. In an exemplary embodiment, the gates are sychronized by shafts so that the ingress ports of each chamber are connected to the egress ports of each other chamber. Thus, one set of gates is closed, while the other is open, thereby allowing water to flow into one chamber and build air pressure therein and allowing water to flow out of the other chamber and create a partial vacuum therein. A pipe connects the chambers, and an air turbine harnesses the air movement within the pipe. When water levels are equilibrated, the open set of gates is closed by a counterweight, and the other set is allowed to open by natural force of the water differential. The water gates may be comprised of a plurality of louvers which are ganged for simultaneous opening and closing. The system is designed to operate with air turbines or other pneumatic devices. Its design minimizes construction cost and environmental impact, yet provides a clean renewable energy source.

  18. Effects of harness transmitters on behavior and reproduction of wild mallards

    USGS Publications Warehouse

    Pietz, Pamela J.; Krapu, Gary L.; Greenwood, Raymond J.; Lokemoen, John T.

    1993-01-01

    Radio telemetry has been an important research tool in waterfowl studies for >20 years, yet little effort has been made to evaluate potential effects of transmitters on the birds that carry them. As part of a 4-year mallard (Anas platyrhynchos) study in the prairie pothole region of North Dakota and Minnesota, we compared radio-marked and unmarked female mallards in terms of percent time observed feeding, resting, and preening; nest initiation date; and clutch size and egg volume. Radio-marked females carried a 23-g back-mounted transmitter attached with a 2-loop harness (Dwyer 1972). On average, radio-marked females tended to feed less, rest and preen more, initiate nests later, and lay smaller clutches and eggs than unmarked females. Thus, behavioral and reproductive data from ducks marked with back-mounted harness-attached transmitters may be biased. We recommend that new designs of radio packages be field tested and caution that effects may be masked under extreme environmental conditions.

  19. The vibrational spectra of 1,3-dithiane-1-oxide and 1,3-dithia-1-oxocyclohept-5-ene

    NASA Astrophysics Data System (ADS)

    Noskov, A. I.; Fishman, A. I.; Galjautdinova, A. N.; Klimovitskii, E. N.

    2010-09-01

    The IR spectra of 1,3-dithiane-1-oxide (I) and 1,3-dithia-1-oxocyclohept-5-ene (II) were recorded in solution, solid and liquid phase over 4000-400 cm -1 spectral range. It was found that both (I) and (II) in liquid phase and solutions exist in two conformations: (I) chair-e ( Ce) and chair-a ( Ca) with equatorial and axial positions of the S dbnd O bond, respectively, and (II) chair-e ( Ce) and boat-e ( Be). The intensity variations with temperature (300-180 K) of the bands 632 ( Ca) and 644 cm -1 ( Ce) of (I) in acetone-d 6 and the bands 482 ( Be) и 448 cm -1 ( Ce) of (II) in melt were employed in Van't Hoff plot and gave the values Δ H°( Ca - Ce) = 380 ± 40 cal mol -1 (I) and Δ H° ( Be - Ce) = 400 ± 100 cal mol -1 (II). Ab initio calculations were carried out with the Gaussian 98 program using the basis set 6-31G(d) for (I) and 6-311++G(d,p) for (II). The energy difference between Ca and Ce conformations for (I) and Be and Ce for (II) are in a good agreement with experimental results. Vibrational frequencies for both conformations (I) and (II) were calculated. After appropriate scaling a reasonably good agreement between the experimental and calculated wave numbers was obtained.

  20. Functional characterization and stability improvement of a ‘thermophilic-like’ ene-reductase from Rhodococcus opacus 1CP

    PubMed Central

    Riedel, Anika; Mehnert, Marika; Paul, Caroline E.; Westphal, Adrie H.; van Berkel, Willem J. H.; Tischler, Dirk

    2015-01-01

    Ene-reductases (ERs) are widely applied for the asymmetric synthesis of relevant industrial chemicals. A novel ER OYERo2 was found within a set of 14 putative old yellow enzymes (OYEs) obtained by genome mining of the actinobacterium Rhodococcus opacus 1CP. Multiple sequence alignment suggested that the enzyme belongs to the group of ‘thermophilic-like’ OYEs. OYERo2 was produced in Escherichia coli and biochemically characterized. The enzyme is strongly NADPH dependent and uses non-covalently bound FMNH2 for the reduction of activated α,β-unsaturated alkenes. In the active form OYERo2 is a dimer. Optimal catalysis occurs at pH 7.3 and 37°C. OYERo2 showed highest specific activities (45-50 U mg-1) on maleimides, which are efficiently converted to the corresponding succinimides. The OYERo2-mediated reduction of prochiral alkenes afforded the (R)-products with excellent optical purity (ee > 99%). OYERo2 is not as thermo-resistant as related OYEs. Introduction of a characteristic intermolecular salt bridge by site-specific mutagenesis raised the half-life of enzyme inactivation at 32°C from 28 to 87 min and improved the tolerance toward organic co-solvents. The suitability of OYERo2 for application in industrial biocatalysis is discussed. PMID:26483784

  1. Facile preparation of biocompatible sulfhydryl cotton fiber-based sorbents by "thiol-ene" click chemistry for biological analysis.

    PubMed

    He, Xiao-Mei; Zhu, Gang-Tian; Zhu, Yuan-Yuan; Chen, Xi; Zhang, Zheng; Wang, Shao-Ting; Yuan, Bi-Feng; Feng, Yu-Qi

    2014-10-22

    Sulfhydryl cotton fiber (SCF) has been widely used as adsorbent for a variety of metal ions since 1971. Thanks to the abundant thiols on SCF, in this study, we reported a universal method for the facile preparation of SCF-based materials using "thiol-ene" click chemistry for the first time. With the proposed method, two types of SCF-based materials, phenylboronic acid grafted sulfhydryl cotton fiber (SCF-PBA) and zirconium phosphonate-modified sulfhydryl cotton fiber (SCF-pVPA-Zr(4+)), were successfully prepared. The grafted functional groups onto the thiol group of SCF were demonstrated by X-ray photoelectron spectroscopy (XPS) and energy dispersive X-ray spectroscopy (EDX). The prepared fibrous materials exhibited excellent fiber strength, good stability in aqueous or nonaqueous solutions, and great biocompatibility. Moreover, we developed filter-free in-pipet-tip SPE using these SCF-based materials as adsorbent for the enrichment of ribonucleosides, glycopeptides and phosphopeptides. Our results showed that SCF-PBA adsorbent can selectively capture ribonucleosides and glycopeptides from complex biological samples. And SCF-pVPA-Zr(4+) adsorbent exhibited high selectivity and capacity in the enrichment of phosphopeptides from the digestion mixture of β-casein and bovine serum albumin (BSA), as well as human serum and nonfat milk digest. Generally, the preparation strategy can be a universal method for the synthesis of other functionalized cotton-based adsorbents with special requirement in microscale biological analysis.

  2. Structure, thermal and spectral study of 16α,17-epoxypregn-4-ene-3,11,20-trione monohydate

    NASA Astrophysics Data System (ADS)

    Nie, Qiang; Wang, JingKang

    2005-10-01

    16α,17-epoxypregn-4-ene-3,11,20-trione is an important steroid intermediate in synthesis of many hormone pharmaceuticals, such as cortisone acetate and betamethason. It does not dissolve in water, but the single crystals grown from acetone with some water shows evident hydration behavior. The thermal analyses by DSC and TG-DTA and the IR spectra characterization of the anhydrous and hydrous crystals were performed and compared. The hydrate was also proved by IR spectral and thermal analyses. Single crystal structure of the hydrate indicates one water molecule per host molecule is included into the host lattice. The incorporation of water molecules does not change the crystal cell dimensions significantly, except for some increment of the cell along the axis b. In the crystal cell, two steroid molecules are linked through the water molecules as a bridge by forming two different hydrogen bonds. The incorporation of one water molecule makes some conformation changes of the molecules in the crystal unit cell.

  3. Fabrication of rigid microstructures with thiol-ene-based soft lithography for continuous-flow cell lysis.

    PubMed

    Burke, Jeffrey M; Pandit, Kunal R; Goertz, John P; White, Ian M

    2014-09-01

    In this work, we introduce a method for the soft-lithography-based fabrication of rigid microstructures and a new, simple bonding technique for use as a continuous-flow cell lysis device. While on-chip cell lysis techniques have been reported previously, these techniques generally require a long on-chip residence time, and thus cannot be performed in a rapid, continuous-flow manner. Microstructured microfluidic devices can perform mechanical lysis of cells, enabling continuous-flow lysis; however, rigid silicon-based devices require complex and expensive fabrication of each device, while polydimethylsiloxane (PMDS), the most common material used for soft lithography fabrication, is not rigid and expands under the pressures required, resulting in poor lysis performance. Here, we demonstrate the fabrication of microfluidic microstructures from off-stoichiometry thiol-ene (OSTE) polymer using soft-lithography replica molding combined with a post-assembly cure for easy bonding. With finite element simulations, we show that the rigid microstructures generate an energy dissipation rate of nearly 10(7), which is sufficient for continuous-flow cell lysis. Correspondingly, with the OSTE device we achieve lysis of highly deformable MDA-MB-231 breast cancer cells at a rate of 85%, while a comparable PDMS device leads to a lysis rate of only 40%.

  4. Synthesis and Characterization of High Performance Polyimides Containing the Bicyclo(2.2.2)oct-7-ene Ring System

    NASA Technical Reports Server (NTRS)

    Alvarado, M.; Harruna, I. I.; Bota, K. B.

    1997-01-01

    Due to the difficulty in processing polyimides with high temperature stability and good solvent resistance, we have synthesized high performance polyimides with bicyclo(2.2.2)-oct-7-ene ring system which can easily be fabricated into films and fibers and subsequently converted to the more stable aromatic polyimides. In order to improve processability, we prepared two polyimides by reacting 1,4-phenylenediamine and 1,3phenylediamine with bicyclo(2.2.2)-7-octene-2,3,5,6-tetracarboxylic dianhydride. The polyimides were characterized by FTIR, FTNMR, solubility and thermal analysis. Thermogravimetric analysis (TGA) showed that the 1,4-phenylenediamine and 1,3-phenylenediamine containing polyimides were stable up to 460 and 379 C, respectively under nitrogen atmosphere. No melting transitions were observed for both polyimides. The 1,4-phenylenediamine containing polyimide is partially soluble in dimethyl sulfoxide, methane sulfonic acid and soluble in sulfuric acid at room temperature. The 1,3-phenylenediamine containing polyimide is partially soluble in dimethyl sulfoxide, tetramethyl urea, N,N-dimethyl acetamide and soluble in methane sulfonic acid and sulfuric acid.

  5. Thiol-ene hydrogels as desmoplasia-mimetic matrices for modeling pancreatic cancer cell growth, invasion, and drug resistance.

    PubMed

    Ki, Chang Seok; Lin, Tsai-Yu; Korc, Murray; Lin, Chien-Chi

    2014-12-01

    The development of pancreatic ductal adenocarcinoma (PDAC) is heavily influenced by local stromal tissues, or desmoplasia. Biomimetic hydrogels capable of mimicking tumor niches are particularly useful for discovering the role of independent matrix cues on cancer cell development. Here, we report a photo-curable and bio-orthogonal thiol-ene (i.e., cross-linked by mutually reactive norbornene and thiol groups via photoinitiation) hydrogel platform for studying the growth, morphogenesis, drug resistance, and cancer stem cell marker expression in PDAC cells cultured in 3D. The hydrogels were prepared from multi-arm poly(ethylene glycol)-norbornene cross-linked with protease-sensitive peptide to permit cell-mediated matrix remodeling. Collagen 1 fibrils were incorporated into the covalent network while cytokines (e.g., EGF and TGF-β1) were supplemented in the culture media for controlling cell fate. We found that the presence of collagen 1 enhanced cell proliferation and Yes-associated protein (YAP) translocation to cell nuclei. Cytokines and collagen 1 synergistically up-regulated MT1-MMP expression and induced cell spreading, suggestive of epithelial-mesenchymal transition (EMT) in the encapsulated cells. Furthermore, PDAC cells cultured in 3D developed chemo-resistance even in the absence of collagen 1 and cytokines. This phenotype is likely a consequence of the enrichment of pancreatic cancer stem cells that expressed high levels of CD24, sonic hedgehog (SHH), and vascular endothelial growth factor (VEGF).

  6. Enantioselective Reduction of Citral Isomers in NCR Ene Reductase: Analysis of an Active-Site Mutant Library.

    PubMed

    Kress, Nico; Rapp, Johanna; Hauer, Bernhard

    2017-02-08

    A deeper understanding of the >99 % S-selective reduction of both isomers of citral catalyzed by NCR ene reductase was achieved by active-site mutational studies and docking simulation. Though structurally similar, the E/Z isomers of citral showed a significantly varying selectivity response to introduced mutations. Although it was possible to invert (E)-citral reduction enantioselectivity to ee 46 % (R) by introducing mutation W66A, for (Z)-citral it remained ≥88 % (S) for all single-residue variants. Residue 66 seems to act as a lever for opposite binding modes. This was underlined by a W66A-based double-mutant library that enhanced the (E)-citral derived enantioselectivity to 63 % (R) and significantly lowered the S selectivity for (Z)-citral to 44 % (S). Formation of (R)-citronellal from an (E/Z)-citral mixture is a desire in industrial (-)-menthol synthesis. Our findings pave the way for a rational enzyme engineering solution.

  7. Measurements and Correlations of cis-1,3,3,3-Tetrafluoroprop-1-ene (R1234ze(Z)) Saturation Pressure

    NASA Astrophysics Data System (ADS)

    Fedele, Laura; Di Nicola, Giovanni; Brown, J. Steven; Bobbo, Sergio; Zilio, Claudio

    2014-01-01

    cis-1,3,3,3-Tetrafluoroprop-1-ene (R1234ze(Z)) is being investigated as a working fluid possessing a low global warming potential (GWP) for high-temperature heat pumping applications, organic Rankine cycles, and air-conditioning and refrigeration applications, and as a potential solvent, propellant, and foam blowing agent. Its GWP is less than one. The open literature contains a total of 79 vapor-pressure data from three sources and the critical state properties from a single source. The current paper provides 64 vapor-pressure data from two different laboratories over the temperature range from 238.13 K to 372.61 K. These data are regressed using Wagner and extended Antoine vapor-pressure correlations and then compared to the existing open literature data and correlations. The normal-boiling-point temperature and acentric factor for R1234ze(Z) are estimated to be 282.73 K and 0.3257, respectively.

  8. Synthesis and Characterization of High Performance Polyimides Containing the Bicyclo(2.2.2)oct-7-ene Ring System

    NASA Technical Reports Server (NTRS)

    Alvarado, M.; Harruna, I. I.; Bota, K. B.

    1997-01-01

    Due to the difficulty in processing polyimides with high temperature stability and good solvent resistance, we have synthesized high performance polyimides with bicyclo(2.2.2)-oct-7-ene ring system which can easily be fabricated into films and fibers and subsequently converted to the more stable aromatic polyimides. In order to improve processability, we prepared two polyimides by reacting 1,4-phenylenediamine and 1,3phenylediamine with bicyclo(2.2.2)-7-octene-2,3,5,6-tetracarboxylic dianhydride. The polyimides were characterized by FTIR, FTNMR, solubility and thermal analysis. Thermogravimetric analysis (TGA) showed that the 1,4-phenylenediamine and 1,3-phenylenediamine containing polyimides were stable up to 460 and 379 C, respectively under nitrogen atmosphere. No melting transitions were observed for both polyimides. The 1,4-phenylenediamine containing polyimide is partially soluble in dimethyl sulfoxide, methane sulfonic acid and soluble in sulfuric acid at room temperature. The 1,3-phenylenediamine containing polyimide is partially soluble in dimethyl sulfoxide, tetramethyl urea, N,N-dimethyl acetamide and soluble in methane sulfonic acid and sulfuric acid.

  9. Crystal structure of di-aqua-(μ2-tri-ethyl-ene-tetra-minehexa-acetato)-dizinc tetra-hydrate.

    PubMed

    Liu, Huan; Lu, Li-Ping

    2015-03-01

    The reaction of ZnO and tri-ethyl-ene-tetra-minehexaacetic acid (H6TTHA) in aqueous solution after refluxing yields the binuclear title compound, [Zn2(C18H26N4O12)(H2O)2]·4H2O. There is a centre of symmetry in the [Zn2(H2TTHA)(H2O)2] mol-ecule in the crystalline state. Both Zn(II) ions are octahedrally surrounded and bound by an N2O3 donor set from the H2TTHA(4-) anion and a water mol-ecule; the N atoms are cis and the water mol-ecule is trans to an N atom. The Zn⋯Zn separation is 7.562 (1) Å. An intra-molecular C-H⋯O inter-action is observed and both carboxyl-ate H atoms are disordered over two adjacent sites. In the crystal, the components are linked by O-H⋯O and C-H⋯O hydrogen bonds generating a three-dimensonal network.

  10. Catalytic dicyanative [4 + 2] cycloaddition triggered by cyanopalladation using ene-enynes and cyclic enynes with methyl acrylate.

    PubMed

    Arai, Shigeru; Koike, Yuka; Hada, Hirohiko; Nishida, Atsushi

    2010-11-19

    Palladium-catalyzed dicyanative [4 + 2] cycloaddition using various ene-enynes was investigated. The key species in this process is a cyanoallene intermediate that is obtained by the cyanopalladation of conjugated enynes followed by 5-exo-cyclization. To achieve an efficient [4 + 2] cycloaddition reaction, both the smooth generation of this species and critical control of regioselectivity in the 6-endo-cyclization step are quite important. A study of the substrate scope revealed that the reaction is strongly affected by the steric bulk of the substituents on the enyne and alkene units and prefers to give trans-fused cycloadducts. The stereochemistry of olefins was reasonably transferred to the corresponding products. Further study proved that this transformation includes not a thermal [4 + 2] cycloaddition process via 1,2-dicyanoalkenes generated in situ but rather a palladium-mediated stepwise cyclization sequence to control a maximum of five contiguous stereogenic centers in a single operation. An intermolecular version using methyl acrylate with conjugated cyclic enynes and TMSCN also gave the corresponding [4 + 2] cycloadducts in a regioselective manner.

  11. Low-Cost Perovskite Solar Cells Employing Dimethoxydiphenylamine-Substituted Bistricyclic Aromatic Enes as Hole Transport Materials.

    PubMed

    Rakstys, Kasparas; Paek, Sanghyun; Grancini, Giulia; Gao, Peng; Jankauskas, Vygintas; Asiri, Abdullah M; Nazeeruddin, Mohammad Khaja

    2017-06-26

    The synthesis, characterization and photovoltaic performance of series of novel molecular hole transport materials (HTMs) based on bistricyclic aromatic enes (BAEs) are presented. The new derivatives were obtained following a simple and straightforward procedure from inexpensive starting reagents mimicking the synthetically challenging 9,9'-spirobifluorene moiety of the well-studied spiro-OMeTAD. The novel HTMs were tested in mixed cations and anions perovskite solar cells (PSCs) yielding a power conversion efficiency (PCE) of 19.2 % under standard global 100 mW cm(-2) AM1.5G illumination using 9-{2,7-bis[bis(4-methoxyphenyl)amino]-9H-fluoren-9-ylidene}-N(2) ,N(2) ,N(7) ,N(7) -tetrakis(4-methoxyphenyl)-9H-thioxanthene-2,7-diamine (coded as KR374). The power conversion efficiency data confirms the easily attainable heteromerous fluorenylidenethioxanthene structure as valuable core for low-cost and highly efficient HTM design and paves the way towards cost-effective PSC technology. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Acute cervical spinal cord injury secondary to air bag deployment without proper use of lap or shoulder harnesses.

    PubMed

    Hart, R A; Mayberry, J C; Herzberg, A M

    2000-02-01

    The authors present a case report of a patient with cervical central spinal cord syndrome caused by a hyperextension injury after a motor vehicle collision in which the air bag deployed in the absence of shoulder or lap belt harnesses. The potential for cervical spine and spinal cord hyperextension injuries in passengers positioned in front of air bags without proper use of shoulder or lap belt harnesses is discussed. Cervical central spinal cord quadriplegia occurred with cervical spondylosis and kyphosis that was managed by early three-level cervical corpectomy in a 58-year-old patient. Early improvement in the patient's neurological status occurred but was incomplete at the time of this report. Cervical hyperextension injuries are possible in passengers positioned in the front seat of cars with air bags when shoulder or lap belt harnesses are not used properly. Previous biomechanical studies have documented the potential for these types of injuries.

  13. Doppler sensors and harnesses for cardiac and peripheral arterial flow monitoring.

    PubMed

    Arbeille, P

    1997-01-01

    The objective of the present work was to design Doppler sensors and harnesses for monitoring in real time the cardiac stroke volume and output, the cerebral flow volume and resistance and the lower limb arterial flow and resistance changes. For the middle cerebral artery investigation we used a 2-MHz transcranial pulsed wave (PW) Doppler probe (commercial probe) mounted on a rotula, fixed on the horizontal branch of a headset designed like an audio headset. The arch of the headset passed over the top of the skull. For the common carotid investigation, a 4-MHz continuous-wave (CW) or PW flat Doppler probe was inserted in a circular silicone support of 5-cm diameter and 0.6-cm thickness. This soft support could adapt to the irregular surface of the neck, and the silicone material, which is fairly adhesive to the skin, made the system stable. The transducers were preoriented at 45 degrees from the support, which provided an acceptable orientation of the Doppler beam. The aortic Doppler harness consisted of a 2-MHz PW Doppler probe, mounted on a rotula fixed on a plastic rigid support 7 x 1.5 cm2 in area (parallel to the sternum) whose length could be changed (4-7 cm) to localize the rotula and its sensor on the suprasternal area. This flat segment was fixed on a rotating platform, part of a solid square plastic support (10 x 10 cm2) placed on the upper part of the sternum. This system was maintained by elastic bands passing around the shoulder and the chest. The femoral Doppler harness consisted of a 4-MHz CW or PW flat Doppler probe, inserted in a flat and rectangular rigid plastic support 10 x 3 cm2 in area. This rigid support was well adapted to the flat surface of the internal part of the thigh, which made the system stable. Two elastic bands passed around the thigh and the abdomen, which avoided any translation of the support and kept the sensor in contact with the skin. The transducers were preoriented at 45 degrees from the support, which provided an acceptable

  14. Let Our Powers Combine! Harnessing NASA's Earth Observatory Natural Event Tracker (EONET) in Worldview

    NASA Technical Reports Server (NTRS)

    Wong, Min Minnie; Ward, Kevin; Boller, Ryan; Gunnoe, Taylor; Baynes, Kathleen; King, Benjamin

    2016-01-01

    Constellations of NASA Earth Observing System (EOS) satellites orbit the earth to collect images and data about the planet in near real-time. Within hours of satellite overpass, you can discover where the latest wildfires, severe storms, volcanic eruptions, and dust and haze events are occurring using NASA's Worldview web application. By harnessing a repository of curated natural event metadata from NASA Earth Observatory's Natural Event Tracker (EONET), Worldview has moved natural event discovery to the forefront and allows users to select events-of-interest from a curated list, zooms to the area, and adds the most relevant imagery layers for that type of natural event. This poster will highlight NASA Worldviews new natural event feed functionality.

  15. Cold water cleaning of brain proteins, biofilm and bone - harnessing an ultrasonically activated stream.

    PubMed

    Birkin, P R; Offin, D G; Vian, C J B; Howlin, R P; Dawson, J I; Secker, T J; Hervé, R C; Stoodley, P; Oreffo, R O C; Keevil, C W; Leighton, T G

    2015-08-28

    In the absence of sufficient cleaning of medical instruments, contamination and infection can result in serious consequences for the health sector and remains a significant unmet challenge. In this paper we describe a novel cleaning system reliant on cavitation action created in a free flowing fluid stream where ultrasonic transmission to a surface, through the stream, is achieved using careful design and control of the device architecture, sound field and the materials employed. Cleaning was achieved with purified water at room temperature, moderate fluid flow rates and without the need for chemical additives or the high power consumption associated with conventional strategies. This study illustrates the potential in harnessing an ultrasonically activated stream to remove biological contamination including brain tissue from surgical stainless steel substrates, S. epidermidis biofilms from glass, and fat/soft tissue matter from bone structures with considerable basic and clinical applications.

  16. Thinking globally, acting locally: harnessing the immune system to deal with recalcitrant pathogens.

    PubMed

    Russell, Michael W

    2015-04-28

    Traditional approaches to harnessing the immune system to confront infectious diseases depend on vaccines, which have generally proven highly effective, but for many infections these either are not available or are of limited effectiveness. Although antibiotic therapy has been extremely successful in reducing the burden of bacterial disease, the emergence of resistance among several important pathogens threatens to undermine this accomplishment, and despite some successes chemotherapeutic treatments for viral, fungal, and parasitic infections are more limited. Understanding the mechanisms whereby pathogens manipulate the immune system to favor their survival, or exploit weaknesses in host immunity, can lead to novel approaches for the treatment of infections by redirecting host immune responses against the pathogen. Such treatments may be most effectively applied at the mucosal locations which are frequently the sites of initial infection and may also suggest new approaches for vaccine development.

  17. Harnessing Supramolecular and Peptidic Self-Assembly for the Construction of Reinforced Polymeric Tissue Scaffolds.

    PubMed

    Thompson, Chase B; Korley, LaShanda T J

    2017-05-17

    The repair and regeneration of the body's tissue using polymeric materials remains a main focus of biomaterials research. While hydrogels and elastomers have shown biocompatibility and high extensibility, they lack the required toughness to host proliferating cells. As the need for robust polymeric scaffolds grows, new technologies must emerge to meet the stringent physical and biological needs of proliferating cells. To this end, the utilization of self-assembling motifs allows for the construction of versatile networks in which cells can grow. In this review, we discuss emerging techniques that harness the assembling capabilities of synthetic supramolecular and natural peptide motifs to construct mechanically robust elastomers and hydrogel scaffolds. In particular, we focus on how the design and structure impact their mechanical properties and interaction with the cellular environment.

  18. Harnessing Geometric Frustration to Form Band Gaps in Acoustic Channel Lattices

    NASA Astrophysics Data System (ADS)

    Wang, Pai; Zheng, Yue; Fernandes, Matheus C.; Sun, Yushen; Xu, Kai; Sun, Sijie; Kang, Sung Hoon; Tournat, Vincent; Bertoldi, Katia

    2017-02-01

    We demonstrate both numerically and experimentally that geometric frustration in two-dimensional periodic acoustic networks consisting of arrays of narrow air channels can be harnessed to form band gaps (ranges of frequency in which the waves cannot propagate in any direction through the system). While resonant standing wave modes and interferences are ubiquitous in all the analyzed network geometries, we show that they give rise to band gaps only in the geometrically frustrated ones (i.e., those comprising of triangles and pentagons). Our results not only reveal a new mechanism based on geometric frustration to suppress the propagation of pressure waves in specific frequency ranges but also open avenues for the design of a new generation of smart systems that control and manipulate sound and vibrations.

  19. Amplifying the response of soft actuators by harnessing snap-through instabilities

    PubMed Central

    Overvelde, Johannes T. B.; Kloek, Tamara; D’haen, Jonas J. A.; Bertoldi, Katia

    2015-01-01

    Soft, inflatable segments are the active elements responsible for the actuation of soft machines and robots. Although current designs of fluidic actuators achieve motion with large amplitudes, they require large amounts of supplied volume, limiting their speed and compactness. To circumvent these limitations, here we embrace instabilities and show that they can be exploited to amplify the response of the system. By combining experimental and numerical tools we design and construct fluidic actuators in which snap-through instabilities are harnessed to generate large motion, high forces, and fast actuation at constant volume. Our study opens avenues for the design of the next generation of soft actuators and robots in which small amounts of volume are sufficient to achieve significant ranges of motion. PMID:26283372

  20. Harnessing Geometric Frustration to Form Band Gaps in Acoustic Channel Lattices.

    PubMed

    Wang, Pai; Zheng, Yue; Fernandes, Matheus C; Sun, Yushen; Xu, Kai; Sun, Sijie; Kang, Sung Hoon; Tournat, Vincent; Bertoldi, Katia

    2017-02-24

    We demonstrate both numerically and experimentally that geometric frustration in two-dimensional periodic acoustic networks consisting of arrays of narrow air channels can be harnessed to form band gaps (ranges of frequency in which the waves cannot propagate in any direction through the system). While resonant standing wave modes and interferences are ubiquitous in all the analyzed network geometries, we show that they give rise to band gaps only in the geometrically frustrated ones (i.e., those comprising of triangles and pentagons). Our results not only reveal a new mechanism based on geometric frustration to suppress the propagation of pressure waves in specific frequency ranges but also open avenues for the design of a new generation of smart systems that control and manipulate sound and vibrations.

  1. Harnessing spectral property of dual wavelength white LED to improve vertical scanning interferometry.

    PubMed

    Chong, Wee Keat; Li, Xiang; Soh, Yeng Chai

    2013-07-01

    Unlike a conventional white light source that emits a continuous and broad spectrum of light, the dual wavelength white light emitting diode (LED) generates white light by mixing blue and yellow lights, so there are two distinct peaks in its intensity spectrum. Prior works had shown that the spectral property of the dual wavelength white LED can affect the vertical scanning interferometry negatively if the spectral effects are not compensated. In this paper, we shall examine this issue by modeling the spectral property and variation of the dual wavelength white LED, followed by investigating its effects on the interference signal of vertical scanning interferometry. Instead of compensating the spectral effects of the dual wavelength white LED, we harness its spectral property to improve the performance of a phase-based height reconstruction algorithm in vertical scanning interferometry.

  2. Harnessing Vehicle Automation for Public Mobility -- An Overview of Ongoing Efforts

    SciTech Connect

    Young, Stanley E.

    2015-11-05

    This presentation takes a look at the efforts to harness automated vehicle technology for public transport. The European CityMobil2 is the leading demonstration project in which automated shuttles were, or are planned to be, demonstrated in several cities and regions. The presentation provides a brief overview of the demonstrations at Oristano, Italy (July 2014), LaRochelle, France (Dec 2014), Lausanne, Switzerland (Apr 2015), Vantaa, Finland (July 2015), and Trikala, Greece (Sept 2015). In addition to technology exposition, the objectives included generating a legal framework for operation in each location and gaging the reaction of the public to unmanned shuttles, both of which were successfully achieved. Several such demonstrations are planned throughout the world, including efforts in North America in conjunction with the GoMentum Station in California. These early demonstration with low-speed automated shuttles provide a glimpse of the possible with a fully automated fleet of driverless vehicle providing a public transit service.

  3. Antiviral Goes Viral: Harnessing CRISPR/Cas9 to Combat Viruses in Humans.

    PubMed

    Soppe, Jasper Adriaan; Lebbink, Robert Jan

    2017-10-01

    The clustered regularly interspaced short palindromic repeats (CRISPR) and CRISPR-associated (Cas) systems are RNA-guided sequence-specific prokaryotic antiviral immune systems. In prokaryotes, small RNA molecules guide Cas effector endonucleases to invading foreign genetic elements in a sequence-dependent manner, resulting in DNA cleavage by the endonuclease upon target binding. A rewired CRISPR/Cas9 system can be used for targeted and precise genome editing in eukaryotic cells. CRISPR/Cas has also been harnessed to target human pathogenic viruses as a potential new antiviral strategy. Here, we review recent CRISPR/Cas9-based approaches to combat specific human viruses in humans and discuss challenges that need to be overcome before CRISPR/Cas9 may be used in the clinic as an antiviral strategy. Copyright © 2017 Elsevier Ltd. All rights reserved.

  4. Harnessing complexity: taking advantage of context and relationships in dissemination of school-based interventions.

    PubMed

    Butler, Helen; Bowes, Glenn; Drew, Sarah; Glover, Sara; Godfrey, Celia; Patton, George; Trafford, Lea; Bond, Lyndal

    2010-03-01

    Schools and school systems are increasingly asked to use evidence-based strategies to promote the health and well-being of students. The dissemination of school-based health promotion research, however, offers particular challenges to conventional approaches to dissemination. Schools and education systems are multifaceted organizations that sit within constantly shifting broader contexts. This article argues that health promotion dissemination needs to be rethought for school communities as complex systems and that this requires understanding and harnessing the dynamic ecology of the sociopolitical context. In developing this argument, the authors draw on their experience of the dissemination process of a multilevel school-based intervention in a complex educational context. Building on this experience, they argue for the need to move beyond conventional dissemination strategies to a focus on active partnerships between developers and users of school-based intervention research and offer a conceptual tool for planning dissemination.

  5. Harnessing the world's biodiversity data: promise and peril in ecological niche modeling of species distributions.

    PubMed

    Anderson, Robert P

    2012-07-01

    Recent advances allow harnessing enormous stores of biological and environmental data to model species niches and geographic distributions. Natural history museums hold specimens that represent the only information available for most species. Ecological niche models (sometimes termed species distribution models) combine such information with digital environmental data (especially climatic) to offer key insights for conservation biology, management of invasive species, zoonotic human diseases, and other pressing environmental problems. Five major pitfalls seriously hinder such research, especially for cross-space or cross-time uses: (1) incorrect taxonomic identifications; (2) lacking or inadequate databasing and georeferences; (3) effects of sampling bias across geography; (4) violation of assumptions related to selection of the study region; and (5) problems regarding model evaluation to identify optimal model complexity. Large-scale initiatives regarding data availability and quality, technological development, and capacity building should allow high-quality modeling on a scale commensurate with the enormous potential of and need for these techniques.

  6. Substantial influence on solar energy harnessing ability by geometries of ordered Si nanowire array

    PubMed Central

    2014-01-01

    The reflectance of the controlled periodic Si nanowire (NW) arrays is systematically explored, which characterizes the influence on the solar energy harnessing ability by the geometries of the NW. A unique dependence of the reflectance of the Si NW array on the diameter, the height, and the bending of the NW are disclosed. The solar energy loss caused by the reflection of the Si NW array exhibits the minimum for the NW with intermediate diameter and length. A plane-wave-based transfer-matrix method (TMM) simulation is performed, which is well consistent with the experimental results. Our results demonstrate the design principle to optimize the Si NW arrays for high-efficiency solar cells. PACS 81.07.-b; 78.67.-n; 81.16.-c PMID:25258613

  7. Harnessing Colloidal Crack Formation by Flow-Enabled Self-Assembly.

    PubMed

    Li, Bo; Jiang, Beibei; Han, Wei; He, Ming; Li, Xiao; Wang, Wei; Hong, Suck Won; Byun, Myunghwan; Lin, Shaoliang; Lin, Zhiqun

    2017-03-02

    Self-assembly of nanomaterials to yield a wide diversity of high-order structures, materials, and devices promises new opportunities for various technological applications. Herein, we report that crack formation can be effectively harnessed by elaborately restricting the drying of colloidal suspension using a flow-enabled self-assembly (FESA) strategy to yield large-area periodic cracks (i.e., microchannels) with tunable spacing. These uniform microchannels can be utilized as a template to guide the assembly of Au nanoparticles, forming intriguing nanoparticle threads. This strategy is simple and convenient. As such, it opens the possibility for large-scale manufacturing of crack-based or crack-derived assemblies and materials for use in optics, electronics, optoelectronics, photonics, magnetic device, nanotechnology, and biotechnology.

  8. The sweetest pill to swallow: how patient neurobiology can be harnessed to maximise placebo effects.

    PubMed

    Jubb, Jayne; Bensing, Jozien M

    2013-12-01

    The burgeoning interest in placebo effects over the last 10-15 years has fallen into two main research areas: elucidation of the neurobiological mechanisms recruited following placebo administration, and investigations into the situations and contexts in which placebo effects are evoked. There has been little attention focused on bridging these two i.e. how to actively translate and apply these neurobiological mechanisms into daily clinical practice in a responsible way. This article addresses this gap, first through a narrative review of the last 15 years of neuroscience findings with special attention focussed on the elucidation of the neurotransmitters, pathways and mechanisms involved in placebo effects, and secondly, at how these psycho(neuro)biological effects could be harnessed in medical care. Copyright © 2013 Elsevier Ltd. All rights reserved.

  9. Let our powers combine! Harnessing NASA's Earth Observatory Natural Event Tracker (EONET) in Worldview

    NASA Astrophysics Data System (ADS)

    Wong, M. M.; Ward, K.; Boller, R. A.; Gunnoe, T.; Baynes, K.; King, B. A.

    2016-12-01

    Constellations of NASA Earth Observing System (EOS) satellites orbit the earth to collect images and data about the planet in near real-time. Within hours of satellite overpass, you can discover where the latest wildfires, severe storms, volcanic eruptions, and dust and haze events are occurring using NASA's Worldview web application. By harnessing a repository of curated natural event metadata from NASA Earth Observatory's Natural Event Tracker (EONET), Worldview has moved natural event discovery to the forefront and allows users to select events-of-interest from a curated list, zooms to the area, and adds the most relevant imagery layers for that type of natural event. This poster will highlight NASA Worldview's new natural event feed functionality.

  10. Harnessing the Endocannabinoid 2-Arachidonoylglycerol to Lower Intraocular Pressure in a Murine Model

    PubMed Central

    Miller, Sally; Leishman, Emma; Hu, Sherry Shujung; Elghouche, Alhasan; Daily, Laura; Murataeva, Natalia; Bradshaw, Heather; Straiker, Alex

    2016-01-01

    Purpose Cannabinoids, such as Δ9-THC, act through an endogenous signaling system in the vertebrate eye that reduces IOP via CB1 receptors. Endogenous cannabinoid (eCB) ligand, 2-arachidonoyl glycerol (2-AG), likewise activates CB1 and is metabolized by monoacylglycerol lipase (MAGL). We investigated ocular 2-AG and its regulation by MAGL and the therapeutic potential of harnessing eCBs to lower IOP. Methods We tested the effect of topical application of 2-AG and MAGL blockers in normotensive mice and examined changes in eCB-related lipid species in the eyes and spinal cord of MAGL knockout (MAGL−/−) mice using high performance liquid chromatography/tandem mass spectrometry (HPLC/MS/MS). We also examined the protein distribution of MAGL in the mouse anterior chamber. Results 2-Arachidonoyl glycerol reliably lowered IOP in a CB1- and concentration-dependent manner. Monoacylglycerol lipase is expressed prominently in nonpigmented ciliary epithelium. The MAGL blocker KML29, but not JZL184, lowered IOP. The ability of CB1 to lower IOP is not desensitized in MAGL−/− mice. Ocular monoacylglycerols, including 2-AG, are elevated in MAGL−/− mice but, in contrast to the spinal cord, arachidonic acid and prostaglandins are not changed. Conclusions Our data confirm a central role for MAGL in metabolism of ocular 2-AG and related lipid species, and that endogenous 2-AG can be harnessed to reduce IOP. The MAGL blocker KML29 has promise as a therapeutic agent, while JZL184 may have difficulty crossing the cornea. These data, combined with the relative specificity of MAGL for ocular monoacylglycerols and the lack of desensitization in MAGL−/− mice, suggest that the development of an optimized MAGL blocker offers therapeutic potential for treatment of elevated IOP. PMID:27333182

  11. The validity and reliability of a customized rigid supportive harness during Smith machine back squat exercise.

    PubMed

    Scott, Brendan R; Dascombe, Ben J; Delaney, Jace A; Elsworthy, Nathan; Lockie, Robert G; Sculley, Dean V; Slattery, Katie M

    2014-03-01

    Although the back squat exercise is commonly prescribed to both athletic and clinical populations, individuals with restricted glenohumeral mobility may be unable to safely support the bar on the upper trapezius using their hands. The aims of this study were to investigate the validity and reliability of a back squat variation using a rigid supportive harness that does not require unrestricted glenohumeral mobility for quantifying 1 repetition maximum (1RM). Thirteen young men (age = 25.3 ± 4.5 years, height = 179.2 ± 6.9 cm, and body mass = 86.6 ± 12.0 kg) with at least 2 years resistance training experience volunteered to participate in the study. Subjects reported to the lab on 3 occasions, each separated by 1 week. During testing sessions, subjects were assessed for 1RM using the traditional back squat (session 1) and harness back squat (HBS; sessions 2 and 3) exercises. Mean 1RM for the traditional back squat, and 2 testing sessions of the HBS (HBS1 and HBS2) were 148.4 ± 25.0 kg, 152.5 ± 25.7 kg, and 150.4 ± 22.6 kg, respectively. Back squat and mean HBS 1RM scores were very strongly correlated (r = 0.96; p < 0.001). There were no significant differences in 1RM scores between the 3 trials. The test-retest 1RM scores with the HBS demonstrated high reliability, with an intraclass correlation coefficient of 0.98 (95% confidence interval [CI] = 0.93-0.99), and a coefficient of variation of 2.6% (95% CI = 1.9-4.3). Taken together, these data suggest that the HBS exercise is a valid and reliable method for assessing 1RM in young men with previous resistance training experience and may be useful for individuals with restricted glenohumeral mobility.

  12. Trunk Muscle Activation and Estimating Spinal Compressive Force in Rope and Harness Vertical Dance.

    PubMed

    Wilson, Margaret; Dai, Boyi; Zhu, Qin; Humphrey, Neil

    2015-12-01

    Rope and harness vertical dance takes place off the floor with the dancer suspended from his or her center of mass in a harness attached to a rope from a point overhead. Vertical dance represents a novel environment for training and performing in which expected stresses on the dancer's body are different from those that take place during dance on the floor. Two male and eleven female dancers with training in vertical dance performed six typical vertical dance movements with electromyography (EMG) electrodes placed bilaterally on rectus abdominus, external oblique, erector spinae, and latissimus dorsi. EMG data were expressed as a percentage of maximum voluntary isometric contraction (MVIC). A simplified musculoskeletal model based on muscle activation for these four muscle groups was used to estimate the compressive force on the spine. The greatest muscle activation for erector spinae and latissimus dorsi and the greatest trunk compressive forces were seen in vertical axis positions where the dancer was moving the trunk into a hyper-extended position. The greatest muscle activation for rectus abdominus and external oblique and the second highest compressive force were seen in a supine position with the arms and legs extended away from the center of mass (COM). The least muscle activation occurred in positions where the limbs were hanging below the torso. These movements also showed relatively low muscle activation compression forces. Post-test survey results revealed that dancers felt comfortable in these positions; however, observation of some positions indicated insufficient muscular control. Computing the relative contribution of muscles, expressed as muscle activation and estimated spinal compression, provided a measure of how much the muscle groups were working to support the spine and the rest of the dancer's body in the different movements tested. Additionally, identifying typical muscle recruitment patterns in each movement will help identify key exercises

  13. Optimizing the respiratory pump: harnessing inspiratory resistance to treat systemic hypotension.

    PubMed

    Convertino, Victor A; Ryan, Kathy L; Rickards, Caroline A; Glorsky, Steven L; Idris, Ahamed H; Yannopoulos, Demetris; Metzger, Anja; Lurie, Keith G

    2011-06-01

    We review the physiology and affects of inspiration through a low level of added resistance for the treatment of hypotension. Recent animal and clinical studies demonstrated that one of the body's natural response mechanisms to hypotension is to harness the respiratory pump to increase circulation. That finding is consistent with observations, in the 1960s, about the effect of lowering intrathoracic pressure on key physiological and hemodynamic variables. We describe studies that focused on the fundamental relationship between the generation of negative intrathoracic pressure during inspiration through a low level of resistance created by an impedance threshold device and the physiologic sequelae of a respiratory pump. A decrease in intrathoracic pressure during inspiration through a fixed resistance resulting in a pressure difference of 7 cm H(2)O has multiple physiological benefits, including: enhanced venous return and cardiac stroke volume, lower intracranial pressure, resetting of the cardiac baroreflex, elevated cerebral blood flow oscillations, increased tissue blood flow/pressure gradient, and maintenance of the integrity of the baroreflex-mediated coherence between arterial pressure and sympathetic nerve activity. While breathing has traditionally been thought primarily to provide gas exchange, studies of the mechanisms involved in animals and humans provide the physiological underpinnings for "the other side of breathing": to increase circulation to the heart and brain, especially in the setting of physiological stress. The existing results support the use of the intrathoracic pump to treat clinical conditions associated with hypotension, including orthostatic hypotension, hypotension during and after hemodialysis, hemorrhagic shock, heat stroke, septic shock, and cardiac arrest. Harnessing these fundamental mechanisms that control cardiopulmonary physiology provides new opportunities for respiratory therapists and others who have traditionally focused on

  14. Modelling the effect of electrical harness on microvibration response of structures

    NASA Astrophysics Data System (ADS)

    Remedia, Marcello; Aglietti, Guglielmo S.; Richardson, Guy

    2015-04-01

    The term "microvibrations" generally refers to accelerations in the region of micro-g, occurring over a wide frequency range, up to say 500-1000 Hz. The main issues related to microvibrations are their control and minimisation, which requires their modelling and analysis. A particular challenge is posed in the mid-frequency range, where many of the micro-vibration sources on board a spacecraft tend to act. In this case, in addition to the typical issues related to predicting responses in the mid-frequency, the low amplitude of the inputs can produce further non-linear behaviour which can manifest as uncertainties. A typical example is the behaviour of cables secured onto panels; when very low forces are applied, the presence of harness can influence the characteristics of the panel in terms of stiffness and damping values. In these circumstances, the cables themselves couple with the panel, hence become paths for vibration transmission. The common practise is to model such cables as Non-Structural Mass; however, this paper illustrates that this method does not yield accurate results. In order to demonstrate this, an experimental campaign was conducted investigating a honeycomb panel, which was tested bare and with different configurations of harness secured to it. The results of this experimental campaign showed significantly different behaviour of the structure depending on the amplitude of the loads and the frequency. In particular, it was found that the effects the addition of the cables had on the panel were different depending on the frequency range considered. Based on this observation, a general methodology to deal with the whole frequency range is presented here and the basis to extend it to the case of more complex structures is also proposed.

  15. Regulation of a putative corticosteroid, 17, 21-dihydroxypregn-4-ene, 3, 20-one, in sea lamprey, Petromyzon marinus.

    USGS Publications Warehouse

    Roberts, Brent W.; Didier, Wes; Satbir, Rai; Johnson, Nicholas S.; Libants, Scot V.; Sang-Seon, Yun; Close, David

    2013-01-01

    In higher vertebrates, in response to stress, the hypothalamus produces corticotropin-releasing hormone (CRH), which stimulates cells in the anterior pituitary to produce adrenocorticotropic hormone (ACTH), which in turn stimulates production of either cortisol (F) or corticosterone (B) by the adrenal tissues. In lampreys, however, neither of these steroids is present. Instead, it has been proposed that the stress steroid is actually 17,21-dihydroxypregn-4-ene-3,20-dione (11-deoxycortisol; S). However, there have been no studies yet to determine its mechanism of regulation or site of production. Here we demonstrate that (1) intraperitoneal injections of lamprey-CRH increase plasma S in a dose dependent manner, (2) intraperitoneal injections of four lamprey-specific ACTH peptides at 100 lg/kg, did not induce changes in plasma S concentrations in either males or females; (3) two lamprey-specific gonadotropin-releasing hormones (GnRH I and III) and arginine-vasotocin (AVT), all at single doses, stimulated S production as well as, or to an even greater extent than CRH; (4) sea lamprey mesonephric kidneys, in vitro, converted tritiated 17a-hydroxyprogesterone (17a-P) into a steroid that had the same chromatographic properties (on HPLC and TLC) as S; (5) kidney tissues released significantly more immunoassayable S into the incubation medium than gill, liver or gonad tissues. One interpretation of these results is that the corticosteroid production of the sea lamprey, one of the oldest extant vertebrates, is regulated through multiple pathways rather than the classical HPI-axis. However, the responsiveness of this steroid to the GnRH peptides means that a reproductive rather than a stress role for this steroid cannot yet be ruled out.

  16. Fabrication of Thiol-Ene "Clickable" Copolymer-Brush Nanostructures on Polymeric Substrates via Extreme Ultraviolet Interference Lithography.

    PubMed

    Dübner, Matthias; Gevrek, Tugce N; Sanyal, Amitav; Spencer, Nicholas D; Padeste, Celestino

    2015-06-03

    We demonstrate a new approach to grafting thiol-reactive nanopatterned copolymer-brush structures on polymeric substrates by means of extreme ultraviolet (EUV) interference lithography. The copolymer brushes were designed to contain maleimide functional groups as thiol-reactive centers. Fluoropolymer films were exposed to EUV radiation at the X-ray interference lithography beamline (XIL-II) at the Swiss Light Source, in order to create radical patterns on their surfaces. The radicals served as initiators for the copolymerization of thiol-ene "clickable" brushes, composed of a furan-protected maleimide monomer (FuMaMA) and different methacrylates, namely, methyl methacrylate (MMA), ethylene glycol methyl ether methacrylate (EGMA), or poly(ethylene glycol) methyl ether methacrylate (PEGMA). Copolymerization with ethylene-glycol-containing monomers provides antibiofouling properties to these surfaces. The number of reactive centers on the grafted brush structures can be tailored by varying the monomer ratios in the feed. Grafted copolymers were characterized by using attenuated total reflection infrared (ATR-IR) spectroscopy. The reactive maleimide methacrylate (MaMA) units were utilized to conjugate thiol-containing moieties using the nucleophilic Michael-addition reaction, which proceeds at room temperature without the need for any metal-based catalyst. Using this approach, a variety of functionalities was introduced to yield polyelectrolytes, as well as fluorescent and light-responsive polymer-brush structures. Functionalization of the brush structures was demonstrated via ATR-IR and UV-vis spectroscopy and fluorescence microscopy, and was also indicated by a color switch. Furthermore, grafted surfaces were generated via plasma activation, showing a strongly increased wettability for polyelectrolytes and a reversible switch in static water contact angle (CA) of up to 18° for P(EGMA-co-MaMA-SP) brushes, upon exposure to alternating visible and UV-light irradiation.

  17. Regulation of a putative corticosteroid, 17,21-dihydroxypregn-4-ene,3,20-one, in sea lamprey, Petromyzon marinus.

    PubMed

    Roberts, Brent W; Didier, Wes; Rai, Satbir; Johnson, Nicholas S; Libants, Scot; Yun, Sang-Seon; Close, David A

    2014-01-15

    In higher vertebrates, in response to stress, the hypothalamus produces corticotropin-releasing hormone (CRH), which stimulates cells in the anterior pituitary to produce adrenocorticotropic hormone (ACTH), which in turn stimulates production of either cortisol (F) or corticosterone (B) by the adrenal tissues. In lampreys, however, neither of these steroids is present. Instead, it has been proposed that the stress steroid is actually 17,21-dihydroxypregn-4-ene-3,20-dione (11-deoxycortisol; S). However, there have been no studies yet to determine its mechanism of regulation or site of production. Here we demonstrate that (1) intraperitoneal injections of lamprey-CRH increase plasma S in a dose dependent manner, (2) intraperitoneal injections of four lamprey-specific ACTH peptides at 100μg/kg, did not induce changes in plasma S concentrations in either males or females; (3) two lamprey-specific gonadotropin-releasing hormones (GnRH I and III) and arginine-vasotocin (AVT), all at single doses, stimulated S production as well as, or to an even greater extent than CRH; (4) sea lamprey mesonephric kidneys, in vitro, converted tritiated 17α-hydroxyprogesterone (17α-P) into a steroid that had the same chromatographic properties (on HPLC and TLC) as S; (5) kidney tissues released significantly more immunoassayable S into the incubation medium than gill, liver or gonad tissues. One interpretation of these results is that the corticosteroid production of the sea lamprey, one of the oldest extant vertebrates, is regulated through multiple pathways rather than the classical HPI-axis. However, the responsiveness of this steroid to the GnRH peptides means that a reproductive rather than a stress role for this steroid cannot yet be ruled out.

  18. Design and fabrication of uniquely shaped thiol-ene microfibers using a two-stage hydrodynamic focusing design.

    PubMed

    Boyd, Darryl A; Shields, Adam R; Howell, Peter B; Ligler, Frances S

    2013-08-07

    Microfluidic systems have advantages that are just starting to be realized for materials fabrication. In addition to the more common use for fabrication of particles, hydrodynamic focusing has been used to fabricate continuous polymer fibers. We have previously described such a microfluidics system which has the ability to generate fibers with controlled cross-sectional shapes locked in place by in situ photopolymerization. The previous fiber fabrication studies produced relatively simple round or ribbon shapes, demonstrated the use of a variety of polymers, and described the interaction between sheath-core flow-rate ratios used to control the fiber diameter and the impact on possible shapes. These papers documented the fact that no matter what the intended shape, higher flow-rate ratios produced rounder fibers, even in the absence of interfacial tension between the core and sheath fluids. This work describes how to fabricate the next generation of fibers predesigned to have a much more complex geometry, as exemplified by the "double anchor" shape. Critical to production of the pre-specified fibers with complex features was independent control over both the shape and the size of the fabricated microfibers using a two-stage hydrodynamic focusing system. Design and optimization of the channels was performed using finite element simulations and confocal imaging to characterize each of the two stages theoretically and experimentally. The resulting device design was then used to generate thiol-ene fibers with a unique double anchor shape. Finally, proof-of-principle functional experiments demonstrated the ability of the fibers to transport fluids and to interlock laterally.

  19. Introduction of thiol moieties, including their thiol-ene reactions and air oxidation, onto polyelectrolyte multilayer substrates.

    PubMed

    Madaan, Nitesh; Romriell, Naomi; Tuscano, Joshua; Schlaad, Helmut; Linford, Matthew R

    2015-12-01

    We describe the derivatization of uncross-linked and cross-linked layer-by-layer (LbL) assemblies of polyelectrolytes (polyallylamine hydrochloride and polyacrylic acid) with sulfydryl groups via Traut's reagent (2-iminothiolane). This thiolation was optimized with regards to temperature, concentration, and pH. The stability of the resulting -SH groups in the air was determined by X-ray photoelectron spectroscopy (XPS). This air oxidation has obvious implications for the use of thiol-ene reactions in materials chemistry, and there appears to be little on this topic in the literature. Three main S 2s signals were observed by XPS: at 231.5 eV (oxidized sulfur), 227.6 eV (thiol groups), and 225.4 eV (thiolate groups). Due to their rapid oxidation, we recommend that thiolated surfaces be used immediately after they are prepared. As driven by 254 nm UV light, thiol groups on polyelectrolyte multilayers react with 1,2-polybutadiene (PBd), and residual carbon-carbon double bonds on adsorbed PBd similarly react with another thiol. In the case of a fluorinated thiol, surfaces with high water contact angles (ca. 120°) are obtained. Modest exposures to light result in derivatization, while longer exposures damage the assemblies. Polyelectrolyte-thiol-PBd-thiol assemblies delaminate from their substrates when immersed for long periods of time in water. Surface silanization with an amino silane prevents this delamination and leads to stable assemblies. These assemblies withstand various stability tests. Techniques used to analyze the materials in this study include X-ray photoelectron spectroscopy (XPS), spectroscopic ellipsometry (SE), atomic force microscopy (AFM), and contact angle goniometry. Copyright © 2015 Elsevier Inc. All rights reserved.

  20. GENERATION OF TWO NOVEL CELL LINES THAT STABLY EXPRESS HAR AND FIREFLY LUCIFERASE GENES FOR ENDOCRINE SCREENING

    EPA Science Inventory

    Generation of Two Novel Cell Lines that Stably Express hAR and Firefly Luciferase Genes for Endocrine Screening
    K.L. Bobseine*1, W.R. Kelce2, P.C. Hartig*1, and L.E. Gray, Jr.1
    1USEPA, NHEERL, Reproductive Toxicology Division, RTP, NC, 2Searle, Reproductive Toxicology Divi...