Science.gov

Sample records for harli jrgenson ene

  1. 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

  2. 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.

  3. 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.

  4. 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.

  5. 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.

  6. Har Crater on Callisto

    NASA Technical Reports Server (NTRS)

    1997-01-01

    This image shows a heavily cratered region near Callisto's equator. It was taken by the Galileo spacecraft Solid State Imaging (CCD) system on its ninth orbit around Jupiter. North is to the top of the image. The 50 kilometer (30 mile) double ring crater in the center of the image is named Har. Har displays an unusual rounded mound on its floor. The origin of the mound is unclear but probably involves uplift of ice-rich materials from below, either as a 'rebound' immediately following the impact that formed the crater or as a later process. Har is older than the prominent 20 kilometer (12 mile) crater superposed on its western rim. The large crater partially visible in the northeast corner of the image is called Tindr. Chains of secondary craters (craters formed from the impact of materials thrown out of the main crater during an impact) originating from Tindr crosscut the eastern rim of Har.

    The image, centered at 3.3 degrees south latitude and 357.9 degrees west longitude, covers an area of 120 kilometers by 115 kilometers (75 miles by 70 miles). The sun illuminates the scene from the west (left). The smallest distinguishable features in the image are about 294 meters (973 feet) across. This image was obtained on June 25, 1997, when Galileo was 14,080 kilometers (8,590 miles) from Callisto.

    The Jet Propulsion Laboratory, Pasadena, CA manages the Galileo mission for NASA's Office of Space Science, Washington, DC. JPL is an operating division of California Institute of Technology (Caltech).

    This image and other images and data received from Galileo are posted on the World Wide Web, on the Galileo mission home page at URL http://galileo.jpl.nasa.gov.

  7. Harnessing our very life.

    PubMed

    Wills, Peter R; Williams, David L F; Trussell, Denys; Mann, L R B

    2013-01-01

    The Aristotelian ideas of nature (physis) and technology (techné) are taken as a starting point for understanding what it would mean for technology to be truly living. Heidegger's critique of the conflation of scientific and technological thinking in the current era is accepted as demonstrating that humanity does not have a deep enough appreciation of the nature of life to harness its essence safely. Could the vision of harnessing life be realized, which we strongly doubt, living technology would give selected humans transforming powers that could be expected to exacerbate, rather than solve, current global problems. The source of human purposefulness, and hence of both technology and ethics, is identified in nature's emergent capability to instantiate informational representations in material forms. Ethics that are properly grounded in an appreciation of intrinsic value, especially that of life, demand that proposals to give humanity the capabilities of living technology address the social, political, economic, and environmental problems inherent in its development and potential deployment. Before any development is embarked on, steps must be taken to avoid living technology, whatever the term eventually designates, becoming available for destructive or antisocial purposes such as those that might devastate humanity or irrevocably damage the natural world. PMID:23889745

  8. Harnessing our very life.

    PubMed

    Wills, Peter R; Williams, David L F; Trussell, Denys; Mann, L R B

    2013-01-01

    The Aristotelian ideas of nature (physis) and technology (techné) are taken as a starting point for understanding what it would mean for technology to be truly living. Heidegger's critique of the conflation of scientific and technological thinking in the current era is accepted as demonstrating that humanity does not have a deep enough appreciation of the nature of life to harness its essence safely. Could the vision of harnessing life be realized, which we strongly doubt, living technology would give selected humans transforming powers that could be expected to exacerbate, rather than solve, current global problems. The source of human purposefulness, and hence of both technology and ethics, is identified in nature's emergent capability to instantiate informational representations in material forms. Ethics that are properly grounded in an appreciation of intrinsic value, especially that of life, demand that proposals to give humanity the capabilities of living technology address the social, political, economic, and environmental problems inherent in its development and potential deployment. Before any development is embarked on, steps must be taken to avoid living technology, whatever the term eventually designates, becoming available for destructive or antisocial purposes such as those that might devastate humanity or irrevocably damage the natural world.

  9. Catalytic Conia-ene and related reactions.

    PubMed

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

    2015-10-01

    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. PMID:26031492

  10. Catalytic Conia-ene and related reactions.

    PubMed

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

    2015-10-01

    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.

  11. 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.

  12. 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

  13. 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.

  14. 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.

  15. Photopolymerized Thiol-Ene Systems as Shape Memory Polymers

    PubMed Central

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

    2010-01-01

    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. PMID:21072253

  16. 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

  17. Harnessing spin precession with dissipation

    PubMed Central

    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. PMID:26816050

  18. 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.

  19. Interfacial thiol-ene photoclick reactions for forming multilayer hydrogels.

    PubMed

    Shih, Han; Fraser, Andrew K; Lin, Chien-Chi

    2013-03-13

    Interfacial visible light-mediated thiol-ene photoclick reactions were developed for preparing step-growth hydrogels with multilayer structures. The effect of a noncleavage type photoinitiator eosin-Y on visible-light-mediated thiol-ene photopolymerization was first characterized using in situ photorheometry, gel fraction, and equilibrium swelling ratio. Next, spectrophotometric properties of eosin-Y in the presence of various relevant macromer species were evaluated using ultraviolet-visible light (UV-vis) spectrometry. It was determined that eosin-Y was able to reinitiate the thiol-ene photoclick reaction, even after light exposure. Because of its small molecular weight, most eosin-Y molecules readily leached out from the hydrogels. The diffusion of residual eosin-Y from preformed hydrogels was exploited for fabricating multilayer step-growth hydrogels. Interfacial hydrogel coating was formed via the same visible-light-mediated gelation mechanism without adding fresh initiator. The thickness of the thiol-ene gel coating could be easily controlled by adjusting visible light exposure time, eosin-Y concentration initially loaded in the core gel, or macromer concentration in the coating solution. The major benefits of this interfacial thiol-ene coating system include its simplicity and cytocompatibility. The formation of thiol-ene hydrogels and coatings neither requires nor generates any cytotoxic components. This new gelation chemistry may have great utilities in controlled release of multiple sensitive growth factors and encapsulation of multiple cell types for tissue regeneration. PMID:23384151

  20. Interfacial thiol-ene photoclick reactions for forming multilayer hydrogels.

    PubMed

    Shih, Han; Fraser, Andrew K; Lin, Chien-Chi

    2013-03-13

    Interfacial visible light-mediated thiol-ene photoclick reactions were developed for preparing step-growth hydrogels with multilayer structures. The effect of a noncleavage type photoinitiator eosin-Y on visible-light-mediated thiol-ene photopolymerization was first characterized using in situ photorheometry, gel fraction, and equilibrium swelling ratio. Next, spectrophotometric properties of eosin-Y in the presence of various relevant macromer species were evaluated using ultraviolet-visible light (UV-vis) spectrometry. It was determined that eosin-Y was able to reinitiate the thiol-ene photoclick reaction, even after light exposure. Because of its small molecular weight, most eosin-Y molecules readily leached out from the hydrogels. The diffusion of residual eosin-Y from preformed hydrogels was exploited for fabricating multilayer step-growth hydrogels. Interfacial hydrogel coating was formed via the same visible-light-mediated gelation mechanism without adding fresh initiator. The thickness of the thiol-ene gel coating could be easily controlled by adjusting visible light exposure time, eosin-Y concentration initially loaded in the core gel, or macromer concentration in the coating solution. The major benefits of this interfacial thiol-ene coating system include its simplicity and cytocompatibility. The formation of thiol-ene hydrogels and coatings neither requires nor generates any cytotoxic components. This new gelation chemistry may have great utilities in controlled release of multiple sensitive growth factors and encapsulation of multiple cell types for tissue regeneration.

  1. 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

  2. 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

  3. Harness cavitation to improve processing

    SciTech Connect

    Pandit, A.G.; Moholkar, V.S.

    1996-07-01

    Mention cavitation to most chemical engineers, and they undoubtedly think of it as an operational problem. Indeed, the rapid creation and then collapse of bubbles, which is after all what cavitation involves, can destroy pumps and erode other equipment. Cavitation, however, also can have a positive side--presuming it is designed for and not unplanned. In this article, the authors look at how cavitation can be harnessed to improve processes, and the mechanisms for inducing cavitation--ultrasonics and hydrodynamics--and their likely roles. Sonication, that is, the use of ultrasound, is the conventional approach for creating cavitation, and so they turn to it first. Over the past few years, a number of groups have attempted to solve the problem of scale-up and design of ultrasonic reactors. The authors review the systems that already exist and also explore a simpler and efficient alternative to the ultrasonic reactor, the hydrodynamic cavitation reactor.

  4. 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.

  5. 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,...

  6. Now To Harness The Sun!

    NASA Astrophysics Data System (ADS)

    Solar Energy Research Institute, E. L.

    1980-09-01

    Recognition of the necessity to fully develop alternative energy resources has resulted in renewed interest in capturing energy from the sun. The daily average amount of energy delivered to the earth by this essentially eternal source is a staggering 14,170 quads (1 quad = 101b Btu), compared to an annual world energy consumption of approximately 225 quads. The United States alone accounts for 35 percent, i.e., 79 quads, of the world's annual energy consumption. The incentives to harness the sun's energy are clear solar energy is free, clean, and abundant. However, the task of harvesting the energy and directing or controlling the manner in which it is used is an arduous one that encompasses diverse technologies, including direct and indirect conversion mechanisms. The solar technologies are photovoltaics, biomass conversion, solar thermal (including passive design), wind, ocean systems, and hydropower. Near-and mid-term energy contributions from solar passive design and active heating and cooling systems, wind energy conversion systems, and elements of biomass conversion such as alcohol production are expected. Later year contributions from photovoltaics, ocean systems, large solar thermal installations, and other biomass conversion processes are very promising. The impact of government policies, energy conservation, and the availability of other energy resources on the development of the solar options is significant and may influence the energy contribution that is achieved.

  7. 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.

  8. Diffusion of pent-1-ene (1); air (2)

    NASA Astrophysics Data System (ADS)

    Winkelmann, J.

    This document is part of Subvolume A `Gases in Gases, Liquids and their Mixtures' of Volume 15 `Diffusion in Gases, Liquids and Electrolytes' of Landolt-Börnstein Group IV `Physical Chemistry'. It is part of the chapter of the chapter `Diffusion in Pure Gases' and contains data on diffusion of (1) pent-1-ene; (2) air

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

    Technology Transfer Automated Retrieval System (TEKTRAN)

    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...

  10. Fabrication of resonant subwavelength grating based on thiol-ene

    NASA Astrophysics Data System (ADS)

    Zhang, Man; Deng, Qiling; Shi, Lifang; Li, Zhiwei; Pang, Hui; Zhang, Yukun; Yu, Jinqing; Hu, Song

    2014-08-01

    This paper presents an approach used to fabricate resonant subwavelength grating based on thiol-ene material. First of all, polydimethylsiloxane soft imprint stamp with opposite structure of the subwavelength grating master mold is made by casting. Then, the desired subwavelength grating with UV-curable thiol-ene material grating structure is fabricated using the polydimethylsioxane soft stamp by UV-curable soft-lithography. Here, we fabricate a subwavelength grating with period of 300nm using the approach, which could reflect blue light with wavelength ranging from 448nm to 482nm at a specific angle and presents the excellent resonant characteristic. The experimental results are consistent with the simulation results, demonstrating that the approach proposed in this paper could effectively fabricate the thiol-ene material resonant subwavelength grating structure. The thiol-ene material is a new green UV-curable polymer material, including a number of advantages such as rapid UV-curing in the natural environment, low-cost, high resolution, and regulative performance characteristic. The fabrication technique in this paper is simple, low-cost, and easy to high throughput, which has broad application prospects in the preparation of micro and nano structures.

  11. 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...

  12. 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...

  13. 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...

  14. 14 CFR 91.521 - Shoulder harness.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 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...

  15. 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...

  16. 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.

  17. 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.

  18. Seizing the Moment: Harnessing the Information Technologies.

    ERIC Educational Resources Information Center

    Bankes, Steve; And Others

    1992-01-01

    Discusses the scope of the Information Revolution, considers initiatives for harnessing information technology, and proposes a research agenda. Seven appendices detail specific initiatives relating to a global communication network, a Council for North American Information, the news media, a pan-European security information agency, multinational…

  19. 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).…

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

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... 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...

  1. 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

  2. 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...

  3. 42 CFR 84.1138 - 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. 84.1138... 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...

  4. 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...

  5. 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...

  6. 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... 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...

  7. 42 CFR 84.121 - 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. 84.121... § 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...

  8. 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...

  9. 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...

  10. 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...

  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 84.201 - 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...

  13. 42 CFR 84.1138 - 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. 84.1138... 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...

  14. 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...

  15. 42 CFR 84.121 - 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. 84.121... § 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...

  16. 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...

  17. 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...

  18. 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...

  19. 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...

  20. 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...

  1. 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...

  2. 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...

  3. 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...

  4. 42 CFR 84.201 - 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. 84.201... 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...

  5. 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...

  6. 42 CFR 84.1138 - 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. 84.1138... 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...

  7. 42 CFR 84.121 - 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. 84.121... § 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...

  8. IS-ENES: The Infrastructure for the European Network for Earth System modelling

    NASA Astrophysics Data System (ADS)

    Joussaume, Sylvie

    2013-04-01

    IS-ENES is the distributed e-infrastructure of models, model data and metadata of the European Network for Earth System Modelling (ENES). This network gathers together the European climate modelling community working on understanding and predicting climate variability and change. It organizes and supports European contributions to international experiments used in assessments of the Intergovernmental Panel on Climate Change, such as the Fifth Coupled Model Intercomparison Project (CMIP5) and the Coordinated regional Climate Downscaling Experiments (CORDEX). IS-ENES is supported by FP7 and is entering its second 4-year phase (http://is.enes.org). IS-ENES integrates the European climate modelling community, stimulates common developments of software for models and their environments, fosters the execution and exploitation of high-end simulations, in particular using the European PRACE facilities, and supports the dissemination of model results to the climate research and climate impact communities. The central point of entry to IS-ENES services, the ENES Portal (http://enes.org), integrates information on the European climate models and provides access to models and software environments needed to run and exploit model simulations, such as the climate data operators, as well as to simulation data, metadata and processing utilities. IS-ENES supports the European contribution to the international Earth System Grid Federation data distribution for CMIP5 and CORDEX. In order to help the use of climate model results for impact studies, e.g. in water management, a prototype portal climate4impact (http://www.climate4impact.eu) has been developed providing access to guidance on how to use global climate model results through documentation of use cases, and will be further developed in IS-ENES2. Adaptation to climate change requires strengthening the integration between the climate and hydro-meteorological communities and the e-infrastructure IS-ENES2 might contribute to this

  9. 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.

  10. Photopolymerizable thiol-ene nanocomposite materials for holographic applications

    NASA Astrophysics Data System (ADS)

    Tomita, Yasuo; Hata, Eiji; Yasui, Satoru; Mitsube, Ken

    2011-06-01

    We describe an experimental investigation of the photopolymerization kinetics and volume holographic recording characteristics of silica nanoparticle-polymer nanocomposites using thiol-ene monomers capable of step-growth polymerization. We characterize the visible light curing kinetics of a thiol-ene monomer system consisting of secondary dithiol with high self-life stability and low odor and triene with rigid structure and high electron density by using real-time Fourier transform spectroscopy and photocalorimetry. In plane-wave volume holographic recording at a wavelength of 532 nm it is shown that while volume holograms recorded in the nanocomposites exhibit high transparency, their saturated refractive index modulation (Δnsat) and material sensitivity (S) are as large as 1x10-2 and 1615 cm/J, respectively. The polymerization shrinkage is reduced as low as 0.4% as a result of the late gelation in conversion. These values meet the acceptable values for holographic data storage media (i.e., 5x10-3, 500 cm/J and 0.5% for Δnsat, S and shrinkage, respectively). The improved thermal stability of volume holograms recorded in the nanocomposites is also confirmed experimentally.

  11. Thiol-ene enabled detection of thiophosphorylated kinase substrates.

    PubMed

    Garber, Kathleen C A; Carlson, Erin E

    2013-08-16

    Protein phosphorylation is a ubiquitous posttranslational modification that regulates cell signaling in both prokaryotes and eukaryotes. Although the study of phosphorylation has made great progress, several major hurdles remain, including the difficulty of the assignment of endogenous substrates to a discrete kinase and of global phosphoproteomics investigations. We have developed a novel chemical strategy for detecting phosphorylated proteins. This method utilizes adenosine 5'-O-(3-thiotriphosphate) (ATPγS), which results in the transfer of a thiophosphate moiety by a kinase to its substrate(s). This group can subsequently be employed as a nucleophilic handle to promote protein detection. To selectively label thiophosphorylated proteins, cellular thiols (e.g., cysteine-containing proteins) must first be blocked. Most common cysteine-capping strategies rely upon the nucleophilicity of the sulfur group and would therefore also modify the thiophosphate moiety. We hypothesized that the radical-mediated thiol-ene reaction, however, would be selective for cysteine over thiophosphorylated amino acids due to the differences in the electronics and pKa values between these groups. Here, we report rapid and specific tagging of thiophosphorylated proteins in vitro following chemoselective thiol capping using the thiol-ene reaction.

  12. Studies on Lewis acid-mediated intramolecular cyclization reactions of allene-ene systems.

    PubMed

    Hiroi, K; Watanabe, T; Tsukui, A

    2000-03-01

    The Lewis acid-mediated reactions of allene-ene compounds, derived from 3-methylcitronellal or dimethyl malonate, were carried out using various Lewis acids such as ethylaluminum dichloride, diethylaluminum chloride, titanium chloride, zinc chloride etherate, or boron trifluoride etherate, affording unexpectedly intramolecular [2+2]cycloaddition products under some particular reaction conditions without any formation of intramolecular ene reaction products.

  13. 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.

  14. 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.

  15. 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.

  16. 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

  17. Thiol–Ene Photopolymerizations Provide a Facile Method To Encapsulate Proteins and Maintain Their Bioactivity

    PubMed Central

    2012-01-01

    Photoinitiated polymerization remains a robust method for fabrication of hydrogels, as these reactions allow facile spatial and temporal control of gelation and high compatibility for encapsulation of cells and biologics. The chain-growth reaction of macromolecular monomers, such as acrylated PEG and hyaluronan, is commonly used to form hydrogels, but there is growing interest in step-growth photopolymerizations, such as the thiol–ene “click” reaction, as an alternative. Thiol–ene reactions are not susceptible to oxygen inhibition and rapidly form hydrogels using low initiator concentrations. In this work, we characterize the differences in recovery of bioactive proteins when exposed to similar photoinitiation conditions during thiol–ene versus acrylate polymerizations. Following exposure to chain polymerization of acrylates, lysozyme bioactivity was approximately 50%; after step-growth thiol–ene reaction, lysozyme retained nearly 100% of its prereaction activity. Bioactive protein recovery was enhanced 1000-fold in the presence of a thiol–ene reaction, relative to recovery from solutions containing identical primary radical concentrations, but without the thiol–ene components. When the cytokine TGFβ was encapsulated in PEG hydrogels formed via the thiol–ene reaction, full protein bioactivity was preserved. PMID:22741550

  18. Understanding the polar mechanism of the ene reaction. A DFT study.

    PubMed

    Domingo, Luis R; Aurell, Maria J; Pérez, Patricia

    2014-10-14

    The molecular mechanism of ene reactions has been characterised by DFT methods at the MPWB1K/6-311G(d,p) level of theory. Most reactions take place along a two-stage one-step mechanism in which the C-C bond formation takes place before the hydrogen transfer process. A very good correlation between the polar character of the reaction measured by the global electron density transfer at the transition state and the activation energy has been found. This behaviour allows establishing a useful classification of ene reactions in N-ene having a very high activation energy, P-ene reactions having activation energies between 35 and 20 kcal mol(-1), and H-ene reactions having activation energies below 20 kcal mol(-1). ELF topological analysis allows the characterisation of the two-stage one-step mechanism associated with a two-centre nucleophilic/electrophilic interaction. Formation of the C-C single bond is achieved by the C-to-C coupling of two pseudoradical centres formed at the two interacting carbon atoms in the first stage of the reaction. This topological analysis establishes that bonding changes are non-concerted. Finally, a DFT reactivity analysis makes it possible to characterise the electrophilic/nucleophilic behaviour of the reagents involved in ene reactions, and consequently, to predict the feasibility of ene reactions. PMID:25139695

  19. The microbiological transformation of 7alpha-hydroxy-ent-kaur-16-ene derivatives by Gibberella fujikuroi.

    PubMed

    Fraga, Braulio M; Bressa, Carlo; González, Pedro; Guillermo, Ricardo; Hernández, Melchor G; Suárez, Sergio

    2007-06-01

    The biotransformation of 7alpha-hydroxy-ent-kaur-16-ene (epi-candol A) by the fungus Gibberella fujikuroi gave 7alpha,16alpha,17-trihydroxy-ent-kaur-16-ene and a seco-ring B derivative, fujenoic acid, whilst the incubation of candicandiol (7alpha,18-dihydroxy-ent-kaur-16-ene) and canditriol (7alpha,15alpha,18-trihydroxy-ent-kaur-16-ene) afforded 7alpha,18,19-trihydroxy-ent-kaur-16-ene and 7alpha,11beta,15alpha,18-tetrahydroxy-ent-kaur-16-ene, respectively. The presence of a 7alpha-hydroxyl group in epi-candol A avoids its biotransformation along the biosynthetic pathway of gibberellins, and directs it to the seco-ring B acids route. The 15alpha-hydroxyl group in canditriol inhibits oxidation at C-19 and direct hydroxylation at C-11(beta). The formation of fujenoic acid, from 7alpha-hydroxy-ent-kaur-16-ene, probably occurs via 7alpha-hydroxykaurenoic acid and 7-oxokaurenoic acid, with subsequent hydroxylation at the C-6(beta) position.

  20. Understanding the polar mechanism of the ene reaction. A DFT study.

    PubMed

    Domingo, Luis R; Aurell, Maria J; Pérez, Patricia

    2014-10-14

    The molecular mechanism of ene reactions has been characterised by DFT methods at the MPWB1K/6-311G(d,p) level of theory. Most reactions take place along a two-stage one-step mechanism in which the C-C bond formation takes place before the hydrogen transfer process. A very good correlation between the polar character of the reaction measured by the global electron density transfer at the transition state and the activation energy has been found. This behaviour allows establishing a useful classification of ene reactions in N-ene having a very high activation energy, P-ene reactions having activation energies between 35 and 20 kcal mol(-1), and H-ene reactions having activation energies below 20 kcal mol(-1). ELF topological analysis allows the characterisation of the two-stage one-step mechanism associated with a two-centre nucleophilic/electrophilic interaction. Formation of the C-C single bond is achieved by the C-to-C coupling of two pseudoradical centres formed at the two interacting carbon atoms in the first stage of the reaction. This topological analysis establishes that bonding changes are non-concerted. Finally, a DFT reactivity analysis makes it possible to characterise the electrophilic/nucleophilic behaviour of the reagents involved in ene reactions, and consequently, to predict the feasibility of ene reactions.

  1. 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

  2. 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.

  3. 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.

  4. Stereoselective nickel-catalyzed [2+2] cycloadditions of ene-allenes.

    PubMed

    Noucti, Njamkou N; Alexanian, Erik J

    2015-04-27

    A stereoselective nickel-catalyzed [2+2] cycloaddition of ene-allenes is reported. This transformation encompasses a broad range of ene-allene substrates, thus providing efficient access to fused cyclobutanes from easily accessed π-components. A simple and inexpensive first-row catalytic system comprised of [Ni(cod)2 ] and dppf was used in this process, thus constituting an attractive approach to synthetically challenging cyclobutane frameworks under mild reaction conditions.

  5. Interfacial thiol-ene photo-click reactions for forming multilayer hydrogels

    PubMed Central

    Shih, Han; Fraser, Andrew K.; Lin, Chien-Chi

    2014-01-01

    Interfacial visible light-mediated thiol-ene photo-click reactions were developed for preparing step-growth hydrogels with multilayer structures. The effect of a non-cleavage type photoinitiator eosin-Y on visible light-mediated thiol-ene photopolymerization was first characterized using in situ photo-rheometry, gel fraction, and equilibrium swelling ratio. Next, spectrophotometric properties of eosin-Y in the presence of various relevant macromer species were evaluated using UV/Vis spectrometry. It was determined that eosin-Y was able to re-initiate thiol-ene photo-click reaction even after light exposure. Due to its small molecular weight, most eosin-Y molecules readily leached out from the hydrogels. The diffusion of residual eosin-Y from pre-formed hydrogels was exploited for fabricating multilayer step-growth hydrogels. Interfacial hydrogel coating was formed via the same visible light-mediated gelation mechanism without adding fresh initiator. The thickness of the thiol-ene gel coating could be easily controlled by adjusting visible light exposure time, eosin-Y concentration initially loaded in the core gel, or macromer concentration in the coating solution. The major benefits of this interfacial thiol-ene coating system include its simplicity and cytocompatibility. The formation of thiol-ene hydrogels and coatings neither requires nor generates any cytotoxic components. This new gelation chemistry may have great utilities in controlled release of multiple sensitive growth factors and encapsulation of multiple cell types for tissue regeneration. PMID:23384151

  6. Direct thiol-ene photocoating of polyorganosiloxane microparticles.

    PubMed

    Kuttner, Christian; Maier, Petra C; Kunert, Carmen; Schlaad, Helmut; Fery, Andreas

    2013-12-31

    This work presents the modification of polyorganosiloxane microparticles by surface-initiated thiol-ene photochemistry. By this photocoating, we prepared different core/shell particles with a polymeric shell within narrow size distributions (PDI = 0.041-0.12). As core particle, we used highly monodisperse spherical polyorganosiloxane particles prepared from (3-mercaptopropyl)trimethoxysilane (MPTMS) with a radius of 0.49 μm. We utilize the high surface coverage of mercaptopropyl functions to generate surface-localized radicals upon irradiation with UVA-light without additional photoinitiator. The continuous generation of radicals was followed by a dye degradation experiment (UV/vis spectroscopy). Surface-localized radicals were used as copolymer anchoring sites ("grafting-onto" deposition of different PB-b-PS diblock copolymers) and polymerization initiators ("grafting-from" polymerization of PS). Photocoated particles were characterized for their morphology (SEM, TEM), size, and size distribution (DLS). For PS-coated particles, the polymer content (up to 24% in 24 h) was controlled by the polymerization time upon UVA exposure. The coating thickness was evaluated by thermogravimetric analysis (TGA) using a simple analytical core/shell model. Raman spectroscopy was applied to directly follow the time-dependent consumption of thiols by photoinitiation. PMID:24320891

  7. Thiol-ene/acrylate substrates for softening intracortical electrodes.

    PubMed

    Ware, Taylor; Simon, Dustin; Liu, Clive; Musa, Tabassum; Vasudevan, Srikanth; Sloan, Andrew; Keefer, Edward W; Rennaker, Robert L; Voit, Walter

    2014-01-01

    Neural interfaces have traditionally been fabricated on rigid and planar substrates, including silicon and engineering thermoplastics. However, the neural tissue with which these devices interact is both 3D and highly compliant. The mechanical mismatch at the biotic-abiotic interface is expected to contribute to the tissue response that limits chronic signal recording and stimulation. In this work, novel ternary thiol-ene/acrylate polymer networks are used to create softening substrates for neural recording electrodes. Thermomechanical properties of the substrates are studied through differential scanning calorimetry and dynamic mechanical analysis both before and after exposure physiological conditions. This substrate system softens from more than 1 GPa to 18 MPa on exposure to physiological conditions: reaching body temperature and taking up less than 3% fluid. The impedance of 177 µm(2) gold electrodes electroplated with platinum black fabricated on these substrates is measured to be 206 kΩ at 1 kHz. Specifically, intracortical electrodes are fabricated, implanted, and used to record driven neural activity. This work describes the first substrate system that can use the full capabilities of photolithography, respond to physiological conditions by softening markedly after insertion, and record driven neural activity for 4 weeks.

  8. 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...

  9. 46 CFR 197.324 - Diver's safety harness.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... 46 Shipping 7 2010-10-01 2010-10-01 false Diver's safety harness. 197.324 Section 197.324 Shipping COAST GUARD, DEPARTMENT OF HOMELAND SECURITY (CONTINUED) MARINE OCCUPATIONAL SAFETY AND HEALTH STANDARDS... harness used in surface-supplied diving must have— (a) A positive buckling device; and (b) An...

  10. 46 CFR 197.324 - Diver's safety harness.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... 46 Shipping 7 2013-10-01 2013-10-01 false Diver's safety harness. 197.324 Section 197.324 Shipping COAST GUARD, DEPARTMENT OF HOMELAND SECURITY (CONTINUED) MARINE OCCUPATIONAL SAFETY AND HEALTH STANDARDS... harness used in surface-supplied diving must have— (a) A positive buckling device; and (b) An...

  11. 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 COAST GUARD, DEPARTMENT OF HOMELAND SECURITY (CONTINUED) MARINE OCCUPATIONAL SAFETY AND HEALTH STANDARDS... harness used in surface-supplied diving must have— (a) A positive buckling device; and (b) An...

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

    Technology Transfer Automated Retrieval System (TEKTRAN)

    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...

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

    Technology Transfer Automated Retrieval System (TEKTRAN)

    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...

  14. 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. PMID:27621440

  15. 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.

  16. 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.

  17. 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.

  18. (η(4)-Cyclo-octa-tetra-ene)(η(8)-cyclo-octa-tetra-ene)iodido-tantalum(V).

    PubMed

    Verma, Pratik; Sussman, Victor J; Brennessel, William W; Ellis, John E

    2014-07-01

    The title complex, [Ta(η(4)-C8H8)(η(8)-C8H8)I], lies across a crystallographic mirror plane that includes the Ta(V) atom and the iodide ligand. One cyclo-octa-tetra-ene (cot) ring is η(4)-coordinating and is bis-ected by the mirror plane. The fold angle between the plane of the coordinating butadiene portion and the middle plane of the ring is 27.4 (4)°. An additional minor fold angle of 9.3 (7)° exists between the final plane in the ring and the middle plane. The other cot ring is η(8)-coordinating and is also cut by the mirror plane. In this case, the ring is disordered over the mirror plane, and one position is modeled with appropriate restraints and constraints with respect to distances, angles and displacement parameters (the second position is generated by symmetry). This ring is nearly planar, with an r.m.s. deviation of only 0.05 Å when all eight C atoms are included in the calculation. Pairs of inter-molecular η(8)-cot rings are parallel stacked and slightly off center, with a centroid-centroid distance of 3.652 Å. No other significant inter-molecular inter-actions are observed. The compound is of inter-est as the first structurally characterized mixed halogen-cot complex of the group 5 metals and contains the longest terminal Ta-I distance [3.0107 (5) Å] reported to date. PMID:25161515

  19. Impact of the Molecular Environment on Thiol-Ene Coupling For Biofunctionalization and Conjugation.

    PubMed

    Colak, Burcu; Da Silva, Julio C S; Soares, Thereza A; Gautrot, Julien E

    2016-09-21

    Thiol-ene radical coupling is increasingly used for the biofunctionalization of biomaterials and the formation of 3D hydrogels enabling cell encapsulation. Indeed, thiol-ene chemistry presents interesting features that are particularly attractive for platforms requiring specific reactions of peptides or proteins, in particular, in situ, during cell culture or encapsulation. Despite such interest, little is known about the factors impacting thiol-ene chemistry in situ, under biologically relevant conditions. Here we explore some of the molecular parameters controlling photoinitiated thiol-ene couplings with a series of alkenes and thiols, including peptides, in buffered conditions. (1)H NMR and HPLC were used to quantify the efficiency of couplings and the impact of the pH of the buffer, as well as the molecular structure and local microenvironment close to alkenes and thiols to be coupled. Some of these observations are supported by molecular dynamics and quantum mechanics calculations. An important finding of our work is that the pKa of thiols (and its variation upon changes in molecular structure) have a striking impact on coupling efficiencies. Similarly, positively charged and aromatic amino acids are found to have some impact on thiol-ene couplings. Hence, our study demonstrates that molecular design should be carefully selected in order to achieve high biofunctionalization levels in biomaterials with peptides or promote the efficient formation of peptide-based hydrogels.

  20. Impact of the Molecular Environment on Thiol-Ene Coupling For Biofunctionalization and Conjugation.

    PubMed

    Colak, Burcu; Da Silva, Julio C S; Soares, Thereza A; Gautrot, Julien E

    2016-09-21

    Thiol-ene radical coupling is increasingly used for the biofunctionalization of biomaterials and the formation of 3D hydrogels enabling cell encapsulation. Indeed, thiol-ene chemistry presents interesting features that are particularly attractive for platforms requiring specific reactions of peptides or proteins, in particular, in situ, during cell culture or encapsulation. Despite such interest, little is known about the factors impacting thiol-ene chemistry in situ, under biologically relevant conditions. Here we explore some of the molecular parameters controlling photoinitiated thiol-ene couplings with a series of alkenes and thiols, including peptides, in buffered conditions. (1)H NMR and HPLC were used to quantify the efficiency of couplings and the impact of the pH of the buffer, as well as the molecular structure and local microenvironment close to alkenes and thiols to be coupled. Some of these observations are supported by molecular dynamics and quantum mechanics calculations. An important finding of our work is that the pKa of thiols (and its variation upon changes in molecular structure) have a striking impact on coupling efficiencies. Similarly, positively charged and aromatic amino acids are found to have some impact on thiol-ene couplings. Hence, our study demonstrates that molecular design should be carefully selected in order to achieve high biofunctionalization levels in biomaterials with peptides or promote the efficient formation of peptide-based hydrogels. PMID:27510221

  1. 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.

  2. Investigations of thiol-modified phenol derivatives for the use in thiol–ene photopolymerizations

    PubMed Central

    Reinelt, Sebastian; Tabatabai, Monir; Fischer, Urs Karl; Moszner, Norbert; Utterodt, Andreas

    2014-01-01

    Summary Thiol–ene photopolymerizations gain a growing interest in academic research. Coatings and dental restoratives are interesting applications for thiol–ene photopolymerizations due to their unique features. In most studies the relative flexible and hydrophilic ester derivative, namely pentaerythritoltetra(3-mercaptopropionate) (PETMP), is investigated as the thiol component. Thus, in the present study we are encouraged to investigate the performance of more hydrophobic ester-free thiol-modified bis- and trisphenol derivatives in thiol–ene photopolymerizations. For this, six different thiol-modified bis- and trisphenol derivatives exhibiting four to six thiol groups are synthesized via the radical addition of thioacetic acid to suitable allyl-modified precursors and subsequent hydrolysis. Compared to PETMP better flexural strength and modulus of elasticity are achievable in thiol–ene photopolymerizations employing 1,3,5-triallyl-1,3,5-triazine-2,4,6-trione (TATATO) as the ene derivative. Especially, after storage in water, the flexural strength and modulus of elasticity is twice as high compared to the PETMP reference system. PMID:25161731

  3. 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

  4. 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.

  5. 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."

  6. 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)

  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. 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."

  9. Characterization of volume holographic recording in photopolymerizable nanoparticle-(thiol-ene) polymer composites at 404 nm

    NASA Astrophysics Data System (ADS)

    Kawana, Masaru; Takahashi, Jun-ichiro; Yasui, Satoru; Tomita, Yasuo

    2015-02-01

    We report on the photopolymerization dynamics and the volume holographic recording properties of a thiol-ene based nanoparticle-polymer composite (NPC) doped with a blue-sensitive photoinitiator, Darocur® TPO, by using a highly coherent blue diode laser operating at a wavelength of 404 nm. Our study indicates that volume gratings recorded in the NPC amount to meeting the material requirements of refractive index modulation and material recording sensitivity for holographic data storage media. It is also found that polymerization shrinkage of recorded NPC gratings is higher than that of the same thiol-ene based NPC with a green (523 nm)-sensitive photoinitiator, Irgacure® 784/BzO2. We attribute such a difference in shrinkage to the photopolymerization dynamics at these recording wavelengths. We show that this shrinkage increase at 404 nm can be mitigated to some extent by controlling the thiol-ene stoichiometry in the NPC.

  10. Pinpointing a Mechanistic Switch Between Ketoreduction and "Ene" Reduction in Short-Chain Dehydrogenases/Reductases.

    PubMed

    Lygidakis, Antonios; Karuppiah, Vijaykumar; Hoeven, Robin; Ní Cheallaigh, Aisling; Leys, David; Gardiner, John M; Toogood, Helen S; Scrutton, Nigel S

    2016-08-01

    Three enzymes of the Mentha essential oil biosynthetic pathway are highly homologous, namely the ketoreductases (-)-menthone:(-)-menthol reductase and (-)-menthone:(+)-neomenthol reductase, and the "ene" reductase isopiperitenone reductase. We identified a rare catalytic residue substitution in the last two, and performed comparative crystal structure analyses and residue-swapping mutagenesis to investigate whether this determines the reaction outcome. The result was a complete loss of native activity and a switch between ene reduction and ketoreduction. This suggests the importance of a catalytic glutamate vs. tyrosine residue in determining the outcome of the reduction of α,β-unsaturated alkenes, due to the substrate occupying different binding conformations, and possibly also to the relative acidities of the two residues. This simple switch in mechanism by a single amino acid substitution could potentially generate a large number of de novo ene reductases. PMID:27411040

  11. 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

  12. 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

  13. 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.

  14. Microbial and chemical transformations of some 12,13-epoxytrichothec-9,10-enes.

    PubMed

    Claridge, C A; Schmitz, H

    1978-07-01

    Resting cells of Streptomyces griseus, Mucor mucedo, and a growing culture of Acinetobacter calcoaceticus when mixed with compounds related to 12,13-epoxytrichothec-9-ene-4beta,15-diacetoxy-3alpha-ol(anguidine) produced a series of derivatives that were either partially hydrolyzed or selectively acylated. These derivatives showed marked differences in activities as assayed by antifungal and tissue culture cytotoxicity tests.

  15. 21 CFR 177.1660 - Poly (tetra-methyl-ene tere-phtha-late).

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 3 2012-04-01 2012-04-01 false Poly (tetra-methyl-ene tere-phtha-late). 177.1660 Section 177.1660 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) FOOD FOR HUMAN CONSUMPTION (CONTINUED) INDIRECT FOOD ADDITIVES: POLYMERS Substances for Use...

  16. Visible-Light-Driven Photocatalytic Initiation of Radical Thiol-Ene Reactions Using Bismuth Oxide.

    PubMed

    Fadeyi, Olugbeminiyi O; Mousseau, James J; Feng, Yiqing; Allais, Christophe; Nuhant, Philippe; Chen, Ming Z; Pierce, Betsy; Robinson, Ralph

    2015-12-01

    A nontoxic and inexpensive photocatalytic initiation of anti-Markovnikov hydrothiolation of olefins using visible light is reported. This method is characterized by low catalyst loading, thereby enabling a mild and selective method for radical initiation in thiol-ene reactions between a wide scope of olefins and thiols. PMID:26572219

  17. Antibiofouling hybrid dendritic Boltorn/star PEG thiol-ene cross-linked networks.

    PubMed

    Bartels, Jeremy W; Imbesi, Philip M; Finlay, John A; Fidge, Christopher; Ma, Jun; Seppala, Jonathan E; Nystrom, Andreas M; Mackay, Michael E; Callow, James A; Callow, Maureen E; Wooley, Karen L

    2011-06-01

    A series of thiol-ene generated amphiphilic cross-linked networks was prepared by reaction of alkene-modified Boltorn polyesters (Boltorn-ene) with varying weight percent of 4-armed poly(ethylene glycol) (PEG) tetrathiol (0-25 wt%) and varying equivalents of pentaerythritol tetrakis(3-mercaptopropionate) (PETMP) (0-64 wt%). These materials were designed to present complex surface topographies and morphologies, with heterogeneity of surface composition and properties and robust mechanical properties, to serve as nontoxic antibiofouling coatings that are amenable to large-scale production for application in the marine environment. Therefore, a two-dimensional matrix of materials compositions was prepared to study the physical and mechanical properties, over which the compositions spanned from 0 to 25 wt% PEG tetrathiol and 0-64 wt% PETMP (the overall thiol/alkene (SH/ene) ratios ranged from 0.00 to 1.00 equiv), with both cross-linker weight percentages calculated with respect to the weight of Boltorn-ene. The Boltorn-ene components were prepared through the esterification of commercially available Boltorn H30 with 3-butenoic acid. The subsequent cross-linking of the Boltorn-PEG-PETMP films was monitored using IR spectroscopy, where it was found that near-complete consumption of both thiol and alkene groups occurred when the stoichiometry was ca. 48 wt% PETMP (0.75 equiv SH/ene, independent of PEG amount). The thermal properties of the films showed an increase in T(g) with an increase in 4-armed PEG-tetrathiol wt%, regardless of the PETMP concentration. Investigation of the bulk mechanical properties in dry and wet states found that the Young's modulus was the greatest at 48 wt% PETMP (0.75 equiv of SH/ene). The ultimate tensile strength increased when PETMP was constant and the PEG concentration was increased. The Young's modulus was slightly lower for wet films at constant PEG or constant PETMP amounts, than for the dry samples. The nanoscopic surface features were

  18. Biosynthesis of Fusarium culmorum trichothecenes. The roles of isotrichodermin and 12,13-epoxytrichothec-9-ene

    SciTech Connect

    Zamir, L.O.; Devor, K.A.; Nikolakakis, A.; Sauriol, F. )

    1990-04-25

    Two different approaches enabled us to unambiguously establish the intermediacy of isotrichodermin and 12,13-epoxytrichothec-9-ene in the biosynthesis of the trichothecenes 3-acetyldeoxynivalenol and sambucinol, respectively. The kinetic pulse-labeling method enabled us to detect a plausible precursor to 3-acetyldeoxynivalenol biosynthesis. Feeding experiments using the pure 14C-labeled intermediate established that it was incorporated 27% into 3-acetyldeoxynivalenol but not to sambucinol. The 14C-precursor was subsequently used as a marker to purify the unlabeled intermediate which was shown to be isotrichodermin by spectroscopic techniques. In order to trace the enriched carbons incorporated into 3-acetylde-oxynivalenol, specifically deuteriated isotrichodermin was synthesized and fed to Fusarium culmorum. The 2H NMR spectrum of the derived 3-acetyldeoxynivalenol proved conclusively the position of the deuteriums and that isotrichodermin is a major biosynthetic precursor. The proof that isotrichodermin is converted in vivo to 3-acetyldeoxynivalenol but not to sambucinol led us to postulate that 12,13-epoxytrichothec-9-ene might have an important role in the biosynthesis of trichothecenes. We synthesized 12,13-epoxytrichothec-9-ene with tritium at C-15 or with two deuteriums at C-4 and two deuteriums at C-15. These labeled compounds enabled us to prove that 12,13-epoxytrichothec-9-ene is a major precursor to sambucinol biosynthesis but is neither converted to isotrichodermin nor to 3-acetyldeoxynivalenol. We also succeeded in isolating a biosynthetic intermediate between 12,13-epoxytrichothec-9-ene and sambucinol and characterized its structure as 3-deoxysambucinol by spectroscopic techniques (1H NMR, 2H NMR, 13C NMR, correlation spectroscopy, two-dimensional heteronuclear correlation experiments, and mass spectroscopy).

  19. 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

  20. 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 84.78 Public Health PUBLIC HEALTH SERVICE, DEPARTMENT OF HEALTH AND HUMAN SERVICES OCCUPATIONAL SAFETY AND HEALTH RESEARCH AND RELATED ACTIVITIES APPROVAL OF RESPIRATORY PROTECTIVE DEVICES...

  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 84.78 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 84.121 - 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. 84.121 Section 84.121 Public Health PUBLIC HEALTH SERVICE, DEPARTMENT OF HEALTH AND HUMAN SERVICES OCCUPATIONAL SAFETY AND HEALTH RESEARCH AND RELATED ACTIVITIES APPROVAL OF RESPIRATORY PROTECTIVE DEVICES Gas...

  3. 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 Section 84.121 Public Health PUBLIC HEALTH SERVICE, DEPARTMENT OF HEALTH AND HUMAN SERVICES OCCUPATIONAL SAFETY AND HEALTH RESEARCH AND RELATED ACTIVITIES APPROVAL OF RESPIRATORY PROTECTIVE DEVICES Gas...

  4. 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…

  5. 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.

  6. 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…

  7. Moving ahead on harnessing synthetic lethality to fight cancer.

    PubMed

    Jerby-Arnon, Livnat; Ruppin, Eytan

    2015-01-01

    We have recently developed a data-mining pipeline that comprehensively identifies cancer unique susceptibilities, following the concept of Synthetic Lethality (SL). The approach enables, for the first time, to identify and harness genome-scale SL-networks to accurately predict gene essentiality, drug response, and clinical prognosis in cancer.

  8. 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.

  9. Rh(I)-catalyzed intramolecular [3 + 2] cycloaddition reactions of 1-ene-, 1-yne- and 1-allene-vinylcyclopropanes.

    PubMed

    Jiao, Lei; Lin, Mu; Yu, Zhi-Xiang

    2010-02-21

    New Rh(I)-catalyzed intramolecular [3 + 2] cycloaddition reactions of 1-ene-, 1-yne and 1-allene-vinylcyclopropanes have been developed, affording an efficient and versatile synthesis of cyclopentane- and cyclopentene-embedded bicyclic structures.

  10. Palladium-catalyzed carbene migratory insertion using conjugated ene-yne-ketones as carbene precursors.

    PubMed

    Xia, Ying; Qu, Shuanglin; Xiao, Qing; Wang, Zhi-Xiang; Qu, Peiyuan; Chen, Li; Liu, Zhen; Tian, Leiming; Huang, Zhongxing; Zhang, Yan; Wang, Jianbo

    2013-09-11

    Palladium-catalyzed cross-coupling reactions between benzyl, aryl, or allyl bromides and conjugated ene-yne-ketones lead to the formation of 2-alkenyl-substituted furans. This novel coupling reaction involves oxidative addition, alkyne activation-cyclization, palladium carbene migratory insertion, β-hydride elimination, and catalyst regeneration. Palladium (2-furyl)carbene is proposed as the key intermediate, which is supported by DFT calculations. The palladium carbene character of the key intermediate is validated by three aspects, including bond lengths, Wiberg bond order indices, and molecular orbitals, by comparison to those reported for stable palladium carbene species. Computational studies also revealed that the rate-limiting step is ene-yne-ketone cyclization, which leads to the formation of the palladium (2-furyl)carbene, while the subsequent carbene migratory insertion is a facile process with a low energy barrier (<5 kcal/mol). PMID:23947689

  11. 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.

  12. Gold-catalyzed intramolecular [3+2] cycloadditions of 1-aryl-1-allene-6-enes.

    PubMed

    Chaudhuri, Rupsha; Liao, Hsin-Yi; Liu, Rai-Shung

    2009-09-01

    Treatment of 1-aryl-1-allen-6-enes with [PPh(3)AuCl]/AgSbF(6) (5 mol %) in CH(2)Cl(2) at 25 degrees C led to intramolecular [3+2] cycloadditions, giving cis-fused dihydrobenzo[a]fluorene products efficiently and selectively. The reactions proceeded with initial formation of trans/cis mixtures of 2-alkyl-1-isopropyl-2-phenyl-1,2-dihydronaphthalene cations B, which were convertible into the desired cis-fused cycloadducts through the combined action of a gold catalyst and a Brønsted acid. Theoretic calculation supports the participation of the trans-B cation as reaction intermediate. Although HOTf showed similar activity towards several 1-aryl-1-allen-6-enes, it lacks generality for this cycloaddition reaction.

  13. Synthesis of new lipid-inspired ionic liquids by thiol-ene chemistry: profound solvent effect on reaction pathway.

    PubMed

    Mirjafari, Arsalan; O'Brien, Richard A; West, Kevin N; Davis, James H

    2014-06-16

    The synthesis of a series of new lipid-inspired ionic liquids through thiol-ene "click" reaction with a single-step process. This synthesis offers considerable promise as an efficient and orthogonal method to construct structurally diverse imidazolium-type ionic liquids with linear and branched cationic tails, as well as versatility in the placement of the sulfur heteroatom. Profound solvent effect in this ene reaction regioselectivity has been observed.

  14. Microbial and chemical transformations of some 12,13-epoxytrichothec-9,10-enes.

    PubMed Central

    Claridge, C A; Schmitz, H

    1978-01-01

    Resting cells of Streptomyces griseus, Mucor mucedo, and a growing culture of Acinetobacter calcoaceticus when mixed with compounds related to 12,13-epoxytrichothec-9-ene-4beta,15-diacetoxy-3alpha-ol(anguidine) produced a series of derivatives that were either partially hydrolyzed or selectively acylated. These derivatives showed marked differences in activities as assayed by antifungal and tissue culture cytotoxicity tests. PMID:100053

  15. Polyhedral Oligomeric Silsesquioxane-Containing Thiol-ene Fibers with Tunable Thermal and Mechanical Properties.

    PubMed

    Fang, Yichen; Ha, Heonjoo; Shanmuganathan, Kadhiravan; Ellison, Christopher J

    2016-05-01

    Polyhedral oligomeric silsesquioxanes (POSS) are versatile inorganic-organic hybrid building blocks that have potential applications as reinforcement nanofillers, thermal stabilizers, and catalyst supports for metal nanoparticles. However, fabrication of fibrous materials with high POSS content has been a challenge because of the aggregation and solubility limits of POSS units. In this paper, we describe a robust and environmentally friendly fabrication approach of inorganic-organic hybrid POSS fibers by integrating UV initiated thiol-ene polymerization and centrifugal fiber spinning. The use of monomeric liquids in this approach not only reduces the consumption of heat energy and solvent, but it also promotes homogeneous mixing of organic and inorganic components that allows integration of large amount of POSS (up to 80 wt %) into the polymer network. The POSS containing thiol-ene fibers exhibited enhanced thermomechanical properties compared to purely organic analogs as revealed by substantial increases in residual weight and a factor of 4 increase in modulus after thermal treatment at 1000 °C. This simple fabrication approach combined with the tunability in fiber properties afforded by tailoring monomer composition make POSS containing thiol-ene fibers attractive candidates for catalyst supports and filtration media, particularly in high-temperature and harsh environments. PMID:27057758

  16. 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.

  17. Cis-pent-2-ene. Electron diffraction, vibrational analysis and molecular mechanics

    NASA Astrophysics Data System (ADS)

    Ter Brake, J. H. M.

    1984-08-01

    The molecular structure of cis-pent-2-ene has been investigated by using electron diffraction, vibrational analysis and molecular mechanics. It is possible to fit a model, describing cis-pent-2-ene as a semi-rigid molecule with one conformer only, to the electron diffraction data. However, molecular mechanics, ab initio self-consistent field molecular orbital calculations and microwave spectroscopy show that cis-pent-2-ene is not a semi-rigid molecule. The large-amplitude motion is described, using all pseudo-conformers at 10° intervals around the circle of rotation. The resulting rα structure is: r[CC] = 149.0(1), r[CC] = 133.8(2), r[CC] = 156.1(2), r[CH] = 109.2(2), r[CH] = 105.8(5) pm, ∠[CCC] = 127.4(2), ∠[CCC] = 112.4(4), ∠[CCH] = 124(2), ∠[CCH] = 114.2(3)° (standard deviations given in parentheses refer to the last significant digit).

  18. Trans-pent-2-ene. Electron diffraction, vibrational analysis and molecular mechanics

    NASA Astrophysics Data System (ADS)

    Ter Brake, J. H. M.; Mijlhoff, F. C.

    1981-12-01

    The molecular structure of trans-pent-2-ene has been investigated, using electron diffraction, vibrational analysis and molecular mechanics. It is possible to Fit a model, describing trans-pent-2-ene as a semi-rigid molecule with one conformer only, to the electron diffraction data. However, molecular mechanics shows that trans-pent-2-ene is not a semi-rigid molecule. The large-amplitude motion is described, using all pseudo-conformers at 10° intervals around the circle of rotation. The resulting rα structure is: r[-C-C] = 148.4(1), r[-CC-] = 133.4(2), r[-C-C-] = 157.6(5), r[C-H] = 108.2(1)pm; ∠[-C-CC-] = 125.4(3), ∠[C-C-C-] = 115.6(6), ∠[-C-C-H] = 12.7(6), ∠[-CC-H] = 129(2)°. Standard deviations given in parentheses refer to the last significant digit.

  19. 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.

  20. Synthesis and Characterization of Thiol-Ene Functionalized Siloxanes and Evaluation of their Crosslinked Network Properties

    PubMed Central

    Cole, Megan A.; Bowman, Christopher N.

    2012-01-01

    Three types of linear thiol-functionalized siloxane oligomers and three types of ene-functionalized oligomers were synthesized and subsequently photopolymerized. Within each type of thiol-functionalized oligomer, the ratio of mercaptan repeat units to non-reactive phenyl repeat units was varied to manipulate both the crosslink density and the degree of secondary interactions through pi-pi stacking. Similarly, the repeat units of the three ene-functionalized oligomers are composed of allyl-functional monomers, benzene-functional monomers, and octyl-functional monomers in varying ratios of benzene:octyl but with a constant fraction of allyl moieties. The structural composition of the siloxane oligomers plays a pivotal role in the observed material properties of networks formed through thiol-ene photopolymerization. Networks with a high concentration of thiol functionalities exhibit higher rubbery moduli, ultimate strengths, and Young’s moduli than networks with lower thiol concentrations. Moreover, the concentration of functionalities capable of participating in secondary interactions via hydrogen bonding or pi-pi stacking directly impacts the network glass transition temperature and elasticity. The combination of low crosslink density and high secondary interactions produces networks with the greatest toughness. Finally, the fraction of octyl repeats correlates with the hydrophobic nature of the network. PMID:23162209

  1. 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

  2. 14 CFR 91.107 - Use of safety belts, shoulder harnesses, and child restraint systems.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... 14 Aeronautics and Space 2 2011-01-01 2011-01-01 false Use of safety belts, shoulder harnesses... OPERATING AND FLIGHT RULES Flight Rules General § 91.107 Use of safety belts, shoulder harnesses, and child... fasten and unfasten that person's safety belt and, if installed, shoulder harness. (2) No pilot may...

  3. 14 CFR 91.107 - Use of safety belts, shoulder harnesses, and child restraint systems.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... Safety Standard No. 213 (49 CFR 571.213)), vest- and harness-type child restraint systems, and lap held... 14 Aeronautics and Space 2 2013-01-01 2013-01-01 false Use of safety belts, shoulder harnesses... OPERATING AND FLIGHT RULES Flight Rules General § 91.107 Use of safety belts, shoulder harnesses, and...

  4. 14 CFR 91.107 - Use of safety belts, shoulder harnesses, and child restraint systems.

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ... Safety Standard No. 213 (49 CFR 571.213)), vest- and harness-type child restraint systems, and lap held... 14 Aeronautics and Space 2 2014-01-01 2014-01-01 false Use of safety belts, shoulder harnesses... OPERATING AND FLIGHT RULES Flight Rules General § 91.107 Use of safety belts, shoulder harnesses, and...

  5. 14 CFR 91.107 - Use of safety belts, shoulder harnesses, and child restraint systems.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... Safety Standard No. 213 (49 CFR 571.213)), vest- and harness-type child restraint systems, and lap held... 14 Aeronautics and Space 2 2012-01-01 2012-01-01 false Use of safety belts, shoulder harnesses... OPERATING AND FLIGHT RULES Flight Rules General § 91.107 Use of safety belts, shoulder harnesses, and...

  6. 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

  7. Harnessing FOXP3+ regulatory T cells for transplantation tolerance

    PubMed Central

    Waldmann, Herman; Hilbrands, Robert; Howie, Duncan; Cobbold, Stephen

    2014-01-01

    Early demonstrations that mice could be tolerized to transplanted tissues with short courses of immunosuppressive therapy and that with regard to tolerance to self, CD4+FOXP3+ regulatory T cells (Tregs) appeared to play a critical role, have catalyzed strategies to harness FOXP3-dependent processes to control rejection in human transplantation. This review seeks to examine the scientific underpinning for this new approach to finesse immunosuppression. PMID:24691478

  8. 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.

  9. 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.

  10. Usability issues concerning child restraint system harness design.

    PubMed

    Rudin-Brown, Christina M; Kumagai, Jason K; Angel, Harry A; Iwasa-Madge, Kim M; Noy, Y Ian

    2003-05-01

    A study was conducted to assess usability issues relating to child restraint system (CRS) harness design. Four convertible child restraint systems representing a wide variety of design features were used. Forty-two participants installed two child test dummies in both forward- and rear-facing configurations either inside or outside a test vehicle. Observer-scored checklists determined the degree to which each harness was installed correctly. Participant-scored questionnaires evaluated the 'ease-of-use' of various design features. While the percentage of correct installations exceeded 83% for all designs when installed in the forward-facing configuration, in the rear-facing position (that intended for children under 9-10 kg), there was a significant (between 65 and 89%) percentage of incorrect installations for all models. This finding is of particular interest and may be indicative of a more generalized problem with 'convertible' CRS designs when they are used in the rear-facing configuration. Furthermore, while certain design features were perceived by users as providing significantly better protection in the event of a collision, these also tended to be the features that were misused most often. The benefits and costs of various design features are discussed, and a method to test harness design usability is presented. PMID:12643951

  11. Network harness: bundles of routes in public transport networks

    NASA Astrophysics Data System (ADS)

    Berche, B.; von Ferber, C.; Holovatch, T.

    2009-12-01

    Public transport routes sharing the same grid of streets and tracks are often found to proceed in parallel along shorter or longer sequences of stations. Similar phenomena are observed in other networks built with space consuming links such as cables, vessels, pipes, neurons, etc. In the case of public transport networks (PTNs) this behavior may be easily worked out on the basis of sequences of stations serviced by each route. To quantify this behavior we use the recently introduced notion of network harness. It is described by the harness distribution P(r, s): the number of sequences of s consecutive stations that are serviced by r parallel routes. For certain PTNs that we have analyzed we observe that the harness distribution may be described by power laws. These power laws indicate a certain level of organization and planning which may be driven by the need to minimize the costs of infrastructure and secondly by the fact that points of interest tend to be clustered in certain locations of a city. This effect may be seen as a result of the strong interdependence of the evolutions of both the city and its PTN. To further investigate the significance of the empirical results we have studied one- and two-dimensional models of randomly placed routes modeled by different types of walks. While in one dimension an analytic treatment was successful, the two dimensional case was studied by simulations showing that the empirical results for real PTNs deviate significantly from those expected for randomly placed routes.

  12. The biosynthesis of some androst-16-enes from C21 and C19 steroids in boar testicular and adrenal tissue

    PubMed Central

    Ahmad, N.; Gower, D. B.

    1968-01-01

    1. The formation of androst-16-enes from [4-14C]progesterone has been investigated with long-term incubations and short-term kinetic studies. After 4hr., 1·7 and 10·3% respectively of 3α- and 3β-hydroxy-5α-androst-16-enes were formed in boar testis minces, but much smaller yields were obtained in boar adrenal. Both tissues formed small quantities of androsta-4,16-dien-3-one. 2. The amounts of androst-4-ene-3,17-dione and testosterone isolated were small, suggesting that androst-16-ene formation may occur preferentially in the boar testis. 3. In the absence of tissue no radioactive androst-16-enes were formed. 4. Incubation of both [4-14C]pregnenolone and [7α-3H]progesterone resulted in 3α- and 3β-hydroxy-5α-androst-16-enes containing 3H/14C ratios of near unity and confirmed that both C21 steroids were precursors. A similar incubation with 17α-hydroxy[4-14C]-progesterone and [7α-3H]progesterone gave the same Δ16-alcohols, but they contained only 3H, indicating that side-chain cleavage of pregnenolone and progesterone occurred before 17α-hydroxylation. 5. Dehydroepiandrosterone, testosterone, testosterone acetate and 16-dehydroprogesterone were not found to be precursors of Δ16-steroids. 6. A pathway is proposed for the biosynthesis of 3α- and 3β-hydroxy-5α-androst-16-enes from pregnenolone and progesterone; this may involve androsta-4,16-dien-3-one as an intermediate, but excludes 17α-hydroxyprogesterone, testosterone and dehydroepiandrosterone. ImagesPLATE 1 PMID:4233122

  13. 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.

  14. 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.

  15. 1H NMR chemical shift studies of pregn-5-ene-3β,20( R)-diol and pregn-5-ene-3β-ol,20-one D-glucopyranoside derivatives

    NASA Astrophysics Data System (ADS)

    Warthen, J. D.; Waters, R. M.; Oliver, J. E.

    The 1H NMR chemical shift and J value data of a series of pregn-5-ene-3β,20( R)-diol/pregn-5-ene-3β-ol, 20-one D-glucopyranosides and D-glucopyranoside derivatives are reported because of their relevance to the structure determination of pregnenediol tri- and diglucosides on tobacco hornworm eggs. Effects of various substituents at the 3β- and 20( R)-positions of the pregn-5-ene nucleus upon chemical shifts of selected protons on the pregn-5-ene nucleus are discussed. Chemical shifts of selected protons on the D-glucopyranoside nucleus/nuclei are also discussed. Differentiation between the pregn-5-ene substitution points, between anomeric glucose configurations and between anomeric protons on β- D-glucosides at 3β and 20( R) is demonstrated. A COSY NMR analysis of the Manduca peracetylated triglucoside is utilized to show the interaction of the three anomeric β- D-glucoside protons and to distinguish the dissimilar one.

  16. 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

  17. Synthesis of Non-linear Protein Dimers through a Genetically Encoded Thiol-ene Reaction

    PubMed Central

    Torres-Kolbus, Jessica; Chou, Chungjung; Liu, Jihe; Deiters, Alexander

    2014-01-01

    Site-specific incorporation of bioorthogonal unnatural amino acids into proteins provides a useful tool for the installation of specific functionalities that will allow for the labeling of proteins with virtually any probe. We demonstrate the genetic encoding of a set of alkene lysines using the orthogonal PylRS/PylTCUA pair in Escherichia coli. The installed double bond functionality was then applied in a photoinitiated thiol-ene reaction of the protein with a fluorescent thiol-bearing probe, as well as a cysteine residue of a second protein, showing the applicability of this approach in the formation of heterogeneous non-linear fused proteins. PMID:25181502

  18. Plasmachemical Double Click Thiol-ene Reactions for Wet Electrical Barrier.

    PubMed

    Fraser, R C; Carletto, A; Wilson, M; Badyal, J P S

    2016-08-24

    Click thiol-ene chemistry is demonstrated for the reaction of thiol containing molecules with surface alkene bonds during electrical discharge activation. This plasmachemical reaction mechanism is shown to be 2-fold for allyl mercaptan (an alkene and thiol group containing precursor), comprising self-cross-linked nanolayer deposition in tandem with interfacial cross-linking to the surface alkene bonds of a polyisoprene base layer. A synergistic multilayer structure is attained which displays high wet electrical barrier performance during immersion in water. PMID:27505445

  19. Organocatalytic Enantioselective Nucleophilic Alkynylation of Allyl Fluorides Affording Chiral Skipped Ene-ynes.

    PubMed

    Okusu, Satoshi; Okazaki, Hiroki; Tokunaga, Etsuko; Soloshonok, Vadim A; Shibata, Norio

    2016-06-01

    Asymmetric methods for preparation of chiral alkynyl-containing compounds are in extremely high demand in many sectors of chemical research. In this work, we report the discovery of a general organocatalytic enantioselective alkynylation based on the idea of Si/F activation of the allylic C-F bond. This approach features reasonably broad substrate scope, functional group tolerance, and relatively neutral, mild, and operationally convenient reaction conditions; all of which bode well for the synthetic value of the discovered method. In particular, this method provides unique chiral skipped 1,4-ene-ynes having two kinds of versatile functional groups. PMID:27111713

  20. 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.

  1. Understanding and Harnessing Placebo Effects: Clearing Away the Underbrush

    PubMed Central

    Miller, Franklin G.; Brody, Howard

    2011-01-01

    Despite strong growth in scientific investigation of the placebo effect, understanding of this phenomenon remains deeply confused. We investigate critically seven common conceptual distinctions that impede clear understanding of the placebo effect: (1) verum/placebo, (2) active/inactive, (3) signal/noise, (4) specific/nonspecific, (5) objective/subjective, (6) disease/illness, and (7) intervention/context. We argue that some of these should be eliminated entirely, whereas others must be used with caution to avoid bias. Clearing away the conceptual underbrush is needed to lay down a path to understanding and harnessing placebo effects in clinical medicine. PMID:21220523

  2. Harnessing geometric and magnetic nonlinearities in phononic meta-plates

    NASA Astrophysics Data System (ADS)

    Bilal, Osama; Foehr, Andre; Daraio, Chiara

    Owing to their physical realization, locally resonant metamaterials retain narrow subwavelength band gaps. Moreover, the fixed geometry and dimensions of the unit cell set a hardbound on the central frequency of the operational bandwidth. Real-time tunable metamaterials extend the range of applications and further enable the realization of new sensors, filters, and switches. Our work harnesses the interaction between geometric nonlinearity and nonlinear magnetic potentials to engineer frequency-agile subwavelength band gaps. The concept is general and applicable to various metamaterials systems. Both numerical simulations and experimental realization of the proposed concept will be presented.

  3. 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.

  4. "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.

  5. 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. PMID:26743654

  6. 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.

  7. 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.

  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. PMID:27378284

  9. Synthesis and characterization of thiol-ene functionalized siloxanes and evaluation of their polymerization kinetics, network properties, and dental applications

    NASA Astrophysics Data System (ADS)

    Cole, Megan A.

    We explored formation-structure-property relationships in thiol-ene functionalized oligosiloxanes to create crosslinked networks. Specifically, nine oligomers were synthesized, three with thiol-functional silane repeats and three with allyl-functional silane repeats. Structural variations in each oligomer were systematically induced through the incorporation of non-reactive repeats bearing either diphenyl or di-n-octyl moieties, and the oligomer molecular weight was limited by the presence of monofunctional silane condensation species. The molecular weights and chain compositions of all oligomers were ascertained and subsequently used in the evaluation of network properties formed upon photopolymerization of thiol- and ene-functional reactants. Polymerization kinetics of the thiol-ene functionalized siloxanes were also investigated using photoinitiation owing to the spatial and temporal control afforded by this technique. In particular, the effects of the viscosity of the ene-functionalized oligomer and the degree of thiol functionalization on the observed polymerization rate were determined. Results showed that the speed of polymerization varied with changes to the rate-limiting step, which was heavily influenced by neighboring non-reactive functionalities. Moreover, the thiol-ene reaction was found to exhibity unimolecular termination exclusively in siloxane-based systems. Proposed use of the thiol-ene functionalized siloxane system as a dental impression material necessitated the development of a redox initiation scheme. Evaluation of the benzoylperoxide/dimethyl-p-toluidine redox pair in traditional systems showed bulk thiol-ene polymerizations comparable to photoinitiation with the added advantage of uninhibited depth control, as also demonstrated in small molecule thiol-ene coupling reactions initiated by this same redox system. Application of the redox pair to the siloxane system allowed for the viscoelastic properties as well as the feature replication

  10. Transition-Metal-Free Cascade Synthesis of 4-Quinolones: Umpolung of Michael Acceptors via Ene Reaction with Arynes.

    PubMed

    Santhosh Reddy, R; Lagishetti, Chandraiah; Kiran, I N Chaithanya; You, Hengyao; He, Yun

    2016-08-01

    A novel "one-pot" aryne transformation is described that affords various 4-quinolone derivatives without recourse to transition-metal catalysis. Arynes react with aza-Morita-Baylis-Hillman (AMBH) adducts through a cascade sequence involving an insertion/cyclization/ene reaction process to afford 4-quinolones in high yields with a broad substrate scope under mild reaction conditions. Essentially, an umpolung of reactivity at the β carbon of α,β-unsaturated ketone has been achieved by an inverse electron demand aryne-ene reaction to provide a C-arylated product. PMID:27434217

  11. Which is the better forecasting model? A comparison between HAR-RV and multifractality volatility

    NASA Astrophysics Data System (ADS)

    Ma, Feng; Wei, Yu; Huang, Dengshi; Chen, Yixiang

    2014-07-01

    In this paper, by taking the 5-min high frequency data of the Shanghai Composite Index as example, we compare the forecasting performance of HAR-RV and Multifractal volatility, Realized volatility, Realized Bipower Variation and their corresponding short memory model with rolling windows forecasting method and the Model Confidence Set which is proved superior to SPA test. The empirical results show that, for six loss functions, HAR-RV outperforms other models. Moreover, to make the conclusions more precise and robust, we use the MCS test to compare the performance of their logarithms form models, and find that the HAR-log(RV) has a better performance in predicting future volatility. Furthermore, by comparing the two models of HAR-RV and HAR-log(RV), we conclude that, in terms of performance forecasting, the HAR-log(RV) model is the best model among models we have discussed in this paper.

  12. Reactions of NO 3 with the man-made emissions 2-methylpent-2-ene, ( Z)-3-methylpent-2-ene, ethyl vinyl ether, and the stress-induced plant emission ethyl vinyl ketone

    NASA Astrophysics Data System (ADS)

    Pfrang, Christian; Tooze, Christopher; Nalty, Andrew; Canosa-Mas, Carlos E.; Wayne, Richard P.

    Rate coefficients for reactions of nitrate radicals (NO 3) with the anthropogenic emissions 2-methylpent-2-ene, ( Z)-3-methylpent-2-ene, ethyl vinyl ether, and the stress-induced plant emission ethyl vinyl ketone (pent-1-en-3-one) were determined to be (9.3±1.1)×10 -12, (9.3±3.2)×10 -12, (1.7±1.3)×10 -12 and (9.4±2.7)×10 -17 cm 3 molecule -1 s -1. We performed kinetic experiments at room temperature and atmospheric pressure using a relative-rate technique with GC-FID analysis. Experiments with ethyl vinyl ether required a modification of our established procedure that might introduce additional uncertainties, and the errors suggested reflect these difficulties. Rate coefficients are discussed in terms of electronic and steric influences. Atmospheric lifetimes with respect to important oxidants in the troposphere were calculated. NO 3-initiated oxidation is found to be the strongly dominating degradation route for 2-methylpent-2-ene, ( Z)-3-methylpent-2-ene and ethyl vinyl ether. Atmospheric concentrations of the alkenes and their relative contribution to the total NMHC emissions from trucks can be expected to increase if plans for the introduction of particle filters for diesel engines are implemented on a global scale. Thus more kinetic data are required to better evaluate the impact of these emissions.

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

    PubMed

    Akbar, Sikkandarkani; Srinivasan, Kannupal

    2016-02-01

    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. PMID:26726826

  14. 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.

  15. 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.

  16. 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. PMID:23799872

  17. Direct covalent attachment of DNA microarrays by rapid thiol-ene "click" chemistry.

    PubMed

    Escorihuela, Jorge; Bañuls, María-José; Grijalvo, Santiago; Eritja, Ramón; Puchades, Rosa; Maquieira, Angel

    2014-03-19

    A rapid strategy for the covalent immobilization of DNA onto silicon-based materials using the UV-initiated radical thiol-ene reaction is presented in this study. Following this approach, thiol- and alkene-modified oligonucleotide probes were covalently attached in microarray format, reaching immobilization densities around 6 pmol·cm(-2). The developed methodology presents the advantages of spatially controlled probe anchoring (using a photomask), direct attachment without using cross-linkers (one-pot fashion), and short irradiation times (20 min). Using the described strategy, hybridization efficiencies up to 65% with full complementary strands were reached. The approach was evaluated by scoring single-base pair mismatches with discrimination ratios around 15. Moreover, the efficacy of the proposed DNA detection scheme is further demonstrated through the assay on a genomic target of bacterial Escherichia coli.

  18. 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

  19. Blue-sensitized nanoparticle-(thiol-ene) polymer composites for volume holographic recording

    NASA Astrophysics Data System (ADS)

    Takahashi, Jun-ichiro; Kawana, Masaru; Tomita, Yasuo

    2016-04-01

    We describe an experimental investigation of volume holographic recording in photopolymerizable thiol-ene based nanoparticle-polymer composites (NPCs) at a wavelength of 404 nm. We introduce a new photoinitiator, Irgacure819, for efficient volume holographic recording in the blue-violet spectral region and measure the photopolymerization dynamics and the holographic recording properties at its varying concentrations. It is found that doping of 0.1 wt.% Irgacure 819 provides the saturated refractive index modulation amplitude as large as 9.5×10-3 and the material recording sensitiviey as high as 1800 cm/J. These measured values are much larger than the minimum required values for holographic data storage media. It is also shown that the out-of-plane shrinkage can be suppressed more with decreasing the photoinitiator concentration. We compare these results with another blue sensitizer, Darocur TPO, to evaluate the performance of Irgacure 819.

  20. 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. PMID:25168644

  1. Highly stretchable thermoset fibers and nonwovens using thiol-ene photopolymerization.

    PubMed

    Shanmuganathan, Kadhiravan; Elliot, Steven M; Lane, Austin P; Ellison, Christopher J

    2014-08-27

    In this report, we describe the preparation and characterization of a new class of thermoset fibers with high elongation and elastic recovery. Integrating UV-activated thiol-ene photopolymerization and electrospinning, we demonstrate an environmentally friendly single step approach to convert small monomeric precursor molecules into highly elastic fibers and nonwoven mats. The fibers were derived by in situ photopolymerization of a trifunctional vinyl ether monomer and a tetrafunctional thiol. Although thermosets often offer good chemical and thermal stability, these fibers also have a high average elongation at break of 62%. The elastomeric nature of these vinyl-ether based fibers can be partly attributed to their subambient Tg and partly to the cross-link density, monomer structure, and resulting network homogeneity. Nonwoven mats of these fibers were also stretchable and exhibited a much higher elongation at break of about 85%. These thermoset stretchable fibers could have potential applications as textile, biomedical, hot chemical filtration, and composite materials. PMID:25075754

  2. 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.

  3. Highly stretchable thermoset fibers and nonwovens using thiol-ene photopolymerization.

    PubMed

    Shanmuganathan, Kadhiravan; Elliot, Steven M; Lane, Austin P; Ellison, Christopher J

    2014-08-27

    In this report, we describe the preparation and characterization of a new class of thermoset fibers with high elongation and elastic recovery. Integrating UV-activated thiol-ene photopolymerization and electrospinning, we demonstrate an environmentally friendly single step approach to convert small monomeric precursor molecules into highly elastic fibers and nonwoven mats. The fibers were derived by in situ photopolymerization of a trifunctional vinyl ether monomer and a tetrafunctional thiol. Although thermosets often offer good chemical and thermal stability, these fibers also have a high average elongation at break of 62%. The elastomeric nature of these vinyl-ether based fibers can be partly attributed to their subambient Tg and partly to the cross-link density, monomer structure, and resulting network homogeneity. Nonwoven mats of these fibers were also stretchable and exhibited a much higher elongation at break of about 85%. These thermoset stretchable fibers could have potential applications as textile, biomedical, hot chemical filtration, and composite materials.

  4. 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

  5. Oxidatively Triggered Carbon-Carbon Bond Formation in Ene-amide Complexes.

    PubMed

    Jacobs, Brian P; Wolczanski, Peter T; Lobkovsky, Emil B

    2016-05-01

    Ene-amides have been explored as ligands and substrates for oxidative coupling. Treatment of CrCl2, Cl2Fe(PMe3)2, and Cl2Copy4 with 2 equiv of {(2,6-(i)Pr2C6H3)(1-(c)Hexenyl)N}Li afforded pseudosquare planar {η(3)-C,C,N-(2,6-(i)Pr2C6H3)(1-(c)Hexenyl)N}2Cr (1-Cr, 78%), trigonal {(2,6-(i)Pr2C6H3)(1-(c)Hexenyl)N}2Fe(PMe3) (2-Fe, 80%), and tetrahedral {(2,6-(i)Pr2C6H3)(1-(c)Hexenyl)N}2Co(py)2 (3-Co, 91%) in very good yields. The addition of CrCl3 to 1-Cr, and FeCl3 to 2-Fe, afforded oxidatively triggered C-C bond formation as rac-2,2'-di(2,6-(i)Pr2C6H3N═)2dicyclohexane (EA2) was produced in modest yields. Various lithium ene-amides were similarly coupled, and the mechanism was assessed via stoichiometric reactions. Some ferrous compounds (e.g., 2-Fe, FeCl2) were shown to catalyze C-arylation of {(2,6-(i)Pr2C6H3)(1-(c)Hexenyl)N}Li with PhBr, but the reaction was variable. Structural characterizations of 1-Cr, 2-Fe, and 3-Co are reported. PMID:27064509

  6. 42 CFR 84.116 - Harnesses; installation and construction; minimum requirements.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... components of the gas mask in position against the wearer's body. (b) Harnesses shall be designed and constructed to permit easy removal and replacement of gas mask parts, and where applicable, provide for... DEVICES Gas Masks § 84.116 Harnesses; installation and construction; minimum requirements. (a) Each...

  7. 42 CFR 84.116 - Harnesses; installation and construction; minimum requirements.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... components of the gas mask in position against the wearer's body. (b) Harnesses shall be designed and constructed to permit easy removal and replacement of gas mask parts, and where applicable, provide for... DEVICES Gas Masks § 84.116 Harnesses; installation and construction; minimum requirements. (a) Each...

  8. 42 CFR 84.116 - Harnesses; installation and construction; minimum requirements.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... components of the gas mask in position against the wearer's body. (b) Harnesses shall be designed and constructed to permit easy removal and replacement of gas mask parts, and where applicable, provide for... DEVICES Gas Masks § 84.116 Harnesses; installation and construction; minimum requirements. (a) Each...

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

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ... 14 Aeronautics and Space 3 2014-01-01 2014-01-01 false Seats, safety belts, and shoulder harnesses... § 121.311 Seats, safety belts, and shoulder harnesses. (a) No person may operate an airplane unless... each person on board the airplane who has reached his second birthday; and (2) An approved safety...

  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... each person on board the airplane who has reached his second birthday; and (2) An approved safety...

  11. 14 CFR 121.311 - Seats, safety belts, and shoulder harnesses.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... 14 Aeronautics and Space 3 2012-01-01 2012-01-01 false Seats, safety belts, and shoulder harnesses... § 121.311 Seats, safety belts, and shoulder harnesses. (a) No person may operate an airplane unless... each person on board the airplane who has reached his second birthday; and (2) An approved safety...

  12. 14 CFR 121.311 - Seats, safety belts, and shoulder harnesses.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... 14 Aeronautics and Space 3 2013-01-01 2013-01-01 false Seats, safety belts, and shoulder harnesses... § 121.311 Seats, safety belts, and shoulder harnesses. (a) No person may operate an airplane unless... each person on board the airplane who has reached his second birthday; and (2) An approved safety...

  13. 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... each person on board the airplane who has reached his second birthday; and (2) An approved safety...

  14. 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…

  15. 14 CFR 135.171 - Shoulder harness installation at flight crewmember stations.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... 14 Aeronautics and Space 3 2013-01-01 2013-01-01 false Shoulder harness installation at flight crewmember stations. 135.171 Section 135.171 Aeronautics and Space FEDERAL AVIATION ADMINISTRATION... harness installed for each flight crewmember station. (b) Each flight crewmember occupying a...

  16. 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 crewmember stations. 135.171 Section 135.171 Aeronautics and Space FEDERAL AVIATION ADMINISTRATION... harness installed for each flight crewmember station. (b) Each flight crewmember occupying a...

  17. 14 CFR 135.171 - Shoulder harness installation at flight crewmember stations.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... 14 Aeronautics and Space 3 2012-01-01 2012-01-01 false Shoulder harness installation at flight crewmember stations. 135.171 Section 135.171 Aeronautics and Space FEDERAL AVIATION ADMINISTRATION... harness installed for each flight crewmember station. (b) Each flight crewmember occupying a...

  18. 14 CFR 135.171 - Shoulder harness installation at flight crewmember stations.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... 14 Aeronautics and Space 3 2011-01-01 2011-01-01 false Shoulder harness installation at flight crewmember stations. 135.171 Section 135.171 Aeronautics and Space FEDERAL AVIATION ADMINISTRATION... harness installed for each flight crewmember station. (b) Each flight crewmember occupying a...

  19. 14 CFR 135.171 - Shoulder harness installation at flight crewmember stations.

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ... 14 Aeronautics and Space 3 2014-01-01 2014-01-01 false Shoulder harness installation at flight crewmember stations. 135.171 Section 135.171 Aeronautics and Space FEDERAL AVIATION ADMINISTRATION... harness installed for each flight crewmember station. (b) Each flight crewmember occupying a...

  20. 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...

  1. 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...

  2. 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...

  3. 42 CFR 84.173 - Harnesses; installation and construction; minimum requirements.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... DEVICES Non-Powered Air-Purifying Particulate Respirators § 84.173 Harnesses; installation and construction; minimum requirements. (a) Each respirator shall, where necessary, be equipped with a suitable harness designed and constructed to hold the components of the respirator in position against the...

  4. 42 CFR 84.196 - Harnesses; installation and construction; minimum requirements.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... 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 and constructed to hold the components of the respirator in position against the wearer's body. (b)...

  5. 42 CFR 84.173 - Harnesses; installation and construction; minimum requirements.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... DEVICES Non-Powered Air-Purifying Particulate Respirators § 84.173 Harnesses; installation and construction; minimum requirements. (a) Each respirator shall, where necessary, be equipped with a suitable harness designed and constructed to hold the components of the respirator in position against the...

  6. 42 CFR 84.133 - Harnesses; installation and construction; minimum requirements.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... 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 designed and constructed to hold the components of the respirator in position against the wearer's body....

  7. 42 CFR 84.196 - Harnesses; installation and construction; minimum requirements.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... 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 and constructed to hold the components of the respirator in position against the wearer's body. (b)...

  8. 42 CFR 84.133 - Harnesses; installation and construction; minimum requirements.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... 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 designed and constructed to hold the components of the respirator in position against the wearer's body....

  9. Epigenetic epidemiology for cancer risk: harnessing germline epigenetic variation.

    PubMed

    Brennan, Kevin; Flanagan, James M

    2012-01-01

    Genetic epidemiology aims to use the natural variation in the genome, namely single nucleotide polymorphisms and copy number variants to look for associations between particular genotypes and disease risk or prognosis. Recent work is now aiming to look further into the genome at the natural variation present in the epigenome, in DNA methylation as well as histone modifications, which both regulate gene expression. Epigenetic epidemiology aims to address the same questions about disease risk and prognosis using the normal epigenetic variability. Some examples of rare "epimutations" that can be detected in peripheral blood DNA have been reported in the genes MLH1, MSH2 and IGF2. Other studies have reported increased cancer risk with skewed distributions of the normal pattern in cancer cases compared to controls, showing the promise of harnessing the normal variation in the epigenome. However, some confounding factors need to be considered including the relationship between the epigenome and increasing age and tissue heterogeneity. Future studies using genome-wide approaches will likely find many more novel epigenetic biomarkers for cancer risk and prognosis.

  10. Harnessing the electromagnetic absorptions of metamaterials for positive applications

    NASA Astrophysics Data System (ADS)

    Xiang, Yuanjiang; Zou, Yanhong; Luo, Hailu; Dai, Xiaoyu; Wen, Shuangchun; Fan, Dianyuan

    2010-08-01

    Absorption or loss is inevitable for the metal-based metamaterials (MMs) due to the intrinsic loss of the metal, and constitutes a major hurdle to the practical realization of most applications such as a sub-wavelength lens. Thus, to reduce the losses becomes one of the major challenges in the MM field. However, the inevitable loss can also be harnessed to take a positive role in the applications of MMs such as stealth technology or other types of cloaking devices. In this presentation, after a brief review of the advances in MMs-based absorbers, we present several schemes to fulfill the desired electromagnetic absorption properties, both linear and nonlinear. For linear absorption, we have experimentally demonstrated that the absorption performance of an ordinary microwave absorbing material can be evidently improved by using the electric resonance resulting from an array of subwavelength metallic circuit elements. For nonlinear absorption, we show theoretically that the active linear magnetic permeability induces a nonlinear absorption, similar to the two-photon absorption (TPA), of electric field in a lossy MM with a Kerr-type nonlinear polarization.

  11. Harnessing the Therapeutic Potential of Th17 Cells

    PubMed Central

    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. PMID:26101460

  12. 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).

  13. Health as foreign policy: harnessing globalization for health.

    PubMed

    Fidler, David P

    2006-12-01

    This paper explores the importance for health promotion of the rise of public health as a foreign policy issue. Although health promotion encompassed foreign policy as part of 'healthy public policy', mainstream foreign policy neglected public health and health promotion's role in it. Globalization forces health promotion, however, to address directly the relationship between public health and foreign policy. The need for 'health as foreign policy' is apparent from the prominence public health now has in all the basic governance functions served by foreign policy. The Secretary-General's United Nations (UN) reform proposals demonstrate the importance of foreign policy to health promotion as a core component of public health because the proposals embed public health in each element of the Secretary-General's vision for the UN in the 21st century. The emergence of health as foreign policy presents opportunities and risks for health promotion that can be managed by emphasizing that public health constitutes an integrated public good that benefits all governance tasks served by foreign policy. Any effort to harness globalization for public health will have to make health as foreign policy a centerpiece of its ambitions, and this task is now health promotion's burden and opportunity.

  14. 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.

  15. Harnessing the protective potential of HIV-1 neutralizing antibodies

    PubMed Central

    Smith, S Abigail; Derdeyn, Cynthia A

    2016-01-01

    Recent biological, structural, and technical advances are converging within the HIV-1 vaccine field to harness the power of antibodies for prevention and therapy. Numerous monoclonal antibodies with broad neutralizing activity against diverse HIV-1 isolates have now been identified, revealing at least five sites of vulnerability on the envelope (Env) glycoproteins. While there are practical and technological barriers blocking a clear path from broadly neutralizing antibodies (bNAb) to a protective vaccine, this is not a dead end. Scientists are revisiting old approaches with new technology, cutting new trails through unexplored territory, and paving new roads in the hopes of preventing HIV-1 infection. Other promising avenues to capitalize on the power of bNAbs are also being pursued, such as passive antibody immunotherapy and gene therapy approaches. Moreover, non-neutralizing antibodies have inhibitory activities that could have protective potential, alone or in combination with bNAbs. With a new generation of bNAbs, and a clinical trial that associated antibodies with reduced acquisition, the field is closer than ever to developing strategies to use antibodies against HIV-1. PMID:26918160

  16. 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.

  17. 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

  18. 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

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. 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.

  4. Single and dual glycoside clustering around calix[4]arene scaffolds via click thiol-ene coupling and azide-alkyne cycloaddition.

    PubMed

    Fiore, Michele; Chambery, Angela; Marra, Alberto; Dondoni, Alessandro

    2009-10-01

    We present the first synthesis of calix[4]arene-based S-glycoclusters via photoinduced multiple thiol-ene coupling of tetra- and octa-allyl calix[4]arenes with peracetylated glucosyl thiol (67-88% yields). Moreover we describe the dual clustering at the upper and lower rim of a calix[4]arene with two different sugars (galactose and glucose) via sequential copper(i)-catalyzed azide-alkyne cycloaddition and photoinduced thiol-ene coupling.

  5. 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.

  6. Copper-catalyzed aerobic oxidation of hydroxamic acids leads to a mild and versatile acylnitroso ene reaction.

    PubMed

    Frazier, Charles P; Engelking, Jarred R; Read de Alaniz, Javier

    2011-07-13

    A mild formation of transient acylnitroso intermediates using a copper chloride catalyst and 1 atm of air as the terminal oxidant is described. The mild reaction conditions enable the inter- and intramolecular acylnitroso ene reaction with a wide range of functionalized alkene partners, as well as the first asymmetric variant. Notably, this transformation provides a practical and operationally simple method for effecting allylic amidation using an environmentally benign oxidant and a readily abundant transition metal. PMID:21678942

  7. Spray-deposition and photopolymerization of organic-inorganic thiol-ene resins for fabrication of superamphiphobic surfaces.

    PubMed

    Xiong, Li; Kendrick, Laken L; Heusser, Hannele; Webb, Jamie C; Sparks, Bradley J; Goetz, James T; Guo, Wei; Stafford, Christopher M; Blanton, Michael D; Nazarenko, Sergei; Patton, Derek L

    2014-07-01

    Superamphiphobic surfaces, exhibiting high contact angles and low contact angle hysteresis to both water and low surface tension liquids, have attracted a great deal attention in recent years because of the potential of these materials in practical applications such as liquid-resistant textiles, self-cleaning surfaces, and antifouling/anticorrosion coatings. In this work, we present a simple strategy for fabricating of superamphiphobic coatings based on photopolymerization of hybrid thiol-ene resins. Spray-deposition and UV photopolymerization of thiol-ene resins containing hydrophobic silica nanoparticles and perfluorinated thiols provide a multiscale topography and low-energy surface that endows the surface with superamphiphobicity. The wettability and chemical composition of the surfaces were characterized by contact-angle goniometry and X-ray photoelectron spectroscopy, respectively. The hierarchical roughness features of the thiol-ene surfaces were investigated with field-emission scanning electron microscopy. Droplet impact and sandpaper abrasion tests indicate the coatings respectively possess a robust antiwetting behavior and good mechanical durability.

  8. 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.

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

    PubMed

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

    2012-11-01

    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.

  10. 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. PMID:23850019

  11. Harnessing mosquito-Wolbachia symbiosis for vector and disease control.

    PubMed

    Bourtzis, Kostas; Dobson, Stephen L; Xi, Zhiyong; Rasgon, Jason L; Calvitti, Maurizio; Moreira, Luciano A; Bossin, Hervé C; Moretti, Riccardo; Baton, Luke Anthony; Hughes, Grant L; Mavingui, Patrick; Gilles, Jeremie R L

    2014-04-01

    Mosquito species, members of the genera Aedes, Anopheles and Culex, are the major vectors of human pathogens including protozoa (Plasmodium sp.), filariae and of a variety of viruses (causing dengue, chikungunya, yellow fever, West Nile). There is lack of efficient methods and tools to treat many of the diseases caused by these major human pathogens, since no efficient vaccines or drugs are available; even in malaria where insecticide use and drug therapies have reduced incidence, 219 million cases still occurred in 2010. Therefore efforts are currently focused on the control of vector populations. Insecticides alone are insufficient to control mosquito populations since reduced susceptibility and even resistance is being observed more and more frequently. There is also increased concern about the toxic effects of insecticides on non-target (even beneficial) insect populations, on humans and the environment. During recent years, the role of symbionts in the biology, ecology and evolution of insect species has been well-documented and has led to suggestions that they could potentially be used as tools to control pests and therefore diseases. Wolbachia is perhaps the most renowned insect symbiont, mainly due to its ability to manipulate insect reproduction and to interfere with major human pathogens thus providing new avenues for pest control. We herein present recent achievements in the field of mosquito-Wolbachia symbiosis with an emphasis on Aedes albopictus. We also discuss how Wolbachia symbiosis can be harnessed for vector control as well as the potential to combine the sterile insect technique and Wolbachia-based approaches for the enhancement of population suppression programs. PMID:24252486

  12. 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

  13. Harnessing mosquito-Wolbachia symbiosis for vector and disease control.

    PubMed

    Bourtzis, Kostas; Dobson, Stephen L; Xi, Zhiyong; Rasgon, Jason L; Calvitti, Maurizio; Moreira, Luciano A; Bossin, Hervé C; Moretti, Riccardo; Baton, Luke Anthony; Hughes, Grant L; Mavingui, Patrick; Gilles, Jeremie R L

    2014-04-01

    Mosquito species, members of the genera Aedes, Anopheles and Culex, are the major vectors of human pathogens including protozoa (Plasmodium sp.), filariae and of a variety of viruses (causing dengue, chikungunya, yellow fever, West Nile). There is lack of efficient methods and tools to treat many of the diseases caused by these major human pathogens, since no efficient vaccines or drugs are available; even in malaria where insecticide use and drug therapies have reduced incidence, 219 million cases still occurred in 2010. Therefore efforts are currently focused on the control of vector populations. Insecticides alone are insufficient to control mosquito populations since reduced susceptibility and even resistance is being observed more and more frequently. There is also increased concern about the toxic effects of insecticides on non-target (even beneficial) insect populations, on humans and the environment. During recent years, the role of symbionts in the biology, ecology and evolution of insect species has been well-documented and has led to suggestions that they could potentially be used as tools to control pests and therefore diseases. Wolbachia is perhaps the most renowned insect symbiont, mainly due to its ability to manipulate insect reproduction and to interfere with major human pathogens thus providing new avenues for pest control. We herein present recent achievements in the field of mosquito-Wolbachia symbiosis with an emphasis on Aedes albopictus. We also discuss how Wolbachia symbiosis can be harnessed for vector control as well as the potential to combine the sterile insect technique and Wolbachia-based approaches for the enhancement of population suppression programs.

  14. 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.

  15. Roll-to-plate fabrication of microfluidic devices with rheology-modified thiol-ene resins

    NASA Astrophysics Data System (ADS)

    Senkbeil, Silja; Aho, Johanna; Yde, Leif; Lindvold, Lars R.; Stensborg, Jan F.; Rantanen, Jukka; Lafleur, Josiane P.; Kutter, Jörg P.

    2016-07-01

    In this paper, the replication possibilities of microfluidic channels by UV-roll-to-plate fabrication were investigated and a study of rheology-modified thiol-ene for the application in such a UV-roll-to-plate setup was conducted. The system allows the manufacture of channels with aspect ratios of 2:1 and a maximal channel depth of 90 μm as well as the sealing of the finished devices with patterning and sealing speeds of up to 19 m min‑1. By adding fumed silica nanoparticles to the uncured resins, it was possible to alter the rheological behavior of the resin system to fabricate shallow microfluidic channels with 40  ×  95 μm cross-sectional dimensions. Moreover, deeper (90 μm) channels can be fabricated with highly viscous resins based on thiol-terminated oligomers. As a demonstration, capillary electrophoresis chips were prepared and tested for a simple separation of two fluorescent dyes.

  16. 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. PMID:26616449

  17. 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

  18. 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

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

    PubMed

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

    2014-03-01

    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. PMID:24564901

  20. Roll-to-plate fabrication of microfluidic devices with rheology-modified thiol-ene resins

    NASA Astrophysics Data System (ADS)

    Senkbeil, Silja; Aho, Johanna; Yde, Leif; Lindvold, Lars R.; Stensborg, Jan F.; Rantanen, Jukka; Lafleur, Josiane P.; Kutter, Jörg P.

    2016-07-01

    In this paper, the replication possibilities of microfluidic channels by UV-roll-to-plate fabrication were investigated and a study of rheology-modified thiol-ene for the application in such a UV-roll-to-plate setup was conducted. The system allows the manufacture of channels with aspect ratios of 2:1 and a maximal channel depth of 90 μm as well as the sealing of the finished devices with patterning and sealing speeds of up to 19 m min-1. By adding fumed silica nanoparticles to the uncured resins, it was possible to alter the rheological behavior of the resin system to fabricate shallow microfluidic channels with 40  ×  95 μm cross-sectional dimensions. Moreover, deeper (90 μm) channels can be fabricated with highly viscous resins based on thiol-terminated oligomers. As a demonstration, capillary electrophoresis chips were prepared and tested for a simple separation of two fluorescent dyes.

  1. Photolithographic fabrication of solid-liquid core waveguides by thiol-ene chemistry

    NASA Astrophysics Data System (ADS)

    Sagar, Kaushal; Gopalakrishnan, Nimi; Brøkner Christiansen, Mads; Kristensen, Anders; Ndoni, Sokol

    2011-09-01

    In this work we demonstrate an efficient and cleanroom compatible method for the fabrication of solid-liquid core waveguides based on nanoporous polymers. We have used thiol-ene photo-grafting to tune and pattern the hydrophilicity of an originally hydrophobic nanoporous 1, 2-polybutadiene. The generated refractive index contrast between the patterned water-filled volume and the surrounding empty hydrophobic porous polymer allows for light confinement within the water-filled volume—the solid-liquid core. The presented fabrication process is simple and fast. It allows a high degree of flexibility on the type and grade of surface chemistry imparted to the large nanoporous area depending upon the application. The fabrication does not need demanding chemical reaction conditions. Thus, it can be readily used on a standard silicon lithography bench. The propagation loss values reported in this work are comparable with literature values for state-of-the-art liquid-core waveguide devices. The demonstrated waveguide function added to the nanoporous polymer with a very high internal surface area makes the system interesting for many applications in different areas, such as diagnostics and bio-chemical sensing.

  2. Responsive hybrid microcapsules by the one-step interfacial thiol-ene photopolymerization.

    PubMed

    Liu, Dandan; Yu, Bing; Jiang, Xuesong; Yin, Jie

    2013-04-30

    We here demonstrated a general, convenient, and robust method to fabricate the hybrid microcapsules through the one-step thiol-ene photopolymerization at the interface between toluene and water. In the presence of amphiphilic polyhedral oligomeric silsesquioxane (POSS) containing thiol groups (PTPS) as reactive surfactants and trimethylolpropane triacrylate (TMPTA) as a cross-linker, the wall of hybrid microcapsules can be photo-cross-linked. The obtained hybrid microcapsules (HMCs) were well-characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), atomic force microscopy (AFM), and confocal laser scanning microscopy (CLSM). The results revealed that the obtained HMCs are uniform with the tunable size in diameter (2-4 μm) and wall thickness (55-120 nm). The size of HMCs increased with the increasing content of toluene. The wall thickness of HMCs decreased with the increasing content of toluene, while the wall thickness of HMCs increased with the increasing content of cross-linker TMPTA. Furthermore, HMCs are thermoresponsive in aqueous solution, can encapsulate both hydrophobic and dydrophilic dyes, and can be used in the controlled dispersion of dyes in different mediums. It is believed that this simple, robust, and general method to fabricate the hybrid microcapsules will extend the potential application fields of microcapsules, such as in the controlled dispersion and drug delivery.

  3. 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.

  4. 14 CFR 91.107 - Use of safety belts, shoulder harnesses, and child restraint systems.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... Vehicle Safety Standard No. 213 (49 CFR 571.213)), vest- and harness-type child restraint systems, and lap... berth, provided that the person being held has not reached his or her second birthday and does...

  5. From Resting State to the Steady State: Mechanistic Studies of Ene-Yne Metathesis Promoted by the Hoveyda Complex.

    PubMed

    Griffiths, Justin R; Keister, Jerome B; Diver, Steven T

    2016-04-27

    The kinetics of intermolecular ene-yne metathesis (EYM) with the Hoveyda precatalyst (Ru1) has been studied. For 1-hexene metathesis with 2-benzoyloxy-3-butyne, the experimental rate law was determined to be first-order in 1-hexene (0.3-4 M), first-order in initial catalyst concentration, and zero-order for the terminal alkyne. At low catalyst concentrations (0.1 mM), the rate of precatalyst initiation was observed by UV-vis and the alkyne disappearance was observed by in situ FT-IR. Comparison of the rate of precatalyst initiation and the rate of EYM shows that a low, steady-state concentration of active catalyst is rapidly produced. Application of steady-state conditions to the carbene intermediates provided a rate treatment that fit the experimental rate law. Starting from a ruthenium alkylidene complex, competition between 2-isopropoxystyrene and 1-hexene gave a mixture of 2-isopropoxyarylidene and pentylidene species, which were trappable by the Buchner reaction. By varying the relative concentration of these alkenes, 2-isopropoxystyrene was found to be 80 times more effective than 1-hexene in production of their respective Ru complexes. Buchner-trapping of the initiation of Ru1 with excess 1-hexene after 50% loss of Ru1 gave 99% of the Buchner-trapping product derived from precatalyst Ru1. For the initiation process, this shows that there is an alkene-dependent loss of precatalyst Ru1, but this does not directly produce the active catalyst. A faster initiating precatalyst for alkene metathesis gave similar rates of EYM. Buchner-trapping of ene-yne metathesis failed to deliver any products derived from Buchner insertion, consistent with rapid decomposition of carbene intermediates under ene-yne conditions. An internal alkyne, 1,4-diacetoxy-2-butyne, was found to obey a different rate law. Finally, the second-order rate constant for ene-yne metathesis was compared to that previously determined by the Grubbs second-generation carbene complex: Ru1 was found to

  6. Molecular mapping of a sunflower rust resistance gene from HAR6.

    PubMed

    Bulos, Mariano; Ramos, María L; Altieri, Emiliano; Sala, Carlos A

    2013-03-01

    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 (R HAR6 ), 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 R HAR6 at a genetic distance of 0.7 cM, while ORS581, a dominant marker linked in the coupling phase, is proximal to R HAR6 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.

  7. 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

  8. Epithelial-to-Mesenchymal Plasticity Harnesses Endocytic Circuitries

    PubMed Central

    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. PMID:25767773

  9. 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

  10. 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.

  11. Paleozoic structural controls on shortening transfer in the Subandean foreland thrust system, Ene and southern Ucayali basins, Peru

    NASA Astrophysics Data System (ADS)

    Espurt, Nicolas; Brusset, StéPhane; Baby, Patrice; Hermoza, Wilber; BolañOs, Rolando; Uyen, Dennys; DéRamond, Joachim

    2008-06-01

    The Neogene evolution of the Ene and southern Ucayali basins of the Subandes has been controlled by two stacked thrust wedges that differ in terms of tectonic styles. The lower thrust wedge is formed by deep-seated décollements within the basement related to thick-skinned foreland structures inherited from an Early Carboniferous thrust system. Seismic reflection data show that this Paleozoic compressional system has been eroded and unconformably covered by Late Carboniferous clastic sediments. It generated an irregular Paleozoic sedimentary architecture controlling the Neogene thrust propagation. The upper thin-skinned thrust wedge developed within this Paleozoic sedimentary series and constitutes the Subandean zone. Cross-section balancing shows an along-strike homogenous horizontal shortening of ˜56 km (˜30%) across the Ene-southern Ucayali thrust system. This amount of shortening was vertically partitioned onto the two stacked thrust wedges. The N-S thickness variations of the Paleozoic sedimentary prism controlled the eastward propagation of the upper thrust wedge. The southern thickening of the Paleozoic series generated major décollements and the shortening excess is of 7 km (16%) in comparison to the north. Consequently, the northern lack of shortening onto the upper thrust wedge was transferred to the Early Carboniferous compressional structures of the lower thrust wedge. We suggest that this vertical partitioning of the shortening was accommodated by a regional oblique ramp: the Tambo transfer zone. This geometrical analysis of the Ene-southern Ucayali thrust system provides new perspectives for future hydrocarbon exploration in this region.

  12. Selective fluorescence quenching of 2,3-diazabicyclo[2.2.2]oct-2-ene by nucleotides.

    PubMed

    Marquez, Cesar; Pischel, Uwe; Nau, Werner M

    2003-10-16

    [reaction: see text] The fluorescence quenching of 2,3-diazabicyclo[2.2.2]oct-2-ene (DBO) by nucleotides has been studied. The quenching mechanism was analyzed on the basis of deuterium isotope effects, tendencies for exciplex formation, and the quenching efficiency in the presence of a molecular container (cucurbit[7]uril). Exciplex-induced quenching appears to prevail for adenosine, cytidine, and uridine, while hydrogen abstraction becomes competitive for thymidine and guanosine. Compared to other fluorescent probes, DBO responds very selectively to the type of nucleotide.

  13. N,O-Nucleosides from ene reactions of nitrosocarbonyl intermediates with the 3-methyl-2-buten-1-ol.

    PubMed

    Quadrelli, Paolo; Mella, Mariella; Carosso, Serena; Bovio, Bruna

    2013-01-18

    Nitrosocarbonyl intermediates undergo ene reactions with allylic alcohols, affording regioisomeric adducts in fair yields. Nitrosocarbonyl benzene reacts with 3-methyl-2-buten-1-ol and follows a Markovnikov orientation and abstracts preferentially the twix hydrogens over the lone ones. With the more sterically demanding nitrosocarbonyl mesitylene and anthracene, the Markovnikov directing effect is relieved and lone abstraction is observed, affording the 5-hydroxy-isoxazolidines that serve as synthons for the preparation of N,O-nucleoside analogues according to the Vorbrüggen protocol.

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

    PubMed Central

    Yuan, Wei; Dong, Xiang; McDowell, Patrick

    2012-01-01

    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. PMID:23098194

  15. Complete crystal structure of decafluorocyclohex-1-ene at 4.2 K from original neutron diffraction data.

    PubMed

    Solovyov, Leonid A; Fedorov, Alexandr S; Kuzubov, Aleksandr A

    2014-04-01

    The crystal structure model of decafluorocyclohex-1-ene at 4.2 K derived from simulated powder diffraction data and solid-state energy minimization [Smrčok et al. (2013). Acta Cryst. B69, 395-404] is found to be incomplete. In this study it is completed by an additional alternative molecular orientation revealed from the difference density analysis and direct space search. The structure is refined by the derivative difference method in the rigid-body approximation leading to perfect agreement between observed and calculated neutron powder patterns. PMID:24675609

  16. 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

    2013-04-01

    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.

  17. 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. PMID:21804987

  18. [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.

  19. 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.

  20. 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

    2013-04-01

    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. PMID:23434082

  1. 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

  2. Cyclopent-4-ene-1,3-diones: a new class of herbicides acting as potent photosynthesis inhibitors.

    PubMed

    Varejão, Jodieh O S; Barbosa, Luiz C A; Varejão, Eduardo V V; Maltha, Célia R A; King-Díaz, Beatriz; Lotina-Hennsen, Blas

    2014-06-25

    In a recent paper, we reported the synthesis and photosynthesis-inhibitory activity of a series of analogues of rubrolides. From quantitative structure-activity relationship (QSAR) studies, we found that the most efficient compounds are those having higher ability to accept electrons. On the basis of those findings, we directed our effort to synthesize new analogues bearing a strong electron-withdrawing group (nitro) in the benzylidene ring and evaluate their effects on photosynthesis. However, the employed synthetic approach led to novel cyclopent-4-ene-1,3-diones as major products. Here, we report the synthesis and mechanism of action of such cyclopent-4-ene-1,3-diones as a new class of photosynthesis inhibitors. These compounds block the electron transport at the QB level by interacting at the D1 protein at the reducing side of Photosystem II and act as Hill reaction inhibitors, with higher activity than the corresponding rubrolides. To the best of our knowledge, this is the first report on the photosynthesis inhibitory activity of cyclopentenediones.

  3. 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

    2016-02-01

    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. PMID:26699696

  4. 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 ").

  5. Gold-Catalyzed Tandem 1,3-Migration/Double Cyclopropanation of 1-Ene-4,n-diyne Esters to Tetracyclodecene and Tetracycloundecene Derivatives.

    PubMed

    Chen, Cuili; Zou, Yongzhen; Chen, Xianxiao; Zhang, Xiaoxiang; Rao, Weidong; Chan, Philip Wai Hong

    2016-09-16

    A synthetic method that relies on Au(I)-catalyzed tandem 1,3-acyloxy migration/double cyclopropanation of 1-ene-4,9-diyne and 1-ene-4,10-diyne esters to construct the respective architecturally challenging tetracyclodecene and tetracycloundecene derivatives is described. Achieved under mild reaction conditions, the transformation was shown to be robust with a wide variety of substitution patterns tolerated to give the two members of the carbocyclic family in good to excellent yields and as a single regio- and diastereomer. PMID:27589481

  6. Polysiloxane-Based Autonomic Self-Healing Elastomers Obtained through Dynamic Boronic Ester Bonds Prepared by Thiol-Ene "Click" Chemistry.

    PubMed

    Zuo, Yujing; Gou, Zhiming; Zhang, Changqiao; Feng, Shengyu

    2016-07-01

    Cross-linked silicone elastomers constructed with dynamic-covalent boronic esters are first synthesized by photoinitiated radical thiol-ene "click" chemistry. The resultant samples can be cut with a sharp knife into two pieces and then healed via the reversibility of the boronic ester cross-linkages to restore the original silicone sample within 30 min. Regulation of luminescent properties is achieved by incorporating organic dye into the elastomers through a "one-pot" thiol-ene reaction. The proposed synthesis procedure demonstrates a new strategy to produce boronic acid silicone materials capable of self-healing without external forces. PMID:27159536

  7. 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...

  8. 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...

  9. 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...

  10. 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...

  11. 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.

  12. 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…

  13. 14 CFR 23.785 - Seats, berths, litters, safety belts, and shoulder harnesses.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... flight and ground load conditions, as defined in the approved operating envelope of the airplane. In... to the seat or structure. (b) Each forward-facing or aft-facing seat/restraint system in normal... forward-facing or aft-facing seat with a safety belt and a shoulder harness, and must provide...

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

    Technology Transfer Automated Retrieval System (TEKTRAN)

    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...

  15. 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…

  16. Exploratory studies of classical conditioning of the preoral cavity in harnessed carpenter ants (Camponotus pennsylvanicus).

    PubMed

    Sauer, Dustin L; Abramson, Charles I; Lawson, Adam L

    2002-06-01

    An attempt was made to classically condition the mouthparts of harnessed worker ants (Camponotus pennsylvanicus) in anticipation of feeding. Experiments were designed to investigate classical conditioning with one CS, discrimination between two CSs, and pseudoconditioning. Analysis indicated a small acquisition effect that could be accounted for by pseudoconditioning. The preparation can be used to study nonassociative learning and some instrumental conditioning situations.

  17. 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…

  18. 14 CFR 29.785 - Seats, berths, litters, safety belts, and harnesses.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... addition— (1) Each pilot seat must be designed for the reactions resulting from the application of the... restraints, such as straps or safety belts, to withstand the forward reaction. In addition— (1) The berth or... forces, and reactions between the occupant, seat, and safety belt or harness corresponding with...

  19. 14 CFR 29.785 - Seats, berths, litters, safety belts, and harnesses.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... addition— (1) Each pilot seat must be designed for the reactions resulting from the application of the... restraints, such as straps or safety belts, to withstand the forward reaction. In addition— (1) The berth or... forces, and reactions between the occupant, seat, and safety belt or harness corresponding with...

  20. 14 CFR 27.785 - Seats, berths, litters, safety belts, and harnesses.

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ... addition— (1) Each pilot seat must be designed for the reactions resulting from the application of the..., such as straps or safety belts, to withstand the forward load reaction. In addition— (1) The berth or..., inertial forces, and reactions between occupant, seat, and safety belt or harness corresponding with...

  1. 14 CFR 29.785 - Seats, berths, litters, safety belts, and harnesses.

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ... addition— (1) Each pilot seat must be designed for the reactions resulting from the application of the... restraints, such as straps or safety belts, to withstand the forward reaction. In addition— (1) The berth or... forces, and reactions between the occupant, seat, and safety belt or harness corresponding with...

  2. 14 CFR 27.785 - Seats, berths, litters, safety belts, and harnesses.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... addition— (1) Each pilot seat must be designed for the reactions resulting from the application of the..., such as straps or safety belts, to withstand the forward load reaction. In addition— (1) The berth or..., inertial forces, and reactions between occupant, seat, and safety belt or harness corresponding with...

  3. 14 CFR 27.785 - Seats, berths, litters, safety belts, and harnesses.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... addition— (1) Each pilot seat must be designed for the reactions resulting from the application of the..., such as straps or safety belts, to withstand the forward load reaction. In addition— (1) The berth or..., inertial forces, and reactions between occupant, seat, and safety belt or harness corresponding with...

  4. 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…

  5. Exploratory studies of classical conditioning of the preoral cavity in harnessed carpenter ants (Camponotus pennsylvanicus).

    PubMed

    Sauer, Dustin L; Abramson, Charles I; Lawson, Adam L

    2002-06-01

    An attempt was made to classically condition the mouthparts of harnessed worker ants (Camponotus pennsylvanicus) in anticipation of feeding. Experiments were designed to investigate classical conditioning with one CS, discrimination between two CSs, and pseudoconditioning. Analysis indicated a small acquisition effect that could be accounted for by pseudoconditioning. The preparation can be used to study nonassociative learning and some instrumental conditioning situations. PMID:12090495

  6. 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 systems. 105.43 Section 105.43 Aeronautics and Space FEDERAL AVIATION ADMINISTRATION, DEPARTMENT OF... from mold, mildew, and other fungi, and other rotting agents propagated in a moist environment; or...

  7. 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 systems. 105.43 Section 105.43 Aeronautics and Space FEDERAL AVIATION ADMINISTRATION, DEPARTMENT OF... from mold, mildew, and other fungi, and other rotting agents propagated in a moist environment; or...

  8. 14 CFR 29.785 - Seats, berths, litters, safety belts, and harnesses.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... addition— (1) Each pilot seat must be designed for the reactions resulting from the application of the... restraints, such as straps or safety belts, to withstand the forward reaction. In addition— (1) The berth or... forces, and reactions between the occupant, seat, and safety belt or harness corresponding with...

  9. 14 CFR 27.785 - Seats, berths, litters, safety belts, and harnesses.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... addition— (1) Each pilot seat must be designed for the reactions resulting from the application of the..., such as straps or safety belts, to withstand the forward load reaction. In addition— (1) The berth or..., inertial forces, and reactions between occupant, seat, and safety belt or harness corresponding with...

  10. 14 CFR 29.785 - Seats, berths, litters, safety belts, and harnesses.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... addition— (1) Each pilot seat must be designed for the reactions resulting from the application of the... restraints, such as straps or safety belts, to withstand the forward reaction. In addition— (1) The berth or... forces, and reactions between the occupant, seat, and safety belt or harness corresponding with...

  11. 14 CFR 27.785 - Seats, berths, litters, safety belts, and harnesses.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... addition— (1) Each pilot seat must be designed for the reactions resulting from the application of the..., such as straps or safety belts, to withstand the forward load reaction. In addition— (1) The berth or..., inertial forces, and reactions between occupant, seat, and safety belt or harness corresponding with...

  12. 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.…

  13. 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…

  14. A rapid and facile preparation of novel macroporous silicone-based cryogels via photo-induced thiol-ene click chemistry.

    PubMed

    Ozmen, Mehmet Murat; Fu, Qiang; Kim, Jinguk; Qiao, Greg G

    2015-12-21

    Novel poly(dimethylsiloxane) based macroporous gels (cryogels) were prepared via a simple and rapid photo-induced thiol-ene click reaction at low temperatures. The cryogels formed were able to float on a water surface and selectively remove oils or organic solvents with excellent recyclability. PMID:26477510

  15. Triggering bilayer to inverted-hexagonal nanostructure formation by thiol-ene click chemistry on cationic lipids: consequences on gene transfection.

    PubMed

    Afonso, Damien; Le Gall, Tony; Couthon-Gourvès, Hélène; Grélard, Axelle; Prakash, Shipra; Berchel, Mathieu; Kervarec, Nelly; Dufourc, Erick J; Montier, Tristan; Jaffrès, Paul-Alain

    2016-05-18

    The ramification of cationic amphiphiles on their unsaturated lipid chains is readily achieved by using the thiol-ene click reaction triggering the formation of an inverted hexagonal phase (HII). The new ramified cationic lipids exhibit different bio-activities (transfection, toxicity) including higher transfection efficacies on 16HBE 14o-cell lines.

  16. Stereospecific and stereoselective rhodium(I)-catalyzed intramolecular [2+2+2] cycloaddition of allene-ene-ynes: construction of bicyclo[4.1.0]heptenes.

    PubMed

    Ohta, Yuu; Yasuda, Shigeo; Yokogawa, Yuka; Kurokawa, Kei; Mukai, Chisato

    2015-01-19

    Treatment of the allene-ene-yne substrates with [{RhCl(CO)2}2] effected the intramolecular [2+2+2]-type ring-closing reaction to produce various of tri- and tetracyclic derivatives containing a cyclopropane ring. The reaction is highly stereoselective as well as stereospecific with good to excellent yields.

  17. Formal synthesis of (±)-galanthamine and (±)-lycoramine using Rh(I)-catalyzed [(3 + 2) + 1] cycloaddition of 1-ene-vinylcyclopropane and CO.

    PubMed

    Feng, Yu; Yu, Zhi-Xiang

    2015-02-01

    An efficient strategy using Rh(I)-catalyzed [(3 + 2) + 1] cycloaddition of 1-ene-vinylcyclopropane and CO as a key step to build the cis-hydrodibenzofuran skeleton has been developed and applied for the formal synthesis of (±)-galanthamine and (±)-lycoramine. PMID:25558884

  18. 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.

  19. Vibrational spectra of cis and trans but-2-enes: assignments, isolated CH stretching frequencies and CH bond lengths

    NASA Astrophysics Data System (ADS)

    McKean, D. C.; Mackenzie, M. W.; Morrisson, A. R.; Lavalley, J. C.; Janin, A.; Fawcett, V.; Edwards, H. G. M.

    Infrared and Raman spectra have been obtained from 11 isotopomers of cis and trans but-2-enes in various phases ( c- and t-CH 3CHCHCH 3, CH 3CHCDCH 3, CD 3CHCHCD 3, CD 3CHCDCD 3, CD 3CDCDCD 3; c-CH 3CDCDCH 3). Nearly all the fundamentals are securely assigned. Isolated CH stretching frequencies ν isCH are observed or deduced from the spectra and used to predict CH bond lengths and dissociation energies. The olefinic CH and methyl CH s bonds are stronger in the cis compound than those in the trans, in keeping with substituent effects previously observed in propene, and with molecular mechanics predictions. Comparison of ν isCH values with local mode fifth overtone spectra for cis-CH 3CHCHCH 3 indicates that the part of the latter associated with the CH a bond cannot be readily interpreted.

  20. Divinyl-end-functionalized polyethylenes: ready access to a range of telechelic polyethylenes through thiol-ene reactions.

    PubMed

    Norsic, Sebastien; Thomas, Coralie; D'Agosto, Franck; Boisson, Christophe

    2015-04-01

    Telechelic α,ω-iodo-vinyl-polyethylenes (Vin-PE-I) were obtained by catalytic ethylene polymerization in the presence of [(C5 Me5 )2 NdCl2 Li(OEt2 )2 ] in combination with a functionalized chain-transfer agent, namely, di(10-undecenyl)magnesium, followed by treatment of the resulting di(vinylpolyethylenyl)magnesium compounds ((vinyl-PE)2 Mg) with I2 . The iodo-functionalized vinylpolyethylenes (Vin-PE-I) were transformed into unique divinyl-functionalized polyethylenes (Vin-PE-Vin) by simple treatment with tBuOK in toluene at 95 °C. Thiol-ene reactions were then successfully performed on Vin-PE-Vin with functionalized thiols in the presence of AIBN. A range of homobifunctional telechelic polyethylenes were obtained on which a hydroxy, diol, carboxylic acid, amine, ammonium chloride, trimethoxysilyl, chloro, or fluoroalkyl group was installed quantitatively at each chain end. PMID:25688747

  1. Unexpected carbon-carbon coupling between organic cyanides and isopropyl {beta}-carbon in a hafnium ene diamide complex

    SciTech Connect

    Bol, J.E.; Hessen, B.; Teuben, J.H.; Smeets, W.J.J.; Spek, A.L.

    1992-06-01

    Reaction of the ene diamide complex Cp*Hf({sigma}{sup 2},{pi}-iPr-DAB)Cl (1; Cp* = {eta}{sup 5}-C{sub 5}Me{sub 5}, iPr-DAB = 1,4-diisopropyl-1,4-diaza-1,3-butadiene) with organic cyanides was investigated. The crystal structure of the product, Cp*Hf[iPrNCH{double_bond}CHNC(Me){double_bond}CHC(tBu){double_bond}NH]Cl, is reported. The reaction is thought to proceed by two hydrogen transfers and a C-C coupling on the {beta}-carbon of an isopropyl group. NMR was used to identify reaction intermediates in the hydrogen transfer scheme.

  2. 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.

  3. 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

  4. '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.

  5. Treatment of congenital dislocation of the hip by the Pavlik harness. Mechanism of reduction and usage.

    PubMed

    Iwasaki, K

    1983-07-01

    The Pavlik harness was used in the treatment of complete congenital dislocation of one or both hips in a series of infants, on either an outpatient or an inpatient basis. The results in the two groups were compared. For the children treated as outpatients the incidence of avascular necrosis of the femoral head was 7.2 per cent and for the group treated as inpatients the rate was 28 per cent. Application of the Pavlik harness allowed reduction of the hip by shifting the femoral head first to the posterior part of the acetabulum through flexion of the hip, followed by movement of the femoral head anteriorly into the acetabulum through abduction of the hip, which is possible because of stretching of the adductor muscles by the weight of the lower extremity. When the reduction is obtained by forced abduction there is a greater danger of avascular necrosis of the femoral head.

  6. 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.

  7. 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. PMID:25408755

  8. 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

  9. 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. PMID:23745623

  10. 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.

  11. Harnessing localized ridges for high-aspect-ratio hierarchical patterns with dynamic tunability and multifunctionality.

    PubMed

    Cao, Changyong; Chan, Hon Fai; Zang, Jianfeng; Leong, Kam W; Zhao, Xuanhe

    2014-03-19

    A simple method for fabricating high-aspect-ratio, hierarchical, and dynamically tunable surface patterns is invented by harnessing localized-ridge instabilities in gold nanofilms coated on elastomer substrates (a); a theoretical model to calculate the critical parameters (e.g., wavelength and amplitude) for designing the new patterns is developed (b); and novel applications of the patterns as super-hydrophobic coatings (c) and biomimetic cell-culture substrates (d) capable of on-demand tunability are demonstrated. PMID:24339233

  12. 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.

  13. 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

  14. 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.

  15. 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

  16. 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.

  17. Harnessing methane

    NASA Astrophysics Data System (ADS)

    Showstack, Randy

    The total methane resource in hydrates—ice-like substances found in deep ocean sediments and Arctic permafrost—exceeds the energy content of all other fossil fuel resources,such as coal, oil, and conventional gas, according to the U.S. Geological Survey (USGS).The Methane Hydrate Research and Development Act, signed into law by U.S. President Bill Clinton on May 3, establishes a new federal commitment to developing methane hydrates, which has been touted as a potentially clean energy source that could make the U.S. less dependent on foreign sources of energy. The bill authorizes $47.5 million over five years for the Department of Energy to establish a federal methane hydrate research and development program.

  18. [3,3]-Sigmatropic shifts and retro-ene rearrangements in cyanates, isocyanates, thiocyanates, and isothiocyanates of the form RX-YCN and RX-NCY.

    PubMed

    Koch, Rainer; Finnerty, Justin J; Murali, Sukumaran; Wentrup, Curt

    2012-02-17

    Retro-ene type [2π + 2π + 2σ] and [3,3]-sigmatropic shift reactions involving the substituent groups R in heteroatom-substituted cyanates and thiocyanates RX-YCN and the isomeric isocyanates and isothiocyanates of the type RX-NCY (X = CR(2), NR', O, or S; Y = O or S) have been investigated computationally at the B3LYP/6-311++G(d,p) level. Retro-ene reactions of alkyl derivatives of the title compounds afford alkenes, imines, carbonyl and thiocarbonyl compounds together with HNCO (HNCS) or HOCN (HSCN). [3,3]-Sigmatropic shifts (hetero-Cope rearrangements) of the corresponding allyl, propargyl, benzyl, and aryl derivatives causes allylic rearrangements, propargyl-allenyl rearrangement, conversion of benzyl cyanates to o-isocyanatotoluenes, and conversion of N-cyanatoarylamines to o-isocyanatoanilines, etc. The corresponding rearrangements of allyl thiocyanates, arylamino thiocyanates and isothiocyanates, and arylsulfenyl thiocyanates and isothiocyanates are also described. PMID:22251012

  19. 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

  20. Extended X-ray absorption fine structure (EXAFS) characterisation of the hydroformylation of oct-1-ene by dilute Rh-PEt3 catalysts in supercritical carbon dioxide.

    PubMed

    Fiddy, Steven G; Evans, John; Neisius, Thomas; Sun, Xue-Zhong; Jie, Zhang; George, Michael W

    2004-03-21

    Dilute EXAFS characterisation has been used to elucidate species involved during the course of the 3 mM Rh-catalysed hydroformylation of oct-1-ene in scCO(2); significant metal clustering occurs with a Rh:P ratio of 1:1 but at a 1:3 ratio, metal clustering is not detected, with the presence of monomer species only. PMID:15010776

  1. 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).

  2. 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.

  3. 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

  4. 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.

  5. 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.

  6. Theoretical study on the photolysis mechanism of 2,3-diazabicyclo[2.2.2]oct-2-ene.

    PubMed

    Chen, Hui; Li, Shuhua

    2005-09-28

    A CASPT2/CASSCF study has been carried out to investigate the mechanism of the photolysis of 2,3-diazabicyclo[2.2.2]oct-2-ene (DBO) under direct and triplet-sensitized irradiation. By exploring the detailed potential energy surfaces including intermediates, transition states, conical intersections, and singlet/triplet crossing points, for the first excited singlet (S(1)) and the low-lying triplet states (T(1), T(2), and T(3)), we provide satisfactory explanations of many experimental findings associated with the photophysical and photochemical processes of DBO. A key finding of this work is the existence of a significantly twisted S(1) minimum, which can satisfactorily explain the envelope of the broad emission band of DBO. It is demonstrated that the S(1) (n-pi*) intermediate can decay to the T(1) (n-pi*) state by undergoing intersystem crossing (rather inefficient) to the T(2) (pi-pi*) state followed by internal conversion to the T(1) state. The high fluorescence yield and the extraordinarily long lifetime of the singlet excited DBO are due to the presence of relatively high barriers, both for intersystem crossing and for C-N cleavage. The short lifetime of the triplet DBO is caused by fast radiationless decay to the ground state.

  7. Investigations on the fluorescence quenching of 2,3-diazabicyclo[2.2.2]oct-2-ene by certain flavonoids.

    PubMed

    Anbazhagan, V; Kalaiselvan, A; Jaccob, M; Venuvanalingam, P; Renganathan, R

    2008-05-29

    The fluorescence quenching of 2,3-diazabicyclo[2.2.2]oct-2-ene (DBO) by seven flavonoids namely flavone, flavanone, quercetin, rutin, genistein, diadzein and chrysin has been investigated in acetonitrile and dichloromethane solvents. The bimolecular quenching rate constants lie in the range of 0.09-5.75 x 10(9)M(-1)s(-1) and are explained in terms of structure of the flavonoids studied. The reactivity of flavonoids are in the order: quercetin>rutin>genistein>diadzein>chrysin>flavone>flavanone. The quenching rate constants (k(q)) increase with increase in the number of -OH groups. The endergonic thermodynamic values of DeltaG(et) reveal that electron transfer quenching mechanism can be ruled out. Bond dissociation enthalpy calculations reveal that the position of -OH is important. Further in vitro-antioxidant activities of flavonoids were evaluated with rat liver catalase by gel electrophoresis. The deuterium isotope effect thus observed in this work provides evidence for hydrogen abstraction involved in the quenching process of singlet excited DBO by flavonoids. The data suggest the involvement of direct hydrogen atom transfer (radical scavenging) in the fluorescence quenching of DBO. Bond dissociation enthalpy calculation performed at B3LYP/6-31G(p')//B3LYP/3-21G level are in excellent agreement with the above observations and further reveal that the number OH groups and position of them decide the quenching ability of the flavonoids.

  8. Thiol-ene hydrogels as desmoplasia-mimetic matrices for modeling pancreatic cancer cell growth, invasion, and drug resistance

    PubMed Central

    Ki, Chang Seok; Lin, Tsai-Yu; Korc, Murray; Lin, Chien-Chi

    2014-01-01

    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). PMID:25176061

  9. 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.

  10. Fabrication of rigid microstructures with thiol-ene-based soft lithography for continuous-flow cell lysis

    PubMed Central

    Burke, Jeffrey M.; Pandit, Kunal R.; Goertz, John P.

    2014-01-01

    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 107, 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%. PMID:25538814

  11. 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.

  12. 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.

  13. Advanced organic optoelectronic materials: harnessing excited-state intramolecular proton transfer (ESIPT) process.

    PubMed

    Kwon, Ji Eon; Park, Soo Young

    2011-08-23

    Recently, organic fluorescent molecules harnessing the excited-state intramolecular proton transfer (ESIPT) process are drawing great attention due to their unique photophysical properties which facilitate novel optoelectronic applications. After a brief introduction to the ESIPT process and related photo-physical properties, molecular design strategies towards tailored emission are discussed in relation to their theoretical aspects. Subsequently, recent studies on advanced ESIPT molecules and their optoelectronic applications are surveyed, particularly focusing on chemical sensors, fluorescence imaging, proton transfer lasers, and organic light-emitting diodes (OLEDs).

  14. 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.

  15. 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. PMID:15362396

  16. Crystal structure of cyclo-tris­(μ-3,4,5,6-tetra­fluoro-o-phenyl­ene-κ2 C 1:C 2)trimercury–tetra­cyano­ethyl­ene (1/1)

    PubMed Central

    Castañeda, Raúl; Timofeeva, Tatiana V.; Khrustalev, Victor N.

    2015-01-01

    The title compound, [Hg3(C6F4)3]·C6N4, contains one mol­ecule of tetra­cyano­ethyl­ene B per one mol­ecule of mercury macrocycle A, i.e., A•B, and crystallizes in the monoclinic space group C2/c. Macrocycle A and mol­ecule B both occupy special positions on a twofold rotation axis and the inversion centre, respectively. The supra­molecular unit [A•B] is built by the simultaneous coordination of one of the nitrile N atoms of B to the three mercury atoms of the macrocycle A. The Hg⋯N distances range from 2.990 (4) to 3.030 (4) Å and are very close to those observed in the related adducts of the macrocycle A with other nitrile derivatives. The mol­ecule of B is almost perpendicular to the mean plane of the macrocycle A at the dihedral angle of 88.20 (5)°. The donor–acceptor Hg⋯N inter­actions do not affect the C N bond lengths [1.136 (6) and 1.140 (6) Å]. The trans nitrile group of B coordinates to another macrocycle A, forming an infinite mixed-stack [A•B]∞ architecture toward [101]. The remaining N atoms of two nitrile groups of B are not engaged in any donor–acceptor inter­actions. In the crystal, the mixed stacks are held together by inter­molecular C—F⋯C N secondary inter­actions [2.846 (5)–2.925 (5) Å]. PMID:26594514

  17. Harnessing large deformation and instabilities of soft dielectrics: Theory, experiment, and application

    NASA Astrophysics Data System (ADS)

    Zhao, Xuanhe; Wang, Qiming

    2014-06-01

    Widely used as insulators, capacitors, and transducers in daily life, soft dielectrics based on polymers and polymeric gels play important roles in modern electrified society. Owning to their mechanical compliance, soft dielectrics subject to voltages frequently undergo large deformation and mechanical instabilities. The deformation and instabilities can lead to detrimental failures in some applications of soft dielectrics such as polymer capacitors and insulating gels but can also be rationally harnessed to enable novel functions such as artificial muscle, dynamic surface patterning, and energy harvesting. According to mechanical constraints on soft dielectrics, we classify their deformation and instabilities into three generic modes: (i) thinning and pull-in, (ii) electro-creasing to cratering, and (iii) electro-cavitation. We then provide a systematic understanding of different modes of deformation and instabilities of soft dielectrics by integrating state-of-the-art experimental methods and observations, theoretical models, and applications. Based on the understanding, a systematic set of strategies to prevent or harness the deformation and instabilities of soft dielectrics for diverse applications are discussed. The review is concluded with perspectives on future directions of research in this rapidly evolving field.

  18. 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.

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. 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

    2015-06-01

    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

  4. 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. PMID:26295196

  5. 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.

  6. 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.

  7. Isolation and characterization of a thermotolerant ene reductase from Geobacillus sp. 30 and its heterologous expression in Rhodococcus opacus.

    PubMed

    Tsuji, Naoto; Honda, Kohsuke; Wada, Mayumi; Okano, Kenji; Ohtake, Hisao

    2014-07-01

    Rhodococcus opacus B-4 cells are adhesive to and even dispersible in water-immiscible hydrocarbons owing to their highly lipophilic nature. In this study, we focused on the high operational stability of thermophilic enzymes and applied them to a biocatalytic conversion in an organic reaction medium using R. opacus B-4 as a lipophilic capsule of enzymes to deliver them into the organic medium. A novel thermo- and organic-solvent-tolerant ene reductase, which can catalyze the enantioselective reduction of ketoisophorone to (6R)-levodione, was isolated from Geobacillus sp. 30, and the gene encoding the enzyme was heterologously expressed in R. opacus B-4. Another thermophilic enzyme which catalyzes NAD(+)-dependent dehydrogenation of cyclohexanol was identified from the gene-expression library of Thermus thermophilus and the gene was coexpressed in R. opacus B-4 for cofactor regeneration. While the recombinant cells were not viable in the mixture due to high reaction temperature, 634 mM of (6R)-levodione could be produced with an enantiopurity of 89.2 % ee by directly mixing the wet cells of the recombinant R. opacus with a mixture of ketoisophorone and cyclohexanol at 50 °C. The conversion rate observed with the heat-killed recombinant cells was considerably higher than that obtained with a cell-free enzyme solution, demonstrating that the accessibility between the substrates and enzymes could be improved by employing R. opacus cells as a lipophilic enzyme capsule. These results imply that a combination of thermophilic enzymes and lipophilic cells can be a promising approach for the biocatalytic production of water-insoluble chemicals.

  8. 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.

  9. 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.

  10. Mechanistic Study of the Asymmetric Carbonyl-Ene Reaction between Alkyl Enol Ethers and Isatin Catalyzed by the N,N'-Dioxide-Mg(OTf)2 Complex.

    PubMed

    Wang, Junming; Su, Zhishan; Yang, Na; Hu, Changwei

    2016-08-01

    The mechanism and origin of the stereoselectivity of the asymmetric carbonyl-ene reaction between N-methyl-protected isatin and 2-methyloxypropene catalyzed by the N,N'-dioxide-Mg(OTf)2 complex were investigated by DFT and ONIOM methods. The background reaction occurred via a two-stage, one-step mechanism with a high activation barrier of 30.4 kcal mol(-1) at the B3LYP-D3(BJ)/6-311G**(SMD, CH2Cl2)//B3LYP/6-31G*(SMD, CH2Cl2) level at 303 K. Good linear correlations between the global nucleophilicity index (N) and the activation energy barrier (ΔG(⧧)) were found. The chiral N,N'-Mg(II) complex catalyst could enhance the electrophilicity of the isatin substrate by forming hexacoordinate Mg(II) reactive species. The substituent at the ortho positions of aniline combined with the aliphatic ring of the backbone in the chiral N,N'-dioxide ligand played an important role in the construction of a favorable "pocket-like" chiral environment (chiral pocket) around the Mg(II) center, directing the preferential orientation of the incoming substrate. An unfavorable steric arrangement in the re-face attack pathway translated into a more destabilizing activation strain of the ene substrate, enhancing enantiodifferentiation of two competing pathways for the desired R product. This work also suggested a new phosphine ligand (N-L1) for the formation of the Mg(II) complex catalyst for the asymmetric carbonyl-ene reaction. The chiral environment and Lewis acidity of the Mg(II) complex could be fine-tuned by introduction of P-donor units into the ligand for highly efficient asymmetric catalysis. PMID:27400326

  11. 1,8-Diazabicyclo[5.4.0]undec-7-ene (DBU) and microwave-accelerated green chemistry in methylation of phenols, indoles, and benzimidazoles with dimethyl carbonate.

    PubMed

    Shieh, W C; Dell, S; Repic, O

    2001-12-27

    1,8-Diazabicyclo[5.4.0]undec-7-ene (DBU) is a novel and active catalyst in promoting the methylation reaction of phenols, indoles, and benzimidazoles with dimethyl carbonate under mild conditions. Additional rate enhancement is accomplished by applying microwave irradiation. By incorporating tetrabutylammonium iodide, the same microwave reactions can be further accelerated. By combining these acceleration strategies, very slow chemical transformations that take up to several days can be performed efficiently in high yield within minutes. [reaction: see text] PMID:11784197

  12. Metabolism of ( sup 14 C)cholesterol to C-20 isomeric ( sup 14 C)pregn-5-ene-3,20-diols in the tobacco hornworm, Manduca sexta

    SciTech Connect

    Lozano, R.; Thompson, M.J.; Svoboda, J.A.; Lusby, W.R.; Wilzer, K.R. Jr. )

    1989-03-01

    After injection into male and female fifth-instar larvae of Manduca sexta, ({sup 14}C)cholesterol was converted to C21 steroids, ({sup 14}C)pregn-5-ene-3 beta,20-diols. These metabolites were isolated from 8-day-old pupae and were identified by TLC, HPLC, and GC-MS as the C-20 isomers of pregnene-3 beta,20-diol. They also were isolated from male and female meconium fluid (of 16-day-old pupae) following injection of ({sup 14}C)cholesterol into 14-day-old pupae.

  13. Thiol-ene click synthesis of L-Cysteine-bonded zwitterionic hydrophilic magnetic nanoparticles for selective and efficient enrichment of glycopeptides.

    PubMed

    Wu, Runqing; Xie, Yang; Deng, Chunhui

    2016-11-01

    Efficient and specific enrichment of low-abundant glycopeptides from complex biological samples is essential to glycoproteomics analysis. Herein, novel magnetic zwitterionic hydrophilic nanoparticles based on thiol-ene click chemistry were synthesized. The functionalized magnetic nanoparticles exhibited superior performance in glycopeptide enrichment of HRP tryptic digest, demonstrating low detection limit (0.04ng/μL), high selectivity (a mixture of HRP and BSA at the mass ratio of 1:50) and reproducibility (5 repeating cycles). In addition, the material was successfully applied to glycopeptide enrichment from human serum. The outstanding results indicate the potential of the method in the development of glycoproteomics analysis in real biological samples. PMID:27591639

  14. A novel triterpene from the roots of Paullinia pinnata: 6α-(3'-methoxy-4'-hydroxybenzoyl)-lup-20(29)-ene-3-one.

    PubMed

    Jackson, Nora; Annan, Kofi; Mensah, Abraham Y; Ekuadzi, Edmund; Mensah, Merlin L K; Habtemariam, Solomon

    2015-04-01

    Paullinia pinnata L. (Sapindaceae) is an endemic West African plant that is extensively used in traditional medicine to treat various diseases. Previous phytochemical analysis by various groups led to the isolation of several novel lupene-based triterpenene derivatives along with other classes of compounds. As part of our continued phytochemical studies on the roots of this plant, we have now identified yet another novel triterpene, 6a-(3'-methoxy-4'-hydroxybenzoyl)-lup-20(29)-ene-3-one. The identification of the compound through comprehensive spectroscopic studies is discussed. PMID:25973476

  15. A novel triterpene from the roots of Paullinia pinnata: 6α-(3'-methoxy-4'-hydroxybenzoyl)-lup-20(29)-ene-3-one.

    PubMed

    Jackson, Nora; Annan, Kofi; Mensah, Abraham Y; Ekuadzi, Edmund; Mensah, Merlin L K; Habtemariam, Solomon

    2015-04-01

    Paullinia pinnata L. (Sapindaceae) is an endemic West African plant that is extensively used in traditional medicine to treat various diseases. Previous phytochemical analysis by various groups led to the isolation of several novel lupene-based triterpenene derivatives along with other classes of compounds. As part of our continued phytochemical studies on the roots of this plant, we have now identified yet another novel triterpene, 6a-(3'-methoxy-4'-hydroxybenzoyl)-lup-20(29)-ene-3-one. The identification of the compound through comprehensive spectroscopic studies is discussed.

  16. C-H Acetoxylation-Based Chemical Synthesis of 17 β-Hydroxymethyl-17 α-methyl-18-norandrost-13-ene Steroids.

    PubMed

    Hurski, Alaksiej L; Barysevich, Maryia V; Dalidovich, Tatsiana S; Iskryk, Marharyta V; Kolasava, Nastassia U; Zhabinskii, Vladimir N; Khripach, Vladimir A

    2016-09-26

    Palladium-catalyzed C-H acetoxylation has been proposed as a key transformation in the first chemical synthesis of steroids bearing a unique 17β-hydroxymethyl-17α-methyl-18-nor-13-ene D-fragment. This C-H functionalization step was crucial for inverting the configuration at the quaternary stereocenter of a readily available synthetic intermediate. The developed approach was applied to prepare the metandienone metabolite needed as a reference substance in anti-doping analysis to control the abuse of this androgenic anabolic steroid. PMID:27463692

  17. Harnessing the Affordable Care Act to Catalyze Delivery System Reform and Strengthen Emergency Care in America

    PubMed Central

    Maa, John

    2015-01-01

    As health care reform in the US evolves beyond insurance reform to encompass delivery system reform, the opportunity arises to harness the Affordable Care Act to strengthen patient care in America. One area for dedicated individuals to lead this effort is by improving transitions in patient care across the continuum of team members, specialties, settings, and systems. This article will describe innovations of the surgicalist and acute care surgeon that have emerged in response to the challenges facing surgery in specialization, geography, and the need to comply with health care reform mandates. Three ways will be described to integrate these innovations with pilot programs in the Affordable Care Act: to promote teamwork, to reduce readmissions, and to strengthen emergency care because the key location where the joint efforts intersect most acutely with patient need is in our nation’s Emergency Departments. PMID:25663212

  18. 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.

  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 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.

  1. Harnessing immune cells to enhance β-cell mass in type 1 diabetes.

    PubMed

    Dirice, Ercument; Kulkarni, Rohit N

    2016-01-01

    Type 1 diabetes is characterized by early β-cell loss leading to insulin dependence in virtually all patients with the disease in order to maintain glucose homeostasis. Most studies over the past few decades have focused on limiting the autoimmune attack on the β cells. However, emerging data from patients with long-standing diabetes who continue to harbor functional insulin-producing cells in their diseased pancreas have prompted scientists to examine whether proliferation of existing β cells can be enhanced to promote better glycemic control. In support of this concept, several studies indicate that mononuclear cells that infiltrate the islets have the capacity to trigger proliferation of islet cells including β cells. These observations indicate the exciting possibility of identifying those mononuclear cell types and their soluble factors and harnessing their ability to promote β-cell growth concomitant with autoimmune therapy to prevent the onset and/or halt the progression of the disease. PMID:26755809

  2. 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. PMID:26200694

  3. Harnessing the plasticity of CD4(+) T cells to treat immune-mediated disease.

    PubMed

    DuPage, Michel; Bluestone, Jeffrey A

    2016-03-01

    CD4(+) T cells differentiate and acquire distinct functions to combat specific pathogens but can also adapt their functions in response to changing circumstances. Although this phenotypic plasticity can be potentially deleterious, driving immune pathology, it also provides important benefits that have led to its evolutionary preservation. Here, we review CD4(+) T cell plasticity by examining the molecular mechanisms that regulate it - from the extracellular cues that initiate and drive cells towards varying phenotypes, to the cytosolic signalling cascades that decipher these cues and transmit them into the cell and to the nucleus, where these signals imprint specific gene expression programmes. By understanding how this functional flexibility is achieved, we may open doors to new therapeutic approaches that harness this property of T cells. PMID:26875830

  4. 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.

  5. Computational chemistry, systems biology and toxicology. Harnessing the chemistry of life: revolutionizing toxicology. a commentary.

    PubMed

    Kimber, Ian; Humphris, Colin; Westmoreland, Carl; Alepee, Nathalie; Negro, Gianni Dal; Manou, Irene

    2011-04-01

    There is a continuing interest in, and increasing imperatives for, the development of alternative methods for toxicological evaluations that do not require the use of animals. Although a significant investment has resulted in some achievements, progress has been patchy and there remain many challenges. Among the most significant hurdles is developing non-animal methods that would permit assessment of the potential for a chemical or drug to cause adverse health effects following repeated systemic exposure. Developing approaches to address this challenge has been one of the objectives of the European Partnership for Alternative Approaches to Animal Testing (EPAA). The EPAA is a unique partnership between the European Commission and industry that has interests in all aspects of reducing, refining and replacing the use of animals (the '3Rs'). One possible strategy that emerged from a broad scientific debate sponsored by the EPAA was the opportunity for developing entirely new paradigms for toxicity testing based upon harnessing the increasing power of computational chemistry in combination with advanced systems biology. This brief commentary summarizes a workshop organized by the EPAA in 2010, that had the ambitious title of 'Harnessing the Chemistry of Life: Revolutionizing Toxicology'. At that workshop international experts in chemistry, systems biology and toxicology sought to map out how best developments in these sciences could be exploited to design new strategies for toxicity testing using adverse effects in the liver as an initial focus of attention. Here we describe the workshop design and outputs, the primary purpose being to stimulate debate about the need to align different areas of science with toxicology if new and truly innovative approaches to toxicity testing are to be developed.

  6. 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

  7. Why Nature Eschews the Concerted [2 + 2 + 2] Cycloaddition of a Nonconjugated Cyanodiyne. Computational Study of a Pyridine Synthesis Involving an Ene – Diels-Alder – Bimolecular Hydrogen Transfer Mechanism

    PubMed Central

    Lan, Yu; Danheiser, Rick L.; Houk, K. N.

    2012-01-01

    An intramolecular formal metal-free intramolecular [2 + 2 + 2] cycloaddition for the formation of pyridines has been investigated with M06-2X and B3LYP density functional theory, and compared to the experimentally established three-step mechanism that involves ene reaction - Diels-Alder reaction -hydrogen transfer. The ene reaction of two alkynes is the rate-determining step. This is considerably easier than other possible mechanisms, such as those involving an ene reaction of an alkyne with a nitrile, a concerted [2 + 2 + 2] cycloaddition, or a 1,4-diradical mechanism. The relative facilities of these processes are analyzed with the distortion-interaction model. A bimolecular hydrogen transfer mechanism involving a radical pair intermediate is proposed rather than a concerted intramolecular 1,5-hydrogen shift for the last step in the mechanism. PMID:22188179

  8. 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...

  9. Opportunities for high aspect ratio micro-electro-magnetic-mechanical systems (HAR-MEMMS) at Lawrence Berkeley Laboratory

    SciTech Connect

    Hunter, S.

    1993-10-01

    This report contains viewgraphs on the following topics: Opportunities for HAR-MEMMS at LBL; Industrial Needs and Opportunities; Deep Etch X-ray Lithography; MEMS Activities at BSAC; DNA Amplification with Microfabricated Reaction Chamber; Electrochemistry Research at LBL; MEMS Activities at LLNL; Space Microsensors and Microinstruments; The Advanced Light Source; Institute for Micromaching; IBM MEMS Interests; and Technology Transfer Opportunities at LBL.

  10. Registration of a male fertility restorer oilseed sunflower germplasm HA-R9 resistant to sunflower rust

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The sunflower (Helianthus annuus L.) germplasm HA-R9 (Reg. No.xxx, PI 667595) was developed by the USDA-ARS, Sunflower and Plant Biology Research Unit in collaboration with the Agricultural Experiment Station of North Dakota State University and released in January, 2013. Sunflower rust (caused by P...

  11. Harnessing the instabilities of soft matter: Dynamically tuning of wetting, assembly and pattern transformation in polymer microstructures

    NASA Astrophysics Data System (ADS)

    Zhang, Ying

    2008-10-01

    In this dissertation, we have investigated the fabrication, mechanical instability and applications of two kinds of polymer micro/nano-structures: high-aspect-ratio (HAR) polymer pillar arrays, and periodic porous elastomer membranes. For HAR polymer pillar arrays, we demonstrated the fabrication of high-aspect-ratio (up to 18) polymer micropillars with different shapes and dimensions by replica molding. Capillary force lithography (CFL) is also demonstrated as a simple and flexible method to fabricate microstructures with controlled aspect ratios. Meanwhile, by introducing conventional photoresist SU-8, CFL is successfully coupled with photolithography and used to create hierarchical 2D or 3D structures, which greatly expand the capability of current capillary force lithography. The mechanical stability of HAR structures with varied materials and different aspect ratio, density and shape were also studied and the results show that the adhesive forces from environment are the major cause of structure collapsing. When HAR polymer pillars are subjected to different solvents treatment, both capillary force and solvent swelling need to be considered to completely understand the structure instability. On HAR micropillar array, thermoresponsive polymer brushes, poly ( N-isopropylacrylamide) (PNIPAAm), were selectively grafted at different locations for dynamically tuning surface wetting or pattern assembly. When the temperature changed from 40°C to 20°, depending on the location of polymer brushes, different wetting transitions, either from a composite solid/air state (Cassie state) to a composite solid/liquid state (Hemi-wicking state) or a transition between two Cassie states were observed. Meanwhile, the dynamically tuning of water contact angle enables us to control capillary drying force and thus harness pattern collapse to create superlattice micropatterns. For periodic porous elastomer membrane, a novel pattern transformation effect is discovered due to the

  12. Kinetics of thermal rearrangements in the Delta2-Thujene system: a full quadrisection of a perturbed bicyclo[3.1.0]hex-2-ene.

    PubMed

    Doering, William von E; Zhang, Ting-Hu; Schmidt, Eckhart K G

    2006-07-21

    Further insight into the behavior of suppositional diradicals in a caldera is sought in the thermal rearrangements among the four "Delta2-thujenes", two 1-isopropyl-4-methylbicyclo[3.1.0]hex-2-enes [(-)-cis-1 and (+)-trans-2] and two isomers, exo- and endo-3-isopropyl-6-methylbicyclo[3.1.0]hex-2-ene [(+)-exo-3 and (-)-endo-4]. Optically pure trans-3-isopropyl-5-vinylcyclopentene (5) is the final, strongly thermochemically favored product, the result of an intramolecular homodienyl shift of a methyl hydrogen atom in (-)-endo-4. The set of twelve specific rate constants, four sets of three each, that define the interrelations among the four isomers has been extracted from data acquired starting from each isomer. An attractive mechanistic hypothesis involving an intermediate diradical of iso conformation, common, for example, to both (-)-cis-1 and (+)-exo-3 (as educts), that proceeds to an anticonformer common to both (+)-trans-2 and (-)-endo-4 does not lead to a satisfactory rationalization of the product distribution. Addition of a second mechanistic conceptual scheme, that of a diradical-in-transit behaving as if there were a measure of continuous bonding (for example, (+)-trans-2 proceeding directly to (-)-cis-1), improves agreement with experiment. Over a 30 degrees C range of temperature, there is no credible change in product distribution. PMID:16839150

  13. (2.2.2-Cryptand)potassium tetra­kis­(η2-ethyl­ene)cobaltate(−I)

    PubMed Central

    Brennessel, William W.; Ellis, John E.

    2012-01-01

    The title salt, [K(C18H36N2O6)][Co(C2H4)4], is one of only two known homoleptic ethyl­enemetalates. The cation and anion are well separated, which gives an unperturbed tetra­hedral anion as is expected for a formally Co−I d 10 metal center. The considerable elongation of the C=C bonds of the ethyl­ene ligands [average 1.401 (6) Å], relative to that of free ethyl­ene (1.333 Å), is consistent with metal→π* back-bonding models. One arm of the 2.2.2-cryptand (4,7,13,16,21,24-hexa­oxa-1,10-diaza­bicyclo­[8.8.8]hexa­cosa­ne) complexant is disordered and was modeled over two positions with a refined occupancy ratio of 0.559 (2):0.441 (2). In the crystal, the cationic K(2.2.2-cryptand) units are linked via C—H⋯O hydrogen bonds, forming inversion dimers. There are no other significant inter­molecular inter­actions in the crystal structure. PMID:23125588

  14. Activation of Ene-Diamido Samarium Methoxide with Hydrosilane for Selectively Catalytic Hydrosilylation of Alkenes and Polymerization of Styrene: an Experimental and Theoretical Mechanistic Study.

    PubMed

    Li, Jianfeng; Zhao, Chaoyue; Liu, Jinxi; Huang, Hanmin; Wang, Fengxin; Xu, Xiufang; Cui, Chunming

    2016-09-01

    Samarium methoxide incorporating the ene-diamido ligand L(DME)Sm(μ-OMe)2Sm(DME)L (1; L = [DipNC(Me)C(Me)NDip](2-), Dip = 2,6-iPr2C6H3, and DME = 1,2-dimethoxyethane) has been prepared and structurally characterized. Complex 1 catalyzed the syndiospecific polymerization of styrene upon activation with phenylsilane and regioselective hydrosilylation of styrenes and nonactivated terminal alkenes. Unprecedented regioselectivity (>99.0%) for both types of alkenes has been achieved with the formation of Markovnikov and anti-Markovnikov products in high yields, respectively, whereas the polymerization of styrene resulted in the formation of syndiotactic silyl-capped oligostyrenes. The kinetic experiments and density functional theory calculations strongly support a samarium hydride intermediate generated by σ-bond metathesis of the Sm-OMe bond in 1 with PhSiH3. In addition, the observed regioselectvity for hydrosilylation and polymerization is consistent with the calculated energy profiles, which suggests that the bulky ene-diamido ligand and samarium hydride intermediate have important roles for regio- and stereoselectivity. PMID:27547859

  15. Assessment of the role of in situ generated (E)-2,4-diene-valproic acid in the toxicity of valproic acid and (E)-2-ene-valproic acid in sandwich-cultured rat hepatocytes

    SciTech Connect

    Surendradoss, Jayakumar; Chang, Thomas K.H.; Abbott, Frank S.

    2012-11-01

    Valproic acid (VPA) undergoes cytochrome P450-mediated desaturation to form 4-ene-VPA, which subsequently yields (E)-2,4-diene-VPA by β-oxidation. Another biotransformation pathway involves β-oxidation of VPA to form (E)-2-ene-VPA, which also generates (E)-2,4-diene-VPA by cytochrome P450-mediated desaturation. Although the synthetic form of (E)-2,4-diene-VPA is more hepatotoxic than VPA as shown in various experimental models, there is no conclusive evidence to implicate the in situ generated (E)-2,4-diene-VPA in VPA hepatotoxicity. The present study investigated the effects of modulating the in situ formation of (E)-2,4-diene-VPA on markers of oxidative stress (formation of 2′,7′-dichlorofluorescein; DCF), steatosis (accumulation of BODIPY 558/568 C{sub 12}), necrosis (release of lactate dehydrogenase; LDH), and on cellular total glutathione (GSH) levels in sandwich-cultured rat hepatocytes treated with VPA or (E)-2-ene-VPA. Treatment with either of these chemicals alone increased each of the toxicity endpoints. In VPA-treated hepatocytes, (E)-2,4-diene-VPA was detected only at trace levels, even after phenobarbital (PB) pretreatment and there was no effect on the toxicity of VPA. Furthermore, pretreatment with a cytochrome P450 enzyme inhibitor, 1-aminobenzotriazole (1-ABT), did not influence the extent of VPA toxicity in both PB-pretreated and vehicle-pretreated hepatocytes. However, in (E)-2-ene-VPA-treated hepatocytes, PB pretreatment greatly enhanced the levels of (E)-2,4-diene-VPA and this was accompanied by a further enhancement of the effects of (E)-2-ene-VPA on DCF formation, BODIPY accumulation, LDH release, and GSH depletion. Pretreatment with 1-ABT reduced the concentrations of (E)-2,4-diene-VPA and the extent of (E)-2-ene-VPA toxicity; however, this occurred in PB-pretreated hepatocytes, but not in control hepatocytes. In conclusion, in situ generated (E)-2,4-diene-VPA is not responsible for the hepatocyte toxicity of VPA, whereas it

  16. Transition through co-optation: Harnessing carbon democracy for clean energy

    NASA Astrophysics Data System (ADS)

    Meng, Kathryn-Louise

    This dissertation explores barriers to a clean energy transition in the United States. Clean energy is demonstrably viable, yet the pace of clean energy adoption in the U.S. is slow, particularly given the immediate threat of global climate change. The purpose of this dissertation is to examine the factors inhibiting a domestic energy transition and to propose pragmatic approaches to catalyzing a transition. The first article examines the current political-economic and socio-technical energy landscape in the U.S. Fossil fuels are central to the functioning of the American economy. Given this centrality, constellations of power have been constructed around the reliable and affordable access of fossil fuels. The fossil fuel energy regime is comprised of: political-economic networks with vested interests in continued fossil fuel reliance, and fixed infrastructure that is minimally compatible with distributed generation. A transition to clean energy threatens the profitability of fossil fuel regime actors. Harnessing structural critiques from political ecology and process and function-oriented socio-technical systems frameworks, I present a multi-level approach to identifying pragmatic means to catalyzing an energy transition. High-level solutions confront the existing structure, mid-level solutions harness synergy with the existing structure, and low-level solutions lie outside of the energy system or foster the TIS. This is exemplified using a case study of solar development in Massachusetts. Article two presents a case study of the clean energy technological innovation system (TIS) in Massachusetts. I examine the actors and institutions that support cleantech development. Further, I scrutinize the actors and institutions that help sustain the TIS support system. The concept of a catalyst is presented; a catalyst is an actor that serves to propel TIS functions. Catalysts are critical to facilitating anchoring. Strategic corporate partners are identified as powerful

  17. Harnessing genomics to improve health in the Eastern Mediterranean Region - an executive course in genomics policy.

    PubMed

    Acharya, Tara; Rab, Mohammed Abdur; Singer, Peter A; Daar, Abdallah S

    2005-01-21

    BACKGROUND: While innovations in medicine, science and technology have resulted in improved health and quality of life for many people, the benefits of modern medicine continue to elude millions of people in many parts of the world. To assess the potential of genomics to address health needs in EMR, the World Health Organization's Eastern Mediterranean Regional Office and the University of Toronto Joint Centre for Bioethics jointly organized a Genomics and Public Health Policy Executive Course, held September 20th-23rd, 2003, in Muscat, Oman. The 4-day course was sponsored by WHO-EMRO with additional support from the Canadian Program in Genomics and Global Health. The overall objective of the course was to collectively explore how to best harness genomics to improve health in the region. This article presents the course findings and recommendations for genomics policy in EMR. METHODS: The course brought together senior representatives from academia, biotechnology companies, regulatory bodies, media, voluntary, and legal organizations to engage in discussion. Topics covered included scientific advances in genomics, followed by innovations in business models, public sector perspectives, ethics, legal issues and national innovation systems. RESULTS: A set of recommendations, summarized below, was formulated for the Regional Office, the Member States and for individuals.* Advocacy for genomics and biotechnology for political leadership;* Networking between member states to share information, expertise, training, and regional cooperation in biotechnology; coordination of national surveys for assessment of health biotechnology innovation systems, science capacity, government policies, legislation and regulations, intellectual property policies, private sector activity;* Creation in each member country of an effective National Body on genomics, biotechnology and health to:- formulate national biotechnology strategies- raise biotechnology awareness- encourage teaching and

  18. A bacteriophage tubulin harnesses dynamic instability to center DNA in infected cells.

    PubMed

    Erb, Marcella L; Kraemer, James A; Coker, Joanna K C; Chaikeeratisak, Vorrapon; Nonejuie, Poochit; Agard, David A; Pogliano, Joe

    2014-01-01

    Dynamic instability, polarity, and spatiotemporal organization are hallmarks of the microtubule cytoskeleton that allow formation of complex structures such as the eukaryotic spindle. No similar structure has been identified in prokaryotes. The bacteriophage-encoded tubulin PhuZ is required to position DNA at mid-cell, without which infectivity is compromised. Here, we show that PhuZ filaments, like microtubules, stochastically switch from growing in a distinctly polar manner to catastrophic depolymerization (dynamic instability) both in vitro and in vivo. One end of each PhuZ filament is stably anchored near the cell pole to form a spindle-like array that orients the growing ends toward the phage nucleoid so as to position it near mid-cell. Our results demonstrate how a bacteriophage can harness the properties of a tubulin-like cytoskeleton for efficient propagation. This represents the first identification of a prokaryotic tubulin with the dynamic instability of microtubules and the ability to form a simplified bipolar spindle.

  19. Harnessing Cerebrospinal Fluid Biomarkers in Clinical Trials for Treating Alzheimer's and Parkinson's Diseases: Potential and Challenges

    PubMed Central

    Kim, Dana; Kim, Young-Sam; Shin, Dong Wun; Park, Chang-Shin

    2016-01-01

    No disease-modifying therapies (DMT) for neurodegenerative diseases (NDs) have been established, particularly for Alzheimer's disease (AD) and Parkinson's disease (PD). It is unclear why candidate drugs that successfully demonstrate therapeutic effects in animal models fail to show disease-modifying effects in clinical trials. To overcome this hurdle, patients with homogeneous pathologies should be detected as early as possible. The early detection of AD patients using sufficiently tested biomarkers could demonstrate the potential usefulness of combining biomarkers with clinical measures as a diagnostic tool. Cerebrospinal fluid (CSF) biomarkers for NDs are being incorporated in clinical trials designed with the aim of detecting patients earlier, evaluating target engagement, collecting homogeneous patients, facilitating prevention trials, and testing the potential of surrogate markers relative to clinical measures. In this review we summarize the latest information on CSF biomarkers in NDs, particularly AD and PD, and their use in clinical trials. The large number of issues related to CSF biomarker measurements and applications has resulted in relatively few clinical trials on CSF biomarkers being conducted. However, the available CSF biomarker data obtained in clinical trials support the advantages of incorporating CSF biomarkers in clinical trials, even though the data have mostly been obtained in AD trials. We describe the current issues with and ongoing efforts for the use of CSF biomarkers in clinical trials and the plans to harness CSF biomarkers for the development of DMT and clinical routines. This effort requires nationwide, global, and multidisciplinary efforts in academia, industry, and regulatory agencies to facilitate a new era.

  20. Harnessing Convective Flows as a Novel Platform for Biochemical Reactions and Transport

    NASA Astrophysics Data System (ADS)

    Ugaz, Victor

    2004-03-01

    Buoyancy driven convection offers a novel and greatly simplified mechanism for generating continuous non-pulsatile flow fields in microfluidic devices. These flows can be harnessed directly to construct micropumps, or used in tandem with the applied temperature gradient to perform thermally activated chemical and biochemical reactions without the need for dynamic external temperature control. We demonstrate the suitability of convective flow-based thermocycling systems for performing rapid biodetection assays by constructing a multiwell device incorporating an array of 35 uL high aspect ratio cylindrical cavities to perform polymerase chain reaction (PCR) amplification of a 191 base pair fragment associated with membrane channel proteins M1 and M2 of the influenza-A virus in as little as 15 minutes with performance comparable to conventional thermocyclers. We present a quantitative analysis of PCR yields and observe consistent performance over four orders of magnitude of initial template loading dilution. We also explore the use of convective flows in closed loop systems designed to execute tunable thermocycling and pumping operations in a format suitable for integration into miniaturized chemical and biochemical analysis systems by constructing microfluidic loop structures in a range of lengths and diameters using biocompatible plastic substrates. We present characterization studies of the flow field within these loops, and demonstrate their use to pump fluids in the horizontal plane by constructing devices incorporating 3-D fluidic networks. These convective flow devices are ideally suited as a platform for a new generation of low-power, portable microfluidic DNA analysis systems.

  1. Harnessing Elastic Instability for the self-assembly of complex patterns

    NASA Astrophysics Data System (ADS)

    Matsumoto, Elisabetta; Zhang, Ying; Peter, Anna; Lin, Pei-Chun; Kamien, Randall; Yang, Shu

    2008-03-01

    Directed pattern formation through the self-assembly of complex polymer systems promises to be a powerful approach in the pursuit of novel, transformative technologies. Current approaches to create desired motifs at the nanoscale utilize flow, shear, fields, and other externally imposed, top-down forces. Nature, on the other hand, provides us with a plethora of examples of intrinsic, bottom-up effects: from the phyllotactic growth of plants to animal stripes to fingerprints, instabilities, packing constraints, and simple geometries can drive the formation of delicate, detailed, and beautiful patterns. By harnessing the elastic instability in flexible poly(dimethylsiloxane) (PDMS) membranes with a square lattice of circular pores exposed to a solvent, we distort the pores into a pattern featuring long-range orientational order. Within linear elasticity theory, we find the groundstate configuration of a lattice of interacting deformation elements, or ``dislocation dipoles'' to be in complete agreement with the observed pattern. Our theory allows us a means to design the patterns formed by such elastic frustration.

  2. Highly sensitive electrochemical lead ion sensor harnessing peptide probe molecules on porous gold electrodes.

    PubMed

    Su, Wenqiong; Cho, Misuk; Nam, Jae-Do; Choe, Woo-Seok; Lee, Youngkwan

    2013-10-15

    Lead ion is one of the most hazardous and ubiquitous heavy metal pollutants and poses an increasing threat to the environment and human health. This necessitates rapid and selective detection and/or removal of lead ions from various soil and water resources. Recently, we identified several Pb²⁺ binding peptides via phage display technique coupled with chromatographic biopanning (Nian et al., 2010) where a heptapeptide (TNTLSNN) capable of recognizing Pb²⁺ with high affinity and specificity evolved. In the present study, an electrochemical sensor harnessing this Pb²⁺ affinity peptide as a probe on a porous gold electrode was developed. The three dimensional porous gold electrode was obtained from electrochemical deposition using the dynamic hydrogen bubble template method. A thin layer of poly(thiophene acetic acid) (PTAA) was coated on the porous gold surface. The Pb²⁺ recognizing peptide was immobilized via amide linkage on the PTAA. The developed biosensor was demonstrated to be fast, selective and reproducible in Pb²⁺ etection, exhibiting Pb²⁺-specific peak current values around -0.15 V in a broad concentration range (1-1×10⁷ nM) in 10 min despite the repeated use after regeneration.

  3. Harnessing disorder: onychophorans use highly unstructured proteins, not silks, for prey capture.

    PubMed

    Haritos, Victoria S; Niranjane, Ajay; Weisman, Sarah; Trueman, Holly E; Sriskantha, Alagacone; Sutherland, Tara D

    2010-11-01

    Onychophora are ancient, carnivorous soft-bodied invertebrates which capture their prey in slime that originates from dedicated glands located on either side of the head. While the biochemical composition of the slime is known, its unusual nature and the mechanism of ensnaring thread formation have remained elusive. We have examined gene expression in the slime gland from an Australian onychophoran, Euperipatoides rowelli, and matched expressed sequence tags to separated proteins from the slime. The analysis revealed three categories of protein present: unique high-molecular-weight proline-rich proteins, and smaller concentrations of lectins and small peptides, the latter two likely to act as protease inhibitors and antimicrobial agents. The predominant proline-rich proteins (200 kDa+) are composed of tandem repeated motifs and distinguished by an unusually high proline and charged residue content. Unlike the highly structured proteins such as silks used for prey capture by spiders and insects, these proteins lack ordered secondary structure over their entire length. We propose that on expulsion of slime from the gland onto prey, evaporative water loss triggers a glass transition change in the protein solution, resulting in adhesive and enmeshing thread formation, assisted by cross-linking of complementary charged and hydrophobic regions of the protein. Euperipatoides rowelli has developed an entirely new method of capturing prey by harnessing disordered proteins rather than structured, silk-like proteins. PMID:20519222

  4. Helmet Use Amongst Equestrians: Harnessing Social and Attitudinal Factors Revealed in Online Forums.

    PubMed

    Haigh, Laura; Thompson, Kirrilly

    2015-01-01

    Equestrian activities pose significant head injury risks to participants. Yet, helmet use is not mandatory in Australia outside of selected competitions. Awareness of technical countermeasures and the dangers of equestrian activities has not resulted in widespread adoption of simple precautionary behaviors like helmet use. Until the use of helmets whilst riding horses is legislated in Australia, there is an urgent need to improve voluntary use. To design effective injury prevention interventions, the factors affecting helmet use must first be understood. To add to current understandings of these factors, we examined the ways horse riders discussed helmet use by analyzing 103 posts on two helmet use related threads from two different Australian equestrian forums. We found evidence of social influence on helmet use behaviors as well as three attitudes that contributed towards stated helmet use that we termed: "I Can Control Risk", "It Does Not Feel Right" and "Accidents Happen". Whilst we confirm barriers identified in previous literature, we also identify their ability to support helmet use. This suggests challenging but potentially useful complexity in the relationship between risk perception, protective knowledge, attitudes, decision-making and behavior. Whilst this complexity is largely due to the involvement of interspecies relationships through which safety, risk and trust are distributed; our findings about harnessing the potential of barriers could be extended to other high risk activities. PMID:26479375

  5. A new technology for harnessing the dye polluted water and dye collection in a chemical factory.

    PubMed

    Pu, J P; Pu, P M; Hu, C H; Qian, J L; Pu, J X; Hua, J K

    2001-04-01

    A new technology for harnessing the dye polluted water and dye collection was developed. It is based on the enhanced evaporation by using solar, wind and air temperature energy and additional heat-electric energy. It consists of four parts: (1) evaporation carrier system (evaporation carrier and frame for evaporation carrier) for polluted water; (2) polluted water circulating system (pumping-spraying-collecting); (3) heating system; (4) workshop with polluted water reservoir-tanks and rainfall prevention roof. The polluted water was (heated in case necessary) sprayed to the evaporation carrier system and the water was evaporated when it moved in the space and downward along the carrier mainly by using natural (solar, wind and air temperature energy). In case, when there is no roof for the carrier system, the polluted water can be stored in the reservoirs (storage volume for about 20 days). The first 10-25 mm rainfall also need to be stored in the reservoirs to meet the state standard for discharging wastewater. The dye may be collected at the surface in the reservoir-tanks and the crystallized salt may be collected at the bottom plate. The black-color wastewater released by the factory is no more discharged to the surface water system of Taihu Lake Basin. About 2 kg dye and 200 kg industrial salt may be collected from each tone of the polluted water. The non-pollution production of dye may be realized by using this technology with environmental, economical and social benefits. PMID:11590742

  6. Harnessing disorder: onychophorans use highly unstructured proteins, not silks, for prey capture.

    PubMed

    Haritos, Victoria S; Niranjane, Ajay; Weisman, Sarah; Trueman, Holly E; Sriskantha, Alagacone; Sutherland, Tara D

    2010-11-01

    Onychophora are ancient, carnivorous soft-bodied invertebrates which capture their prey in slime that originates from dedicated glands located on either side of the head. While the biochemical composition of the slime is known, its unusual nature and the mechanism of ensnaring thread formation have remained elusive. We have examined gene expression in the slime gland from an Australian onychophoran, Euperipatoides rowelli, and matched expressed sequence tags to separated proteins from the slime. The analysis revealed three categories of protein present: unique high-molecular-weight proline-rich proteins, and smaller concentrations of lectins and small peptides, the latter two likely to act as protease inhibitors and antimicrobial agents. The predominant proline-rich proteins (200 kDa+) are composed of tandem repeated motifs and distinguished by an unusually high proline and charged residue content. Unlike the highly structured proteins such as silks used for prey capture by spiders and insects, these proteins lack ordered secondary structure over their entire length. We propose that on expulsion of slime from the gland onto prey, evaporative water loss triggers a glass transition change in the protein solution, resulting in adhesive and enmeshing thread formation, assisted by cross-linking of complementary charged and hydrophobic regions of the protein. Euperipatoides rowelli has developed an entirely new method of capturing prey by harnessing disordered proteins rather than structured, silk-like proteins.

  7. Harnessing surface-bound enzymatic reactions to organize microcapsules in solution.

    PubMed

    Shklyaev, Oleg E; Shum, Henry; Sen, Ayusman; Balazs, Anna C

    2016-03-01

    By developing new computational models, we examine how enzymatic reactions on an underlying surface can be harnessed to direct the motion and organization of reagent-laden microcapsules in a fluid-filled microchannel. In the presence of appropriate reagents, surface-bound enzymes can act as pumps, which drive large-scale fluid flows. When the reagents diffuse through the capsules' porous shells, they can react with enzymatic sites on the bottom surface. The ensuing reaction generates fluid density variations, which result in fluid flows. These flows carry the suspended microcapsules and drive them to aggregate into "colonies" on and near the enzyme-covered sites. This aggregation continues until the reagent has been depleted and the convection stops. We show that the shape of the assembled colonies can be tailored by patterning the distribution of enzymes on the surface. This fundamental physicochemical mechanism could have played a role in the self-organization of early biological cells (protocells) and can be used to regulate the autonomous motion and targeted delivery of microcarriers in microfluidic devices. PMID:27034990

  8. Harnessing intrinsic localized modes to identify impurities in nonlinear periodic systems

    NASA Astrophysics Data System (ADS)

    Thota, M.; Harne, R. L.; Wang, K. W.

    2015-02-01

    Intrinsic localized modes (ILMs) are concentrations of vibrational energy in periodic systems/lattices due to the combined influences of nonlinearity and discreteness. Moreover, ILMs can move within the system and may strongly interact with an impurity, such as a stiffness change, mass variation, etc. Numerous scientific fields have uncovered examples and evidence of ILMs, motivating a multidisciplinary pursuit to rigorously understand the underlying principles. In spite of the diverse technical studies, a characterization of ILM interaction behaviors with multiple impurities in dissipative lattices remains outstanding. The insights on such behaviors may be broadly useful when dynamic measurements are the only accessible features of the periodic system. For instance, one may guide an ILM within the lattice using a deliberately applied and steered impurity and harness the observed interaction behaviors with a second, static (immovable) impurity/defect to identify how the underlying lattice is different at the second, defected site, whether or not one knew the position of the defect a priori. In this spirit, this research studies, analyzes, and characterizes the interaction types amongst an ILM and multiple impurities, and devises a method to identify a static defect impurity using quantitatively and qualitatively distinct interaction phenomena. The method is found to be robust to moderate levels of lattice stiffness heterogeneity and is applicable to monitor various property changes that represent impurities. Finally, experimental studies verify that ILMs interact with multiple impurities in unique ways such that defect features may be effectively identified.

  9. Harnessing the secretome of cardiac stem cells as therapy for ischemic heart disease.

    PubMed

    Khanabdali, Ramin; Rosdah, Ayeshah A; Dusting, Gregory J; Lim, Shiang Y

    2016-08-01

    Adult stem cells continue to promise opportunities to repair damaged cardiac tissue. However, precisely how adult stem cells accomplish cardiac repair, especially after ischemic damage, remains controversial. It has been postulated that the clinical benefit of adult stem cells for cardiovascular disease results from the release of cytokines and growth factors by the transplanted cells. Studies in animal models of myocardial infarction have reported that such paracrine factors released from transplanted adult stem cells contribute to improved cardiac function by several processes. These include promoting neovascularization of damaged tissue, reducing inflammation, reducing fibrosis and scar formation, as well as protecting cardiomyocytes from apoptosis. In addition, these factors might also stimulate endogenous repair by activating cardiac stem cells. Interestingly, stem cells discovered to be resident in the heart appear to be functionally superior to extra-cardiac adult stem cells when transplanted for cardiac repair and regeneration. In this review, we discuss the therapeutic potential of cardiac stem cells and how the proteins secreted from these cells might be harnessed to promote repair and regeneration of damaged cardiac tissue. We also highlight how recent controversies about the efficacy of adult stem cells in clinical trials of ischemic heart disease have not dampened enthusiasm for the application of cardiac stem cells and their paracrine factors for cardiac repair: the latter have proved superior to the mesenchymal stem cells used in most clinical trials in the past, some of which appear to have been conducted with sub-optimal rigor.

  10. Strategies and Advancements in Harnessing the Immune System for Gastric Cancer Immunotherapy

    PubMed Central

    Subhash, Vinod Vijay; Yeo, Mei Shi; Tan, Woei Loon; Yong, Wei Peng

    2015-01-01

    In cancer biology, cells and molecules that form the fundamental components of the tumor microenvironment play a major role in tumor initiation, and progression as well as responses to therapy. Therapeutic approaches that would enable and harness the immune system to target tumor cells mark the future of anticancer therapy as it could induce an immunological memory specific to the tumor type and further enhance tumor regression and relapse-free survival in cancer patients. Gastric cancer is one of the leading causes of cancer-related mortalities that has a modest survival benefit from existing treatment options. The advent of immunotherapy presents us with new approaches in gastric cancer treatment where adaptive cell therapies, cancer vaccines, and antibody therapies have all been used with promising outcomes. In this paper, we review the current advances and prospects in the gastric cancer immunotherapy. Special focus is laid on new strategies and clinical trials that attempt to enhance the efficacy of various immunotherapeutic modalities in gastric cancer. PMID:26579545

  11. Harnessing the Power of Genomics and Immunoinformatics To Produce Improved Vaccines

    PubMed Central

    Moise, Leonard; Cousens, Leslie; Fueyo, Joanna; De Groot, Anne S.

    2014-01-01

    The role of cellular immunity as a mediator of protection against disease is gaining recognition, particularly in regard to the many pathogens for which we presently lack effective vaccines. As a result, there is an ever-increasing need to understand the T cell populations induced by vaccination and therefore T cell epitopes responsible for triggering their activation. Although the characterization and harnessing of cellular immunity for vaccine development is an active area of research interest, the field still needs to rigorously define T cell epitope specificities, above all, on a genomic level. New immunoinformatic epitope mapping tools now make it possible to identify pathogen epitopes and perform comparisons against human and microbial genomic datasets. Such information will help determine whether adaptive immune responses elicited by a vaccine are both pathogen-specific and protective, but not cross-reactive against host or host-associated sequences that could jeopardize self-tolerance and/or human microbiome-host homeostasis. Here, we discuss advances in genomics and vaccine design and their relevance to the development of safer, more effective vaccines. PMID:22646824

  12. Harnessing the power of reputation: strengths and limits for promoting cooperative behaviors.

    PubMed

    Barclay, Pat

    2012-01-01

    Evolutionary approaches have done much to identify the pressures that select for cooperative sentiment. This helps us understand when and why cooperation will arise, and applied research shows how these pressures can be harnessed to promote various types of cooperation. In particular, recent evidence shows how opportunities to acquire a good reputation can promote cooperation in laboratory and applied settings. Cooperation can be promoted by tapping into forces like indirect reciprocity, costly signaling, and competitive altruism. When individuals help others, they receive reputational benefits (or avoid reputational costs), and this gives people an incentive to help. Such findings can be applied to promote many kinds of helping and cooperation, including charitable donations, tax compliance, sustainable and pro-environmental behaviors, risky heroism, and more. Despite the potential advantages of using reputation to promote positive behaviors, there are several risks and limits. Under some circumstances, opportunities for reputation will be ineffective or promote harmful behaviors. By better understanding the dynamics of reputation and the circumstances under which cooperation can evolve, we can better design social systems to increase the rate of cooperation and reduce conflict. PMID:23253792

  13. Harnessing surface-bound enzymatic reactions to organize microcapsules in solution

    PubMed Central

    Shklyaev, Oleg E.; Shum, Henry; Sen, Ayusman; Balazs, Anna C.

    2016-01-01

    By developing new computational models, we examine how enzymatic reactions on an underlying surface can be harnessed to direct the motion and organization of reagent-laden microcapsules in a fluid-filled microchannel. In the presence of appropriate reagents, surface-bound enzymes can act as pumps, which drive large-scale fluid flows. When the reagents diffuse through the capsules’ porous shells, they can react with enzymatic sites on the bottom surface. The ensuing reaction generates fluid density variations, which result in fluid flows. These flows carry the suspended microcapsules and drive them to aggregate into “colonies” on and near the enzyme-covered sites. This aggregation continues until the reagent has been depleted and the convection stops. We show that the shape of the assembled colonies can be tailored by patterning the distribution of enzymes on the surface. This fundamental physicochemical mechanism could have played a role in the self-organization of early biological cells (protocells) and can be used to regulate the autonomous motion and targeted delivery of microcarriers in microfluidic devices. PMID:27034990

  14. Harnessing Wisdom of the Crowds Dynamics for Time-dependent Reputation and Ranking

    NASA Astrophysics Data System (ADS)

    Daly, Elizabeth M.

    The "wisdom of the crowds" is a concept used to describe the utility of harnessing group behaviour, where user opinion evolves over time and the opinion of the masses collectively demonstrates wisdom. Web 2.0 is a new medium where users are not just consumers, but are also contributors. By contributing content to the system, users become part of the network and relationships between users and content can be derived. Example applications are collaborative bookmarking networks such as dcl.icio.us and file sharing applications such as You Tube and Fliekr. These networks rely on user contributed content, described and classified using tags. The wealth of user generated content can be hard to navigate and search due to difficulties in comparing documents with similar tags and the application of traditional information retrieval scoring techniques are limited. Evaluating the time evolving interests of users may be used to derive quality of content. In this chapter, we explore a technique to rank documents based on reputation. The reputation is a combination of the number of bookmarkers, the reputation of the bookmarking user and the time dynamics of the document. Additionally, this reputation measure is extended to take into account the time-dependent, term-dependent reputation of a document. Experimental results and analysis are presented on a large collaborative IBM bookmarking network called Dogear.

  15. Auxiliary Basis Sets for Density Fitting in Explicitly Correlated Calculations: The Atoms H-Ar.

    PubMed

    Kritikou, Stella; Hill, J Grant

    2015-11-10

    Auxiliary basis sets specifically matched to the correlation consistent cc-pVnZ-F12 and cc-pCVnZ-F12 orbital basis sets for the elements H-Ar have been optimized at the density-fitted second-order Møller-Plesset perturbation theory level of theory for use in explicitly correlated (F12) methods, which utilize density fitting for the evaluation of two-electron integrals. Calculations of the correlation energy for a test set of small to medium sized molecules indicate that the density fitting error when using these auxiliary sets is 2 to 3 orders of magnitude smaller than the F12 orbital basis set incompleteness error. The error introduced by the use of these fitting sets within the resolution-of-the-identity approximation of the many-electron integrals arising in F12 theory has also been assessed and is demonstrated to be negligible and well-controlled. General guidelines are proposed for the optimization of density fitting auxiliary basis sets for use with F12 methods for other elements.

  16. Harnessing structural darkness in the visible and infrared wavelengths for a new source of light

    NASA Astrophysics Data System (ADS)

    Huang, Jianfeng; Liu, Changxu; Zhu, Yihan; Masala, Silvia; Alarousu, Erkki; Han, Yu; Fratalocchi, Andrea

    2016-01-01

    Engineering broadband light absorbers is crucial to many applications, including energy-harvesting devices and optical interconnects. The performances of an ideal absorber are that of a black body, a dark material that absorbs radiation at all angles and polarizations. Despite advances in micrometre-thick films, the absorbers available to date are still far from an ideal black body. Here, we describe a disordered nanostructured material that shows an almost ideal black-body absorption of 98-99% between 400 and 1,400 nm that is insensitive to the angle and polarization of the incident light. The material comprises nanoparticles composed of a nanorod with a nanosphere of 30 nm diameter attached. When diluted into liquids, a small concentration of nanoparticles absorbs on average 26% more than carbon nanotubes, the darkest material available to date. By pumping a dye optical amplifier with nanosecond pulses of ˜100 mW power, we harness the structural darkness of the material and create a new type of light source, which generates monochromatic emission (˜5 nm wide) without the need for any resonance. This is achieved through the dynamics of light condensation in which all absorbed electromagnetic energy spontaneously generates single-colour energy pulses.

  17. Harnessing Potential Evaporation as a Renewable Energy Resource With Water-Saving Benefits

    NASA Astrophysics Data System (ADS)

    Cavusoglu, A. H.; Chen, X.; Gentine, P.; Sahin, O.

    2015-12-01

    Water's large latent heat of vaporization makes evaporation a critical component of the energy balance at the Earth's surface. An immense amount of energy drives the hydrological cycle and is an important component of various weather and climate patterns. However, the potential of harnessing evaporation has received little attention as a renewable energy resource compared to wind and solar energy. Here, we investigate the potential of harvesting energy from naturally evaporating water. Using weather data across the contiguous United States and a modified model of potential evaporation, we estimate the power availability, intermittency, and the changes in evaporation rates imposed by energy conversion. Our results indicate that natural evaporation can deliver power densities similar to existing renewable energy platforms and require little to no energy storage to match the varying power demands of urban areas. This model also predicts additional, and substantial, water savings by reducing evaporative losses. These findings suggest that evaporative energy harvesting can address significant challenges with water/energy interactions that could be of interest to the hydrology community.

  18. Harnessing snap-through instability for shape-recoverable energy-absorbing structure

    NASA Astrophysics Data System (ADS)

    Kang, Sung; Shan, Sicong; Raney, Jordan; Wang, Pai; Candido, Francisco; Lewis, Jennifer; Bertoldi, Katia

    2015-03-01

    Energy absorbing materials and structures are used in numerous areas for maintaining structural integrity, protection and comfort. To absorb/dissipate energy from shock/vibration, one generally relies on processes such as plastic deformation and damping as the case of metal foams and suspensions. Because plastic deformation and damping induce irreversible change in the energy-absorbing systems such as shape changes and degradation of damping elements by heat dissipation, it would be desirable to develop a new energy-absorption mechanism with reversibility. Furthermore, it would be desirable to implement energy-absorption mechanisms whose behavior is not affected by the rate of loading. Here, we report a shape-recoverable system that absorbs energy without degradation by harnessing multistability in elastic structures. Using numerical simulations, we investigate geometrical parameters that determine the onset of the snap-through and multi-stability. We subsequently manufacture structures with different geometrical parameters and sizes using a scalable direct-write 3D printing approach. We experimentally demonstrate reversible energy-absorption in these structures at strain rates over three orders of magnitudes, with reduced peak acceleration under impact by up to one order of magnitude compared with control samples. Our findings can open new opportunities for scalable design and manufacturing of energy-absorbing materials and structures.

  19. A Bottom-Up Engineered Broadband Optical Nanoabsorber for Radiometry and Energy Harnessing Applications

    NASA Technical Reports Server (NTRS)

    Kaul, Anupama B.; Coles, James B.; Megerian, Krikor G.; Eastwood, Michael; Green, Robert O.; Bandaru, Prabhakar R.

    2013-01-01

    Optical absorbers based on vertically aligned multi-walled carbon nanotubes (MWCNTs), synthesized using electric-field assisted growth, are described here that show an ultra-low reflectance, 100X lower compared to Au-black from wavelength lamba approximately 350 nm - 2.5 micron. A bi-metallic Co/Ti layer was shown to catalyze a high site density of MWCNTs on metallic substrates and the optical properties of the absorbers were engineered by controlling the bottom-up synthesis conditions using dc plasma-enhanced chemical vapor deposition (PECVD). Reflectance measurements on the MWCNT absorbers after heating them in air to 400deg showed negligible changes in reflectance which was still low, approximately 0.022 % at lamba approximately 2 micron. In contrast, the percolated structure of the reference Au-black samples collapsed completely after heating, causing the optical response to degrade at temperatures as low as 200deg. The high optical absorption efficiency of the MWCNT absorbers, synthesized on metallic substrates, over a broad spectral range, coupled with their thermal ruggedness, suggests they have promise in solar energy harnessing applications, as well as thermal detectors for radiometry.

  20. Harnessing the power of reputation: strengths and limits for promoting cooperative behaviors.

    PubMed

    Barclay, Pat

    2012-12-20

    Evolutionary approaches have done much to identify the pressures that select for cooperative sentiment. This helps us understand when and why cooperation will arise, and applied research shows how these pressures can be harnessed to promote various types of cooperation. In particular, recent evidence shows how opportunities to acquire a good reputation can promote cooperation in laboratory and applied settings. Cooperation can be promoted by tapping into forces like indirect reciprocity, costly signaling, and competitive altruism. When individuals help others, they receive reputational benefits (or avoid reputational costs), and this gives people an incentive to help. Such findings can be applied to promote many kinds of helping and cooperation, including charitable donations, tax compliance, sustainable and pro-environmental behaviors, risky heroism, and more. Despite the potential advantages of using reputation to promote positive behaviors, there are several risks and limits. Under some circumstances, opportunities for reputation will be ineffective or promote harmful behaviors. By better understanding the dynamics of reputation and the circumstances under which cooperation can evolve, we can better design social systems to increase the rate of cooperation and reduce conflict.

  1. Project WEALTH (Water, Energy, Agriculture, Lighting, Training and Health): Harnessing the wealth of nations

    SciTech Connect

    Kashkari, C.

    1996-12-31

    Project WEALTH, hereafter referred to as WEALTH, is a global plan for the economic development of an estimated one million villages in the world, where one billion people live. The plan will focus on the provision of: Water, Energy, Agriculture, Lighting, Training and Health (WEALTH), by harnessing the natural resources of the villages and utilizing the technologies available in the industrialized countries. In the first phase of the project, one model village (WEALTH Center) will be established in every developing country of the world. The Center will serve as the training and demonstration center and promote the project in the country. WEALTH will provide economic opportunities for the industrialized and the developing countries. The Small Business Sector will play a major role in the implementation of the project. The project will be developed and implemented, not by governments, but by private sector, in cooperation with national governments. When fully operational, the project has the potential of generating business to the tune of billions of dollars every year. The Inner-cities of the US can participate in the project resulting in their own rapid development. WEALTH will spur global economic growth and lay the foundation for prosperity and peace in the twenty-first century.

  2. Towards safer, better healthcare: harnessing the natural properties of complex sociotechnical systems

    PubMed Central

    Braithwaite, J; Runciman, W B; Merry, A F

    2009-01-01

    Objectives: To sustain an argument that harnessing the natural properties of sociotechnical systems is necessary to promote safer, better healthcare. Methods: Triangulated analyses of discrete literature sources, particularly drawing on those from mathematics, sociology, marketing science and psychology. Results: Progress involves the use of natural networks and exploiting features such as their scale-free and small world nature, as well as characteristics of group dynamics like natural appeal (stickiness) and propagation (tipping points). The agenda for change should be set by prioritising problems in natural categories, addressed by groups who self select on the basis of their natural interest in the areas in question, and who set clinical standards and develop tools, the use of which should be monitored by peers. This approach will facilitate the evidence-based practice that most agree is now overdue, but which has not yet been realised by the application of conventional methods. Conclusion: A key to health system transformation may lie under-recognised under our noses, and involves exploiting the naturally-occurring characteristics of complex systems. Current strategies to address healthcare problems are insufficient. Clinicians work best when their expertise is mobilised, and they flourish in groupings of their own interests and preference. Being invited, empowered and nurtured rather than directed, micro-managed and controlled through a hierarchy is preferable. PMID:19204130

  3. The responses of young people to their experiences of first-episode psychosis: harnessing resilience.

    PubMed

    Henderson, Anthony R; Cock, Alan

    2015-04-01

    There is a burgeoning literature on first-episode psychosis, the focus of which is early intervention. Little emphasis has been placed on the responses of young people to their experiences of psychosis. This study, therefore, aimed to describe and explain the responses of young people to their first episode of psychosis. Data obtained from ten young people who attended a community early intervention recovery program in Perth Western Australia were analysed using a grounded theory method. The results revealed that the basic psychosocial problem experienced by participants was loss of control resulting in disrupted lives and that the core variable, harnessing resilience, accounted for most of the variance in their behaviour to overcome this problem. The resultant framework described and explained how participants resiled and established direction in their lives. Although there are limitations with this qualitative study, such as the small size and the demographics of the sample, the findings have potential implications for approaches to service provision and phase specific interventions. PMID:25064090

  4. Energy-Looping Nanoparticles: Harnessing Excited-State Absorption for Deep-Tissue Imaging.

    PubMed

    Levy, Elizabeth S; Tajon, Cheryl A; Bischof, Thomas S; Iafrati, Jillian; Fernandez-Bravo, Angel; Garfield, David J; Chamanzar, Maysamreza; Maharbiz, Michel M; Sohal, Vikaas S; Schuck, P James; Cohen, Bruce E; Chan, Emory M

    2016-09-27

    Near infrared (NIR) microscopy enables noninvasive imaging in tissue, particularly in the NIR-II spectral range (1000-1400 nm) where attenuation due to tissue scattering and absorption is minimized. Lanthanide-doped upconverting nanocrystals are promising deep-tissue imaging probes due to their photostable emission in the visible and NIR, but these materials are not efficiently excited at NIR-II wavelengths due to the dearth of lanthanide ground-state absorption transitions in this window. Here, we develop a class of lanthanide-doped imaging probes that harness an energy-looping mechanism that facilitates excitation at NIR-II wavelengths, such as 1064 nm, that are resonant with excited-state absorption transitions but not ground-state absorption. Using computational methods and combinatorial screening, we have identified Tm(3+)-doped NaYF4 nanoparticles as efficient looping systems that emit at 800 nm under continuous-wave excitation at 1064 nm. Using this benign excitation with standard confocal microscopy, energy-looping nanoparticles (ELNPs) are imaged in cultured mammalian cells and through brain tissue without autofluorescence. The 1 mm imaging depths and 2 μm feature sizes are comparable to those demonstrated by state-of-the-art multiphoton techniques, illustrating that ELNPs are a promising class of NIR probes for high-fidelity visualization in cells and tissue. PMID:27603228

  5. Dams, environment and regional development--harnessing the "elixir of life: water" for overall development.

    PubMed

    Vyas, Jay Narayan

    2002-01-01

    Water--the Elixir of Life--has the potential to sustain human life and also to develop it further, and that is why various international instruments have aptly recognized its role in sustainable development. This paper reviews the global and Indian water scenario before presenting the case of Gujarat State, where perennial water scarcity has raised serious threats to the existence of millions of people and cattle and has led to environmental degradation and constrained economic development. More than 13,000 villages out of 18,028 villages of the State are facing scarcity in terms of crop failure this year. Drinking water supply is maintained by transporting water by road tankers, "water special" trains and even by ships via a sea route. Lack of access to safe and clean water for domestic use has a detrimental effect on the social fabric, and even incidences of migration and water riots are recorded. The paper discusses the efficacy of available options including rain water harvesting. The efforts of the State to harness the untapped waters of Narmada for the survival of millions and sustainable development of western India, are discussed adjudging socioeconomic and environmental impacts. The paper concludes that assured water supply is essentially critical for overall development.

  6. Invited Commentary: Harnessing Housing Natural Experiments Is Important, but Beware Differential Misclassification of Difference in Difference.

    PubMed

    Bentley, Rebecca; Baker, Emma; Blakely, Tony

    2016-09-15

    In this issue of the Journal, Reeves et al. (Am J Epidemiol. 2016;184(6):421-429) present the findings of a natural experiment analyzing the association between reduced housing affordability and mental ill health. Their difference-in-difference analysis of cross-sectional, quarterly population health surveys administered before and after implementation of a policy to reduce Housing Benefit payments in the United Kingdom in April 2011 represents an important way to assess the impact of a national housing policy shift on public health. It is a well-conducted study harnessing a natural experiment and adds to the weight of evidence supporting an association between housing costs and mental health. However, quantitative bias analysis based on the reported findings suggests that a small amount of differential (by unblinded Housing Benefit status) misclassification bias in the outcome may be enough to explain the observed association. Our analysis of possible misclassification bias in the outcome used in the study highlights the need for caution when a difference-in-difference estimate is small, the population is not blinded to its postintervention exposure status, and the outcome measure is subjective and prone to differential (by unblinded exposure or treatment status) misclassification. PMID:27613661

  7. MRI Evaluation of Spinal Length and Vertebral Body Angle During Loading with a Spinal Compression Harness

    NASA Technical Reports Server (NTRS)

    Campbell, James A.; Hargens, Alan R.; Murthy, G.; Ballard, R. E.; Watenpaugh, D. E.; Hargens, Alan, R.; Sanchez, E.; Yang, C.; Mitsui, I.; Schwandt, D.; Fechner, K. P.; Holton, Emily M. (Technical Monitor)

    1998-01-01

    Weight bearing by the spinal column during upright posture often plays a role in the common problem of low back pain. Therefore, we developed a non-ferromagnetic spinal compression harness to enable MRI investigations of the spinal column during axial loading. Human subjects were fitted with a Nest and a footplate which were connected by adjustable straps to an analog load cell. MRI scans of human subjects (5 males and 1 female with age range of 27-53 yrs) during loaded and unloaded conditions were accomplished with a 1.5 Tesla GE Signa scanner. Studies of two subjects undergoing sequentially increasing spinal loads revealed significant decreases (r(sup 2) = 0.852) in spinal length between T4 and L5 culminating in a 1.5 to 2% length decrease during loading with 75% body weight. Sagittal vertebral body angles of four subjects placed under a constant 50% body weight load for one hour demonstrated increased lordotic and kyphotic curvatures. In the lumbar spine, the L2 vertebral body experienced the greatest angular change (-3 deg. to -5 deg.) in most subjects while in the thoracic spine, T4 angles increased from the unloaded state by +2 deg. to +9 deg. Overall, our studies demonstrate: 1) a progressive, although surprisingly small, decrease in spinal length with increasing load and 2) relatively large changes in spinal column angulation with 50% body weight.

  8. Harnessing Geothermal Energy from CO2 Enhanced Oil Recovery (EOR) Operations

    NASA Astrophysics Data System (ADS)

    Saar, M. O.; Randolph, J. B.

    2012-12-01

    Recent geotechnical research shows that geothermal heat can be efficiently mined by circulating CO2 through naturally permeable, porous rock formations. This method, called CO2 Plume Geothermal (CPG), targets the same geologic reservoirs that are suitable for deep saline aquifer CO2 sequestration or enhanced oil recovery (EOR). While previous investigations have focused on CO2-based heat mining from saline aquifers, here we present new research that is primarily concerned with EOR reservoirs, specifically those using a CO2 flood. EOR operations provide excellent opportunities for economically-favorable geothermal energy recovery, assuming subsurface temperatures are sufficient, because the majority of costly infrastructure (i.e., wells) is in place. Moreover, the subsurface characteristics that make a site suitable for hydrocarbon recovery -- at least moderate reservoir permeability and porosity, and a low-permeability capping feature -- help ensure that fluid can be circulated for heat extraction and that CO2 will be contained. However, heat extraction from the CO2 + water/brine + hydrocarbon EOR production stream is challenging, requiring fluid separation and multiple binary and/or direct power systems (depending on site-specific fluid composition and conditions). We discuss several scenarios, encompassing multiple power system configurations, for harnessing geothermal energy from CO2 EOR operations. In addition, we present preliminary numerical modeling results for net power production from such EOR operations -- accounting for wide variation in produced fluid temperature, pressure, and composition -- and consider the economic implications of power sales for EOR sites.

  9. LncRNAWiki: harnessing community knowledge in collaborative curation of human long non-coding RNAs.

    PubMed

    Ma, Lina; Li, Ang; Zou, Dong; Xu, Xingjian; Xia, Lin; Yu, Jun; Bajic, Vladimir B; Zhang, Zhang

    2015-01-01

    Long non-coding RNAs (lncRNAs) perform a diversity of functions in numerous important biological processes and are implicated in many human diseases. In this report we present lncRNAWiki (http://lncrna.big.ac.cn), a wiki-based platform that is open-content and publicly editable and aimed at community-based curation and collection of information on human lncRNAs. Current related databases are dependent primarily on curation by experts, making it laborious to annotate the exponentially accumulated information on lncRNAs, which inevitably requires collective efforts in community-based curation of lncRNAs. Unlike existing databases, lncRNAWiki features comprehensive integration of information on human lncRNAs obtained from multiple different resources and allows not only existing lncRNAs to be edited, updated and curated by different users but also the addition of newly identified lncRNAs by any user. It harnesses community collective knowledge in collecting, editing and annotating human lncRNAs and rewards community-curated efforts by providing explicit authorship based on quantified contributions. LncRNAWiki relies on the underling knowledge of scientific community for collective and collaborative curation of human lncRNAs and thus has the potential to serve as an up-to-date and comprehensive knowledgebase for human lncRNAs. PMID:25399417

  10. Periodic trends governing the interactions between impurity atoms [H-Ar] and (alpha)-U

    SciTech Connect

    Taylor, Christopher David

    2008-01-01

    The binding energies, geometries, charges and electronic structures of a series of impurity atoms [H-Ar] interacting with the {alpha}-U lattice in various configurations were assessed by means of density functional theory calculations. Periodic trends governing the binding energy were highlighted and related to the electronic properties of the impurity atoms, with some consideration given to the band-structure of {alpha}-U. The strongest bound impurity atoms include [C, N, O] and [Si, P, S]. The general trends in the binding energy can be reproduced by a simple parameterisation in terms of the electronegativity (charge-transfer) and covalent radius (elasticity theory) of the impurity atom. The strongest bound atoms deviate from this model, due to their ability to bind with an optimum mixture of covalency and ionicity. This last point is evidenced by the partial overlap of the impurity atom p-band with the hybrid d-/f-band of {alpha}-U. It is expected that the trends and general behaviour reported in this work can be extended to the interactions of impurity atoms with other metallic systems.

  11. Highly sensitive electrochemical lead ion sensor harnessing peptide probe molecules on porous gold electrodes.

    PubMed

    Su, Wenqiong; Cho, Misuk; Nam, Jae-Do; Choe, Woo-Seok; Lee, Youngkwan

    2013-10-15

    Lead ion is one of the most hazardous and ubiquitous heavy metal pollutants and poses an increasing threat to the environment and human health. This necessitates rapid and selective detection and/or removal of lead ions from various soil and water resources. Recently, we identified several Pb²⁺ binding peptides via phage display technique coupled with chromatographic biopanning (Nian et al., 2010) where a heptapeptide (TNTLSNN) capable of recognizing Pb²⁺ with high affinity and specificity evolved. In the present study, an electrochemical sensor harnessing this Pb²⁺ affinity peptide as a probe on a porous gold electrode was developed. The three dimensional porous gold electrode was obtained from electrochemical deposition using the dynamic hydrogen bubble template method. A thin layer of poly(thiophene acetic acid) (PTAA) was coated on the porous gold surface. The Pb²⁺ recognizing peptide was immobilized via amide linkage on the PTAA. The developed biosensor was demonstrated to be fast, selective and reproducible in Pb²⁺ etection, exhibiting Pb²⁺-specific peak current values around -0.15 V in a broad concentration range (1-1×10⁷ nM) in 10 min despite the repeated use after regeneration. PMID:23707872

  12. Salinity stress induced lipid synthesis to harness biodiesel during dual mode cultivation of mixotrophic microalgae.

    PubMed

    Venkata Mohan, S; Devi, M Prathima

    2014-08-01

    Influence of salinity as a stress factor to harness biodiesel was assessed during dual mode cultivation of microalgae by integrating biomass growth phase (BGP) and salinity induced lipid induction phase (LIP). BGP was evaluated in mixotrophic mode employing nutrients (NPK) and carbon (glucose) source while LIP was operated under stress environment with varying salt concentrations (0, 0.5, 1 and 2gNaCl/l). Salinity stress triggered both biomass growth and lipid synthesis in microalgae significantly. BGP showed higher increments in biomass growth (2.55g/l) while LIP showed higher lipid productivity (1gNaCl/l; total/neutral lipid, 23.4/9.2%) than BGP (total/neutral lipid, 15.2/6%). Lower concentrations of salinity showed positive influence on the process while higher concentrations showed marked inhibition. Salinity stress also facilitated in maintaining saturated fatty acid methyl esters in higher amounts which associates with the improved fuel properties. Efficient wastewater treatment was observed during BGP operation indicating the assimilation of carbon/nutrients by microalgae.

  13. Harnessing Innovative Technologies to Advance Children’s Mental Health: Behavioral Parent Training As an Example

    PubMed Central

    Jones, Deborah J.; Forehand, Rex; Cuellar, Jessica; Kincaid, Carlye; Parent, Justin; Fenton, Nicole; Goodrum, Nada

    2012-01-01

    Disruptive behaviors of childhood are among the most common reasons for referral of children to mental health professionals. Behavioral parent training (BPT) is the most efficacious intervention for these problem behaviors, yet BPT is substantially underutilized beyond university research and clinic settings. With the aim of addressing this research-to-practice gap, this article highlights the considerable, but largely unrealized, potential for technology to overcome the two most pressing challenges hindering the diffusion of BPT: (1). The dearth of BPT training and supervision opportunities for therapists who work with families of children with disruptive behaviors and; (2). The failure to engage and retain families in BPT services when services are available. To this end, this review presents a theoretical framework to guide technological innovations in BPT and highlights examples of how technology is currently being harnessed to overcome these challenges. This review also discusses recommendations for using technology as a delivery vehicle to further advance the field of BPT and the potential implications of technological innovations in BPT for other areas of children’s mental health are discussed. PMID:23313761

  14. Harnessing heterologous and endogenous CRISPR-Cas machineries for efficient markerless genome editing in Clostridium

    PubMed Central

    Pyne, Michael E.; Bruder, Mark R.; Moo-Young, Murray; Chung, Duane A.; Chou, C. Perry

    2016-01-01

    Application of CRISPR-Cas9 systems has revolutionized genome editing across all domains of life. Here we report implementation of the heterologous Type II CRISPR-Cas9 system in Clostridium pasteurianum for markerless genome editing. Since 74% of species harbor CRISPR-Cas loci in Clostridium, we also explored the prospect of co-opting host-encoded CRISPR-Cas machinery for genome editing. Motivation for this work was bolstered from the observation that plasmids expressing heterologous cas9 result in poor transformation of Clostridium. To address this barrier and establish proof-of-concept, we focus on characterization and exploitation of the C. pasteurianum Type I-B CRISPR-Cas system. In silico spacer analysis and in vivo interference assays revealed three protospacer adjacent motif (PAM) sequences required for site-specific nucleolytic attack. Introduction of a synthetic CRISPR array and cpaAIR gene deletion template yielded an editing efficiency of 100%. In contrast, the heterologous Type II CRISPR-Cas9 system generated only 25% of the total yield of edited cells, suggesting that native machinery provides a superior foundation for genome editing by precluding expression of cas9 in trans. To broaden our approach, we also identified putative PAM sequences in three key species of Clostridium. This is the first report of genome editing through harnessing native CRISPR-Cas machinery in Clostridium. PMID:27157668

  15. An overhead harness and trolly system for balance and ambulation assessment and training.

    PubMed

    Harburn, K L; Hill, K M; Kramer, J F; Noh, S; Vandervoort, A A; Matheson, J E

    1993-02-01

    Safe assessment of standing balance and gait is often jeopardized by the potential for falls, which may have major physical and legal consequences. This article describes the design and use of a system that enhances the safety of the patient and clinician during balance and gait assessment and training. The system consists of an overhead track and moveable trolly that allows the patient, while secured in a simple body harness, the freedom to ambulate, perform functional types of activities, and fall with minimal risk of injury. As a result, a single therapist can more readily assess balance and ambulation, as well as provide training for these skills. In addition, the therapist is free to observe the patient's movements from any position, without direct physical contact. Practically, the system described may allow ambulation training sooner after injury or surgery, permit training in weight-bearing or partial weight-bearing activities with or without assistive devices, and allow the clinician to focus on assessment and training, rather than on patient safety.

  16. Harnessing the heightened public awareness of celebrity HIV disclosures: "Magic" and "Cookie" Johnson and HIV testing.

    PubMed

    Tesoriero, J M; Sorin, M D; Burrows, K A; LaChance-McCullough, M L

    1995-06-01

    This article investigates the impact NBA basketball star Earvin ("Magic") Johnson's HIV disclosure had on changes in demand for HIV counseling and testing services in New York State's 61 Anonymous HIV Counseling and Testing sites. Interrupted time-series analyses were conducted on weekly data from over 34,000 clients seeking anonymous HIV counseling and testing services from January 1991 to June 1992, to determine whether demand for these services changed as a result of the disclosure. Results indicated that immediately following the HIV disclosure, there was a substantial increase in service demand, which transcended all sex, race, age, and most HIV risk-related boundaries. Seven months later, demand had not returned to pre-disclosure levels. The strong impact on females, coupled with additional data analyses in obstetrical settings, suggests that previous research has been too narrow in focus, and that the effect of Johnson's HIV disclosure has been enhanced, in part, by the publicity surrounding his wife and baby. The importance of harnessing the heightened public awareness of celebrity HIV disclosures is discussed.

  17. Silver-catalyzed oxidative coupling of aniline and ene carbonyl/acetylenic carbonyl compounds: an efficient route for the synthesis of quinolines.

    PubMed

    Zhang, Xu; Xu, Xuefeng

    2014-11-01

    An efficient silver-mediated coupling of aniline with ene carbonyl/acetylenic carbonyl compounds for the synthesis of quinolines is reported. The transformation is effective for a broad range of substrates, thus enabling the expansion of substituent architectures on the heterocyclic framework. The electronic properties of the substituents on the amine have been investigated. It was found that molecules with both electron-donating and electron-withdrawing substituents were suitable substrates for this transformation, and the expected products were obtained in moderate to excellent yields. The use of a single catalytic system to mediate chemical transformations in a synthetic operation is important for the development of new atom-economic strategies and this strategy is efficient in building complex structures from simple starting materials in an environmentally benign fashion.

  18. Mass spectral characteristics of the chlorinated disinfection byproduct 2,2,4-trichloro-5-methoxy-cyclopent-4-ene-1,3-dione

    NASA Astrophysics Data System (ADS)

    Gong, Huijuan; Bao, Yanchu; Yang, Jihong; Jiang, Qin; Chen, Zezhi

    2010-06-01

    The objective of this paper was to correct the mistakes of a previous interpretation of electron impact ionization (EI) mass spectrum of the chlorinated disinfection byproduct (DBP) in drinking water naming 2,2,4-trichloro-5-methoxy-cyclopent-4-ene-1,3-dione (TCMCD). Moreover the positive-ion chemical ionization (CI +) and electrospray ionization (ESI +) mass spectra were also studied. As the search of new chlorinated disinfection byproducts in drinking water is a challenge and researchers generally have to attempt to identify unknown chlorinated products generated from incompletely defined starting materials, fully understanding the mass spectra of this compound may do some help for the analysis of other unknown chlorinated disinfection byproducts.

  19. Oxidation of 3-amino-1-phenylprop-1-enes by monoamine oxidase and their use in a continuous assay of the enzyme.

    PubMed Central

    Williams, C H; Lawson, J; Backwell, F R

    1988-01-01

    3-Amino-1-phenylprop-1-ene (cinnamylamine) and some derivatives were examined as substrates for monoamine oxidases A and B in mitochondria. All of the amines examined were readily oxidized by monoamine oxidase B but much less readily by monoamine oxidase A. E-Cinnamylamine was found to have Km 0.025 mM and Vmax. 3.9 nmol/min per mg of mitochondrial protein. Corresponding values with monoamine oxidase A were 0.026 mM and 0.85 nmol/min per mg respectively. Despite their different stereochemistry, E- and Z-N-methylcinnamylamines were almost equally effective as substrates for monoamine oxidase B. The characteristic u.v. absorbance and high absorption coefficient of cinnamaldehyde, the product produced by enzymic oxidation of cinnamylamine, is utilized in a sensitive continuous spectrophotometric assay for both enzymes in the rat and for the assay of a purified monoamine oxidase B from bovine liver. PMID:3223960

  20. Monodisperse colloidal metal particle from nonaqueous solutions: catalytic behavior in hydrogenation of but-1-ene of platinum, palladium, and rhodium particles supported on pumice

    SciTech Connect

    Boutonnet, M.; Kizling, J.; Mintsa-Eya, V.; Choplin, A.; Touroude, R.; Maire, G.; Stenius, P.

    1987-01-01

    Metal catalysts have been prepared by depositing monodisperse particles of platinum (2-3 nm), rhodium (2-3 nm), or palladium (5 nm) prepared in reversed micellar solutions on pumice. The particles are well dispersed on the support whereas particles deposited from aqueous or alcoholic solution give large aggregates. The catalytic properties of these different catalysts in the deuteration, isomerization, and hydrogen-deuterium exchange of but-1-ene have been compared. The activities calculated per metal surface atom are similar. However, platinum prepared from microemulsions show unusually high selectivity in the isomerization reaction, and for such particles dehydrogenated species are active in the exchange reaction. The specificity of rhodium and palladium catalysts is independent of the mode of preparation. The reaction mechanisms are discussed.

  1. A dual-polymer electrochromic device with high coloration efficiency and fast response time: poly(3,4-(1,4-butylene-(2-ene)dioxy)thiophene)-polyaniline ECD.

    PubMed

    Kang, Joo-Hee; Xu, Zhaochao; Paek, Seung-Min; Wang, Fang; Hwang, Seong-Ju; Yoon, Juyoung; Choy, Jin-Ho

    2011-08-01

    A new dual-polymer electrochromic device (ECD) composed of poly(3,4-(1,4-butylene-(2-ene)dioxy)thiophene) (PBueDOT) and polyaniline (PANI) with a hydrophobic molten salt electrolyte has been developed. To build this system, an alkylenedioxy ring in the BueDOT backbone was expanded to include a strongly electron-donating alkylenedioxy bridge, and the thickness and surface morphology of the corresponding PBueDOT film were controlled systematically. Not only the dual-electrochromic-polymer-electrode system, but also the expanded alkylenedioxy ring in the BueDOT backbone, synergistically improved the electrochromic performance. From the coloration efficiency (CE) value calculations, we found that the CE was enhanced up to 930 cm(2) C(-1). Furthermore, these ECDs showed an extremely fast response time of less than 80 ms.

  2. catena-Poly[[[tetra-aqua-magnesium]-trans-μ-[(piperazine-1,4-diium-1,4-di-yl)bis-(methyl-ene)]di-phospho-nato] hemihydrate].

    PubMed

    Schilling, Lars-Hendrik; Stock, Norbert

    2013-01-01

    The structure of the title polymer, }[Mg(C6H14N2O6P2)(H2O)4]·0.5H2O} n , is based on centrosymmetric MgO6 octahedra, which are linked by [(piperazine-1,4-diium-1,4-di-yl)bis-(methyl-ene)]di-phospho-nate ligands, forming chains parallel to [1-1-1]. These chains are connected via hydrogen bonds primarily formed between the phospho-nate groups and water mol-ecules. The latter constitute four of the corners of the MgO6 polyhedra and bind to the O atoms of the phospho-nate groups of neighbouring chains. The lattice water molecule is disordered around an inversion centre, exhibiting an occupancy of 0.25. PMID:24109276

  3. A highly regio- and stereoselective formation of bicyclo[4.2.0]oct-5-ene derivatives through thermal intramolecular [2 + 2] cycloaddition of allenes.

    PubMed

    Ohno, Hiroaki; Mizutani, Tsuyoshi; Kadoh, Yoichi; Aso, Akimasa; Miyamura, Kumiko; Fujii, Nobutaka; Tanaka, Tetsuaki

    2007-06-01

    Thermal [2 + 2] cycloaddition of allenes with an additional multiple bond is described. By simply heating the allenenes or allenynes having a three-atom tether in an appropriate solvent such as dioxane or DMF, the distal double bond of the allenic moiety regioselectively participates in the cycloaddition to form bicyclo[4.2.0]oct-5-ene derivatives in good to excellent yields. In all the reactions of allenenes, the olefin geometry was completely transferred to the cycloadducts. While the reaction of terminal allenes afforded bicyclic cyclobutane derivatives as a single isomer, the cycloaddition of some internal allenes with axial chirality yielded a diastereomeric mixture of cycloadducts. These results are in good accordance with the stepwise mechanism through a biradical intermediate with a coplanar allyl radical.

  4. Rhodium(I)-catalyzed intramolecular ene reaction of vinylidenecyclopropanes and alkenes for the formation of bicyclo[5.1.0]octylenes.

    PubMed

    Li, Wei; Yuan, Wei; Shi, Min; Hernandez, Erik; Li, Guigen

    2010-01-01

    An efficient catalytic system for the intramolecular ene reaction of allene and alkene of diarylvinylidenecyclopropanes has been established. The reaction was achieved by using [RhCl(CO)(2)](2) as the catalyst in co-solvents of toluene and acetonitrile. MeCN was found to play a crucial role in controlling the reaction toward formation of bicyclo[5.1.0]octylene derivatives. An alternative system consisting of [RhCl(CO)(2)](2) and toluene in the absence of MeCN was found to give [2 + 2] cycloaddition adducts. The structures have been unambiguously determined by X-ray structural analysis. Deuterium labeling experiments were conducted to confirm the mechanism hypothesis.

  5. New Lewis-Acidic Molybdenum(II) and Tungsten(II) Catalysts for Intramolecular Carbonyl Ene and Prins Reactions. Reversal of the Stereoselectivity of Cyclization of Citronellal.

    PubMed

    Kocovský, Pavel; Ahmed, Ghafoor; Srogl, Jirí; Malkov, Andrei V.; Steele, John

    1999-04-16

    New Mo(II) complexes BnEt(3)N(+)[Mo(CO)(4)ClBr(2)](-) (A) and Mo(CO)(5)(OTf)(2) (B) and their W(II) congeners D and E have been developed as catalysts for the title reactions. Unlike other Lewis acids, the latter catalysts exhibit cis-stereoselectivity in the cyclization of citronellal (1 --> 3 with A and 1 --> 5 with B). Isotopic labeling allowed formulation of the reaction mechanism, according to which these complexes act as bulky Lewis acids, eta(1)-coordinated to the carbonyl oxygen. The stereochemistry appears to be controlled by the protruding ligand L(p), which dictates the boatlike transition state III. The kinetically formed cis-alkenol 3 can be equilibrated by [Mo(CO)(4)Br(2)](2) (C) or ZnCl(2) to its trans-epimer 2 via a retro-ene reaction.

  6. One-pot preparation of glutathione-silica hybrid monolith for mixed-mode capillary liquid chromatography based on "thiol-ene" click chemistry.

    PubMed

    Lin, Zian; Tan, Xiaoqing; Yu, Ruifang; Lin, Jiashi; Yin, Xiaofei; Zhang, Lan; Yang, Huanghao

    2014-08-15

    A novel glutathione (GSH)-silica hybrid monolithic column synthesized via a combination of thiol-ene click reaction and one-pot process was described, where thiol-end GSH organic monomer and 2,2-azobisisobutyronitrile (AIBN) were mixed with hydrolyzed tetramethyloxysilane (TMOS) and γ-methacryloxypropyltrimethoxysilane (γ-MAPS) and then introduced into a fused-silica capillary for simultaneous polycondensation and "thiol-ene" click reaction to form the GSH-silica hybrid monolith. The effects of the molar ratio of TMOS/γ-MAPS, the amount of GSH, and the volume of porogen on the morphology, permeability and pore properties of the prepared GSH-silica hybrid monoliths were studied in detail. A uniform monolithic network with high porosity was obtained. A series of test compounds including alkylbenzenes, amides, and anilines were used to evaluate the retention behaviors of the GSH-silica hybrid monolithic column. The results demonstrated that the prepared GSH-silica hybrid monolith exhibited multiple interactions including hydrophobicity, hydrophilicity, as well as cation exchange interaction. The run-to-run, column-to-column and batch-to-batch reproducibilities of the GSH-silica hybrid monolith for phenols' retention were satisfactory with the relative standard deviations (RSDs) less than 1.3% (n=5), 2.6% (n=3) and 3.2% (n=3), respectively, indicating the effectiveness and practicability of the proposed method. In addition, the GSH-silica hybrid monolith was applied to the separation of nucleotides, peptides and protein tryptic digests, respectively. The successful applications suggested the potential of the GSH-silica hybrid monolith in complex sample analysis.

  7. Preparation of polyhedral oligomeric silsesquioxane-based hybrid monolith by ring-opening polymerization and post-functionalization via thiol-ene click reaction.

    PubMed

    Liu, Zhongshan; Ou, Junjie; Lin, Hui; Wang, Hongwei; Dong, Jing; Zou, Hanfa

    2014-05-16

    A polyhedral oligomeric silsesquioxane (POSS) hybrid monolith was simply prepared by using octaglycidyldimethylsilyl POSS (POSS-epoxy) and cystamine dihydrochloride as monomers via ring-opening polymerization. The effects of composition of prepolymerization solution and polycondensation temperature on the morphology and permeability of monolithic column were investigated in detail. The obtained POSS hybrid monolithic column showed 3D skeleton morphology and exhibited high column efficiency of ∼71,000 plates per meter in reversed-phase mechanism. Owing to this POSS hybrid monolith essentially possessing a great number of disulfide bonds, the monolith surface would expose thiol groups after reduction with dithiothreitol (DTT), which supplied active sites to functionalize with various alkene monomers via thiol-ene click reaction. The results indicated that the reduction with DTT could not destroy the 3D skeleton of hybrid monolith. Both stearyl methylacrylate (SMA) and benzyl methacrylate (BMA) were selected to functionalize the hybrid monolithic columns for reversed-phase liquid chromatography (RPLC), while [2-(methacryloyloxy)ethyl]-dimethyl-(3-sulfopropyl)-ammonium hydroxide (MSA) was used to modify the hybrid monolithic column in hydrophilic interaction chromatography (HILIC). These modified hybrid monolithic columns could be successfully applied for separation of small molecules with high efficiency. It is demonstrated that thiol-ene click reaction supplies a facile way to introduce various functional groups to the hybrid monolith possessing thiol groups. Furthermore, due to good permeability of the resulting hybrid monoliths, we also prepared long hybrid monolithic columns in narrow-bore capillaries. The highest column efficiency reached to ∼70,000 plates using a 1-m-long column of 75μm i.d. with a peak capacity of 147 for isocratic chromatography, indicating potential application in separation and analysis of complex biosamples.

  8. Assessment of gustatory responses to different sugars in harnessed and free-moving bumblebee workers (Bombus terrestris).

    PubMed

    Mommaerts, Veerle; Wäckers, Felix; Smagghe, Guy

    2013-06-01

    For bumblebee colony survival, sugar responses are crucial as nectar is the main carbohydrate source and flower choice is likely determined by sugar composition. This study used a bioassay both with harnessed and with free-moving workers of the bumblebee Bombus terrestris to study the gustatory response to the 3 major plant sugars by both groups. In harnessed workers of B. terrestris, a concentration of 5.5% of fructose and glucose was required to induce the proboscis extension reflex in 50% of the workers, whereas for sucrose, a much higher concentration of 40% was needed. In contrast, free-moving workers given a choice between 30% glucose, 30% sucrose, 30% fructose, and water showed a strong preference for sucrose (66% of individuals) compared with 18% for glucose and 16% for fructose; water was never chosen. Familiarization with 30% fructose provoked a significant increase in preference toward fructose, indicating plasticity. In addition, by amputation of the tarsi, it was found that tarsi plays a role in the sugar response with especially the foreleg tarsi being involved in the response to fructose. Our results demonstrated that sugar response is different in free-moving versus harnessed bumblebee workers and that tarsi plays a role in sugar perception.

  9. The HARNESS Workbench: Unified and Adaptive Access to Diverse HPC Platforms

    SciTech Connect

    Sunderam, Vaidy S.

    2012-03-20

    The primary goal of the Harness WorkBench (HWB) project is to investigate innovative software environments that will help enhance the overall productivity of applications science on diverse HPC platforms. Two complementary frameworks were designed: one, a virtualized command toolkit for application building, deployment, and execution, that provides a common view across diverse HPC systems, in particular the DOE leadership computing platforms (Cray, IBM, SGI, and clusters); and two, a unified runtime environment that consolidates access to runtime services via an adaptive framework for execution-time and post processing activities. A prototype of the first was developed based on the concept of a 'system-call virtual machine' (SCVM), to enhance portability of the HPC application deployment process across heterogeneous high-end machines. The SCVM approach to portable builds is based on the insertion of toolkit-interpretable directives into original application build scripts. Modifications resulting from these directives preserve the semantics of the original build instruction flow. The execution of the build script is controlled by our toolkit that intercepts build script commands in a manner transparent to the end-user. We have applied this approach to a scientific production code (Gamess-US) on the Cray-XT5 machine. The second facet, termed Unibus, aims to facilitate provisioning and aggregation of multifaceted resources from resource providers and end-users perspectives. To achieve that, Unibus proposes a Capability Model and mediators (resource drivers) to virtualize access to diverse resources, and soft and successive conditioning to enable automatic and user-transparent resource provisioning. A proof of concept implementation has demonstrated the viability of this approach on high end machines, grid systems and computing clouds.

  10. Harnessing Petaflop-Scale Multi-Core Supercomputing for Problems in Space Science

    NASA Astrophysics Data System (ADS)

    Albright, B. J.; Yin, L.; Bowers, K. J.; Daughton, W.; Bergen, B.; Kwan, T. J.

    2008-12-01

    The particle-in-cell kinetic plasma code VPIC has been migrated successfully to the world's fastest supercomputer, Roadrunner, a hybrid multi-core platform built by IBM for the Los Alamos National Laboratory. How this was achieved will be described and examples of state-of-the-art calculations in space science, in particular, the study of magnetic reconnection, will be presented. With VPIC on Roadrunner, we have performed, for the first time, plasma PIC calculations with over one trillion particles, >100× larger than calculations considered "heroic" by community standards. This allows examination of physics at unprecedented scale and fidelity. Roadrunner is an example of an emerging paradigm in supercomputing: the trend toward multi-core systems with deep hierarchies and where memory bandwidth optimization is vital to achieving high performance. Getting VPIC to perform well on such systems is a formidable challenge: the core algorithm is memory bandwidth limited with low compute-to-data ratio and requires random access to memory in its inner loop. That we were able to get VPIC to perform and scale well, achieving >0.374 Pflop/s and linear weak scaling on real physics problems on up to the full 12240-core Roadrunner machine, bodes well for harnessing these machines for our community's needs in the future. Many of the design considerations encountered commute to other multi-core and accelerated (e.g., via GPU) platforms and we modified VPIC with flexibility in mind. These will be summarized and strategies for how one might adapt a code for such platforms will be shared. Work performed under the auspices of the U.S. DOE by the LANS LLC Los Alamos National Laboratory. Dr. Bowers is a LANL Guest Scientist; he is presently at D. E. Shaw Research LLC, 120 W 45th Street, 39th Floor, New York, NY 10036.

  11. Harnessing Diversity towards the Reconstructing of Large Scale Gene Regulatory Networks

    PubMed Central

    Yamanaka, Ryota; Kitano, Hiroaki

    2013-01-01

    Elucidating gene regulatory network (GRN) from large scale experimental data remains a central challenge in systems biology. Recently, numerous techniques, particularly consensus driven approaches combining different algorithms, have become a potentially promising strategy to infer accurate GRNs. Here, we develop a novel consensus inference algorithm, TopkNet that can integrate multiple algorithms to infer GRNs. Comprehensive performance benchmarking on a cloud computing framework demonstrated that (i) a simple strategy to combine many algorithms does not always lead to performance improvement compared to the cost of consensus and (ii) TopkNet integrating only high-performance algorithms provide significant performance improvement compared to the best individual algorithms and community prediction. These results suggest that a priori determination of high-performance algorithms is a key to reconstruct an unknown regulatory network. Similarity among gene-expression datasets can be useful to determine potential optimal algorithms for reconstruction of unknown regulatory networks, i.e., if expression-data associated with known regulatory network is similar to that with unknown regulatory network, optimal algorithms determined for the known regulatory network can be repurposed to infer the unknown regulatory network. Based on this observation, we developed a quantitative measure of similarity among gene-expression datasets and demonstrated that, if similarity between the two expression datasets is high, TopkNet integrating algorithms that are optimal for known dataset perform well on the unknown dataset. The consensus framework, TopkNet, together with the similarity measure proposed in this study provides a powerful strategy towards harnessing the wisdom of the crowds in reconstruction of unknown regulatory networks. PMID:24278007

  12. Genetic mapping of rust resistance genes in confection sunflower line HA-R6 and oilseed line RHA 397.

    PubMed

    Gong, L; Gulya, T J; Markell, S G; Hulke, B S; Qi, L L

    2013-08-01

    Few widely effective resistance sources to sunflower rust, incited by Puccinia helianthi Schwein., have been identified in confection sunflower (Helianthus annuus L.). The USDA inbred line HA-R6 is one of the few confection sunflower lines resistant to rust. A previous allelism test indicated that rust resistance genes in HA-R6 and RHA 397, an oilseed-type restorer line, are either allelic or closely linked; however, neither have been characterized nor molecularly mapped. The objectives of this study are (1) to locate the rust resistance genes in HA-R6 and RHA 397 on a molecular map, (2) to develop closely linked molecular markers for rust resistance diagnostics, and (3) to determine the resistance spectrum of two lines when compared with other rust-resistant lines. Two populations of 140 F2:3 families each from the crosses of HA 89, as susceptible parent, with HA-R6 and RHA 397 were inoculated with race 336 of P. helianthi in the greenhouse. The resistance genes (R-genes) in HA-R6 and RHA 397 were molecularly mapped to the lower end of linkage group 13, which encompasses a large R-gene cluster, and were designated as R 13a and R 13b, respectively. In the initial maps, SSR (simple sequence repeat) and InDel (insertion and deletion) markers revealed 2.8 and 8.2 cM flanking regions for R 13a and R 13b, respectively, linked with a common marker set of four co-segregating markers, ORS191, ORS316, ORS581, and ZVG61, in the distal side and one marker ORS464 in the proximal side. To identify new markers closer to the genes, sunflower RGC (resistance gene candidate) markers linked to the downy mildew R-gene Pl 8 and located at the same region as R 13a and R 13b were selected to screen the two F2 populations. The RGC markers RGC15/16 and a newly developed marker SUN14 designed from a BAC contig anchored by RGC251 further narrowed down the region flanking R 13a and R 13b to 1.1 and 0.1 cM, respectively. Both R 13a and R 13b are highly effective against all rust races

  13. Helmet Use Amongst Equestrians: Harnessing Social and Attitudinal Factors Revealed in Online Forums

    PubMed Central

    Haigh, Laura; Thompson, Kirrilly

    2015-01-01

    relationship between risk perception, protective knowledge, attitudes, decision-making and behavior. Whilst this complexity is largely due to the involvement of interspecies relationships through which safety, risk and trust are distributed; our findings about harnessing the potential of barriers could be extended to other high risk activities. PMID:26479375

  14. Hydrodynamic modeling and feasibility study of harnessing tidal power at the Bay of Fundy

    NASA Astrophysics Data System (ADS)

    Chang, Jen

    Due to rising fuel costs and environmental concerns, energy generation from alternative power source has become one of the most important issues in energy policy. Tidal power is one of the alternative energy sources. The tidal range at the Bay of Fundy is the largest in the world (approximately 16 meters). It represents a prime location for harnessing tidal power using the daily rising and ebbing tide. In this study, a two dimensional finite element model has been developed and applied to simulate the tidal responses, including water level and flow velocity, in the Bay of Fundy region. The simulation results are used to choose the suitable location for energy development and to predict possible energy generated from different types of generation methods. Fluid motion is assumed to be governed by the shallow water equation since the wave length associated with tide is much longer than the water depth in the Bay of Fundy. By using a real time series of water elevation at the entrance of the bay, the computer model finds tidal response for each node in the study area, which is then verified by the observation record from several tidal gauge stations inside the bay. This study shows that the at-site cost of the energy for barrage type tidal power plants is around 0.065 to 0.097 per kWh at the recommended Shepody Bay, Cumberland Basin, and Cobequid Bay. The cost of energy for the current turbine type tidal power plants is 0.13/kWh to 0.24/kWh at the area with highest current velocity. Compared with the recent bill of the local power company, the at-site unit cost of energy from the barrage type of tidal power plant is feasible, but the environmental concerns of channel blocking by barrage present a formidable constraint. For the current turbine type of tidal power plant, even the most suitable sites are not financially feasible under current technology, but this type of power generation may become feasible as oil prices continue to increase and more efficient turbines

  15. A method to harness global crowd-sourced data to understand travel behavior in avalanche terrain.

    NASA Astrophysics Data System (ADS)

    Hendrikx, J.; Johnson, J.

    2015-12-01

    To date, most studies of the human dimensions of decision making in avalanche terrain has focused on two areas - post-accident analysis using accident reports/interviews and, the development of tools as decision forcing aids. We present an alternate method using crowd-sourced citizen science, for understanding decision-making in avalanche terrain. Our project combines real-time GPS tracking via a smartphone application, with internet based surveys of winter backcountry users as a method to describe and quantify travel practices in concert with group decision-making dynamics, and demographic data of participants during excursions. Effectively, we use the recorded GPS track taken within the landscape as an expression of the decision making processes and terrain usage by the group. Preliminary data analysis shows that individual experience levels, gender, avalanche hazard, and group composition all influence the ways in which people travel in avalanche terrain. Our results provide the first analysis of coupled real-time GPS tracking of the crowd while moving in avalanche terrain combined with psychographic and demographic correlates. This research will lead to an improved understanding of real-time decision making in avalanche terrain. In this paper we will specifically focus on the presentation of the methods used to solicit, and then harness the crowd to obtain data in a unique and innovative application of citizen science where the movements within the terrain are the desired output data (Figure 1). Figure 1: Example GPS tracks sourced from backcountry winter users in the Teton Pass area (Wyoming), from the 2014-15 winter season, where tracks in red represent those recorded as self-assessed experts (as per our survey), and where tracks in blue represent those recorded as self-assessed intermediates. All tracks shown were obtained under similar avalanche conditions. Statistical analysis of terrain metrics showed that the experts used steeper terrain than the

  16. Harnessing the power of mobile technologies for collaborating, crowdsourcing, and creating

    NASA Astrophysics Data System (ADS)

    Crompton, H.

    2015-12-01

    Today's digital technologies can have a powerful influence on teaching and learning. M-learning and u-learning in particular are changing pedagogical practice. Sub categories are rapidly emerging, such as context-aware ubiquitous learning, that involve students learning subject content while immersed in authentic and relevant surroundings. Learning cultures are a nebulous blend of traditions, values, beliefs, and rituals built up over time. For a long time, education has long been conceived as classroom-based and predominantly sedentary (Merchant, 2012). Recent mobile technologies are disrupting this culture in favor of learning that is contextualized, personalized, on demand, and ubiquitous (Crompton, 2013). 21st century students are a different breed than past generations (Prensky, 2001). These students have grown up in a time that has not only altered their perceptions and practices but modified the wiring of the brain through neuroplasticity (Crompton, 2012). Students now cognitively receive information quickly through non-linear methods (Gross, 2003, Oblinger & Oblinger, 2005). They think differently. They also seem to be attached to mobile devices 24/7, although the content of the lesson does not match what they seem to be doing on the mobile devices. This presentation will showcase how to get your students to harness the power of mobile devices for educational purposes. For example, students in your classes will be using devices to collaborate on activities with Google Forms, crowdsourcing the best class questions in Slido, and screencasting thoughts and ideas to share with others with Educreations. These are examples of free apps or Web 2.0 tools that can be used on all the major mobile platforms. Crompton, H. (2013). Mobile learning: New approach, new theory. In Z. L. Berge & L. Y. Muilenburg (Eds.), Handbook of mobile learning (pp. 47-57). Prensky, M. (2001). Digital natives, digital immigrants. Mcb University Press, 9(5). Oblinger, D., & Oblinger, J

  17. Determining Damping Trends from a Range of Cable Harness Assemblies on a Launch Vehicle Panel from Test Measurements

    NASA Technical Reports Server (NTRS)

    Smith, Andrew; Davis, R. Ben; LaVerde, Bruce; Jones, Douglas

    2012-01-01

    The team of authors at Marshall Space Flight Center (MSFC) has been investigating estimating techniques for the vibration response of launch vehicle panels excited by acoustics and/or aero-fluctuating pressures. Validation of the approaches used to estimate these environments based on ground tests of flight like hardware is of major importance to new vehicle programs. The team at MSFC has recently expanded upon the first series of ground test cases completed in December 2010. The follow on tests recently completed are intended to illustrate differences in damping that might be expected when cable harnesses are added to the configurations under test. This validation study examines the effect on vibroacoustic response resulting from the installation of cable bundles on a curved orthogrid panel. Of interest is the level of damping provided by the installation of the cable bundles and whether this damping could be potentially leveraged in launch vehicle design. The results of this test are compared with baseline acoustic response tests without cables. Damping estimates from the measured response data are made using a new software tool that employs a finite element model (FEM) of the panel in conjunction with advanced optimization techniques. This paper will report on the \\damping trend differences. observed from response measurements for several different configurations of cable harnesses. The data should assist vibroacoustics engineers to make more informed damping assumptions when calculating vibration response estimates when using model based analysis approach. Achieving conservative estimates that have more flight like accuracy is desired. The paper may also assist analysts in determining how ground test data may relate to expected flight response levels. Empirical response estimates may also need to be adjusted if the measured response used as an input to the study came from a test article without flight like cable harnesses.

  18. Harnessing the Risk-Related Data Supply Chain: An Information Architecture Approach to Enriching Human System Research and Operations Knowledge

    NASA Technical Reports Server (NTRS)

    Buquo, Lynn E.; Johnson-Throop, Kathy A.

    2011-01-01

    An Information Architecture facilitates the understanding and, hence, harnessing of the human system risk-related data supply chain which enhances the ability to securely collect, integrate, and share data assets that improve human system research and operations. By mapping the risk-related data flow from raw data to useable information and knowledge (think of it as a data supply chain), the Human Research Program (HRP) and Space Life Science Directorate (SLSD) are building an information architecture plan to leverage their existing, and often shared, IT infrastructure.

  19. Harness That S.O.B.: Distributing Remote Sensing Analysis in a Small Office/Business

    NASA Astrophysics Data System (ADS)

    Kramer, J.; Combe, J.; McCord, T. B.

    2009-12-01

    Researchers in a small office/business (SOB) operate with limited funding, equipment, and software availability. To mitigate these issues, we developed a distributed computing framework that: 1) leverages open source software to implement functionality otherwise reliant on proprietary software and 2) harnesses the unused power of (semi-)idle office computers with mixed operating systems (OSes). This abstract outlines some reasons for the effort, its conceptual basis and implementation, and provides brief speedup results. The Multiple-Endmember Linear Spectral Unmixing Model (MELSUM)1 processes remote-sensing (hyper-)spectral images. The algorithm is computationally expensive, sometimes taking a full week or more for a 1 million pixel/100 wavelength image. Analysis of pixels is independent, so a large benefit can be gained from parallel processing techniques. Job concurrency is limited by the number of active processing units. MELSUM was originally written in the Interactive Data Language (IDL). Despite its multi-threading capabilities, an IDL instance executes on a single machine, and so concurrency is limited by the machine's number of central processing units (CPUs). Network distribution can access more CPUs to provide a greater speedup, while also taking advantage of (often) underutilized extant equipment. appropriately integrating open source software magnifies the impact by avoiding the purchase of additional licenses. Our method of distribution breaks into four conceptual parts: 1) the top- or task-level user interface; 2) a mid-level program that manages hosts and jobs, called the distribution server; 3) a low-level executable for individual pixel calculations; and 4) a control program to synchronize sequential sub-tasks. Each part is a separate OS process, passing information via shell commands and/or temporary files. While the control and low-level executables are short-lived, the top-level program and distribution server run (at least) for the entirety of

  20. "Harnessing genomics to improve health in Africa" - an executive course to support genomics policy.

    PubMed

    Smith, Alyna C; Mugabe, John; Singer, Peter A; Daar, Abdallah S

    2005-01-24

    BACKGROUND: Africa in the twenty-first century is faced with a heavy burden of disease, combined with ill-equipped medical systems and underdeveloped technological capacity. A major challenge for the international community is to bring scientific and technological advances like genomics to bear on the health priorities of poorer countries. The New Partnership for Africa's Development has identified science and technology as a key platform for Africa's renewal. Recognizing the timeliness of this issue, the African Centre for Technology Studies and the University of Toronto Joint Centre for Bioethics co-organized a course on Genomics and Public Health Policy in Nairobi, Kenya, the first of a series of similar courses to take place in the developing world. This article presents the findings and recommendations that emerged from this process, recommendations which suggest that a regional approach to developing sound science and technology policies is the key to harnessing genome-related biotechnology to improve health and contribute to human development in Africa. METHODS: The objectives of the course were to familiarize participants with the current status and implications of genomics for health in Africa; to provide frameworks for analyzing and debating the policy and ethical questions; and to begin developing a network across different sectors by sharing perspectives and building relationships. To achieve these goals the course brought together a diverse group of stakeholders from academic research centres, the media, non-governmental, voluntary and legal organizations to stimulate multi-sectoral debate around issues of policy. Topics included scientific advances in genomics innovation systems and business models, international regulatory frameworks, as well as ethical and legal issues. RESULTS: Seven main recommendations emerged: establish a network for sustained dialogue among participants; identify champions among politicians; use the New Plan for African

  1. Three decades of harnessing the GPS data explosion for geophysics (Vening Meinesz Medal Lecture)

    NASA Astrophysics Data System (ADS)

    Blewitt, Geoffrey

    2015-04-01

    In this presentation, I attempt to convey the immensity of the task that faced the geodesy community three decades ago, and continues to challenge us, to harness all potentially valuable GPS data available in the world for geophysical science. It would be fair to see that three decades ago, we were struggling with controlled tests just to get GPS geodesy working, and had little time to imagine the flood of data today. Yet the geodesy community has succeeded in meeting this challenge. Today, for example, the Nevada Geodetic Laboratory produces and makes publicly available coordinate time series for over 12,000 geodetic GPS station around the globe with various data intervals, latencies, and reference frames. About 8,000 stations have their daily time series updated every week, with 4,000 being updated the next day with coordinates at daily and 5 minute intervals. About 2,000 stations have their time series updated every hour with coordinates at 5 minute intervals. I will show examples of how these time series are being used by NGL and many other scientists to study a wide variety of geophysical topics, including plate tectonics, earthquake modeling, seismic and tsunami hazard, volcanic deformation, water resources, mountain growth, terrestrial reference frame realization, glacial isostatic adjustment, ice sheet melting, sea level rise and coastal subsidence, and even fundamental physics, using GPS atomic clocks to probe the nature of dark matter in the universe. The explosion in GPS data has challenged us to invent new data processing algorithms and develop robust automation in order to keep up with the flood. This explosion has been exponential, and therefore it can be said that it is not a recent phenomena, but rather that it began in the earliest years of GPS geodesy, and has always posed a challenge to us. Over the course of my post-doctoral career starting in late 1985, I have had the good fortune to witness the key developments that have taken place since the

  2. "Harnessing genomics to improve health in Africa" – an executive course to support genomics policy

    PubMed Central

    Smith, Alyna C; Mugabe, John; Singer, Peter A; Daar, Abdallah S

    2005-01-01

    Background Africa in the twenty-first century is faced with a heavy burden of disease, combined with ill-equipped medical systems and underdeveloped technological capacity. A major challenge for the international community is to bring scientific and technological advances like genomics to bear on the health priorities of poorer countries. The New Partnership for Africa's Development has identified science and technology as a key platform for Africa's renewal. Recognizing the timeliness of this issue, the African Centre for Technology Studies and the University of Toronto Joint Centre for Bioethics co-organized a course on Genomics and Public Health Policy in Nairobi, Kenya, the first of a series of similar courses to take place in the developing world. This article presents the findings and recommendations that emerged from this process, recommendations which suggest that a regional approach to developing sound science and technology policies is the key to harnessing genome-related biotechnology to improve health and contribute to human development in Africa. Methods The objectives of the course were to familiarize participants with the current status and implications of genomics for health in Africa; to provide frameworks for analyzing and debating the policy and ethical questions; and to begin developing a network across different sectors by sharing perspectives and building relationships. To achieve these goals the course brought together a diverse group of stakeholders from academic research centres, the media, non-governmental, voluntary and legal organizations to stimulate multi-sectoral debate around issues of policy. Topics included scientific advances in genomics innovation systems and business models, international regulatory frameworks, as well as ethical and legal issues. Results Seven main recommendations emerged: establish a network for sustained dialogue among participants; identify champions among politicians; use the New Plan for African

  3. Origin and palaeoenvironmental significance of C25 and C27n-alk-1-enes in a 25,000-year lake-sedimentary record from equatorial East Africa

    NASA Astrophysics Data System (ADS)

    van Bree, L. G. J.; Rijpstra, W. I. C.; Cocquyt, C.; Al-Dhabi, N. A.; Verschuren, D.; Sinninghe Damsté, J. S.; de Leeuw, J. W.

    2014-11-01

    We studied the distribution of long-chain alkenes (n-C23 to n-C31) in well-dated sediments from Lake Challa, a deep crater lake near Mt. Kilimanjaro in equatorial East Africa, to reveal signatures of palaeo-environmental and palaeo-climatic changes affecting the production of these compounds during the last 25 kyr. The apolar fractions of organic sediment extracts dated to the last 16 kyr showed an unusual dominance of δ13C-depleted n-C25:1 and n-C27:1 alk-1-enes. These alkenes were not detected in soil and litter from near the shoreline and from the inner rim of the crater, pointing to an autochthonous, aquatic source. Analysis of suspended particulate matter indicated that the n-alk-1-enes are produced in the well-oxygenated upper 30 m of the water column, indicating a phytoplanktonic origin. Sedimenting particles collected monthly from December 2006 to November 2007 showed increased fluxes of n-alk-1-enes following the locally prominent short rain season in November-December. Green algae and/or cyanobacteria were identified as candidate sources of these alkenes. Production of the n-C25:1 and n-C27:1 alkenes in Lake Challa was much reduced during the Last Glacial Maximum and early late-glacial period, suggesting a temperature or CO2 effect on habitat suitability. We explored the potential of n-alk-1-ene accumulation rates, and of a derived Alkene Index [n-C27:1]/([n-C25:1] + [n-C27:1]), to record longer-term climatic changes. The Alkene Index record of Lake Challa over the past 25 kyr shows clear periodicity with a dominant frequency of ∼2.3 kyr, potentially indicative of monsoon variability directly or indirectly forced by variation in solar radiation.

  4. Identification of 5alpha-androst-1-ene-3beta,17beta-diol in the fat of Sus scrofa L.: a "nutritional supplement" not found previously in the food supply.

    PubMed

    McGregor, Stephen J; Erickson, Andrew J

    2003-09-01

    5alpha-Androst-1-ene-3beta,17beta-diol (1) was detected in extracts from fat of Sus scrofa L. (pig) by comparison with the commercially available synthetic compound, using gas chromatography-mass spectrometry. This observation is unprecedented because 1 is currently sold as a nutritional supplement, yet has not been previously reported as naturally occurring in the food supply. PMID:14510586

  5. Westphalen’s diol diacetate: 19(10→5)-abeo-5β-cholest-9-ene-3β,6β-diyl diacetate

    PubMed Central

    Ramírez Hernández, Johana; Sandoval-Ramírez, Jesús; Meza-Reyes, Socorro; Vega Báez, José Luis; Bernès, Sylvain

    2012-01-01

    The structure of the title steroid [alternative name: 3β,6β-diacet­oxy-5β-methyl-19-norcholest-9(10)-ene], C31H50O4, confirms the generally accepted mechanism for the rearrangement of a cholestan-5α-ol derivative reported a century ago by Westphalen. The methyl group at position 10 of the starting material migrates to position 5 in the steroidal nucleus, while a Δ9 bond is formed, as indicated by the C=C bond length of 1.347 (4) Å. The methyl transposition leaves the 5R configuration unchanged, with the methyl oriented towards the β face. During the rearrangement, the steroidal B ring experiences a conformational distortion from chair to envelope with the C atom at position 6 as the flap. In the title structure, the isopropyl group of the side chain is disordered over two positions, with occupancies of 0.733 (10) and 0.267 (10). The carbonyl O atom in the acetyl group at C3 is also disordered with an occupancy ratio of 0.62 (4):0.38 (4). PMID:23476170

  6. Photoinduced intramolecular charge transfer and photophysical characteristics of (2Z)-3-[4-(dimethylamino) phenyl]-2-(2-methylphenyl) prop-2-ene-nitrile (DPM) in different media

    NASA Astrophysics Data System (ADS)

    Asiri, Abdullah M.; El-Daly, Samy A.; Alamry, Khalid A.; Arshad, Muhammad Nadeem; Pannipara, Mehboobali

    2015-10-01

    A new fluorophore, (2Z)-3-[4-(dimethylamino) phenyl]-2-(2-methylphenyl) prop-2-ene-nitrile (DPM), was synthesized by knoevenagel condensation of 4-(dimethylamino) benzaldehyde and 2-methylbenzyl cyanide in ethanol using NaOH as base. The electronic absorption and emission characteristic of DPM was studied in different solvents. The X-ray crystallographic structure of DPM was also investigated. A crystalline solid of DPM gives a strong green emission at about 533 nm; these phenomena are important for the application of DPM dye in organic photo emitting diode. DPM exhibits a red shift in its emission spectrum as solvent polarity increases, indicating a large change in the dipole moment of dye molecule upon excitation due to intramolecular charge transfer in excited DPM*. The fluorescence quantum yield depends strongly on the properties of the solvents, which was attributed to positive and negative solvatokinetic effects. The DPM dye displays solubilization in cationic (CTAB) micelle and could be used as a probe to determine the critical micelle concentration (CMC) of CTAB.

  7. Poly[diaqua-[μ6-4,4'-(1,4-phenyl-ene)bis-(2,6-dimethyl-pyridine-3,5-dicarboxyl-ato)]dilead(II)].

    PubMed

    Zhu, Yi; Zhang, Ming-Xing; Yang, Shan-Shan; Xiao, Feng; Zhang, Xiao-Ping; Gao, Yuan-Yuan; Li, Bing-Jie; Huang, Kun-Lin

    2013-04-01

    The asymmetric unit of the title Pb-based coordination polymer, [Pb2(C24H16N2O8)(H2O)2] n , consists of one Pb(II) cation, half of a 4,4'-(1,4-phenyl-ene)bis-(2,6-dimethyl-pyridine-3,5-di-carb-oxyl-ate (L (4-)) ligand and one coordinating water mol-ecule. The centers of the benzene ring of the ligand and the four-membered Pb/O/Pb/O ring are located on centers of inversion. The Pb(II) ion is coordinated in form of a distorted polyhedron by seven O atoms from four separate L (4-) ligands and by one water O atom. The PbO7 polyhedra share O atoms, forming infinite zigzag [PbO4(H2O)] n chains along [100] that are bridged by L (4-) ligands, forming a two-dimensional coordination network parallel to (001). O-H⋯O hydrogen bonds involving the water mol-ecule are observed. PMID:23634022

  8. Developing Activity Localization Fluorescence Peptide Probe Using Thiol-Ene Click Reaction for Spatially Resolved Imaging of Caspase-8 in Live Cells.

    PubMed

    Liu, Wei; Liu, Si-Jia; Kuang, Yong-Qing; Luo, Feng-Yan; Jiang, Jian-Hui

    2016-08-01

    Small molecule probes suitable for high-resolution fluorescence imaging of enzyme activity pose a challenge in chemical biology. We developed a novel design of activity localization fluorescence (ALF) peptide probe, which enables spatially resolved, highly sensitive imaging of peptidase in live cells. The ALF probe was synthesized by a facile thiol-ene click reaction of a cysteine-appended peptide with an acryloylated fluorophore. Upon cleavage by peptidase, the probe undergoes a seven-membered intramolecular cyclization and releases the fluorophore with the excited-state intramolecular photon transfer (ESIPT) effect. A highly fluorescent, insoluble aggregate was formed around the enzyme, which facilitates high-sensitivity and high-resolution imaging. This design is demonstrated for detection of caspase-8 activation. The results show that our design allows easy, high-yield synthesis of the probe, and the probe affords high sensitivity for caspase-8 detection. Live cell imaging reveals that the probe is able to render highly localized and high-contrast fluorescence signal for caspase-8. Our design holds the potential as a generally applicable strategy for developing high-sensitivity and high-resolution imaging peptide probes in cell biology and diagnostics. PMID:27388162

  9. “Grafting to” of RAFTed Responsive Polymers to Glass Substrates by Thiol–Ene and Critical Comparison to Thiol–Gold Coupling

    PubMed Central

    2016-01-01

    Surface-grafted polymers have been widely applied to modulate biological interfaces and introduce additional functionality. Polymers derived from reversible addition–fragmentation transfer (RAFT) polymerization have a masked thiol at the ω-chain end providing an anchor point for conjugation and in particular displays high affinity for gold surfaces (both flat and particulate). In this work, we report the direct grafting of RAFTed polymers by a “thiol–ene click” (Michael addition) onto glass substrates rather than gold, which provides a more versatile surface for subsequent array-based applications but retains the simplicity. The immobilization of two thermoresponsive polymers are studied here, poly[oligo(ethylene glycol) methyl ether methacrylate] (pOEGMA) and poly(N-isopropylacrylamide) (pNIPAM). Using a range of surface analysis techniques the grafting efficiency was compared to thiol–gold and was quantitatively compared to the gold alternative using quartz crystal microbalance. It is shown that this method gives easy access to grafted polymer surfaces with pNIPAM resulting in significantly increased surface coverage compared to pOEGMA. The nonfouling (protein resistance) character of these surfaces is also demonstrated. PMID:27409356

  10. Mechanistic investigations into the enantioselective Conia-ene reaction catalyzed by cinchona-derived amino urea pre-catalysts and Cu(I).

    PubMed

    Sladojevich, Filippo; Fuentes de Arriba, Ángel L; Ortín, Irene; Yang, Ting; Ferrali, Alessandro; Paton, Robert S; Dixon, Darren J

    2013-10-11

    The enantioselective Conia-ene cyclization of alkyne-tethered β-ketoesters is efficiently catalyzed by the combination of cinchona-derived amino-urea pre-catalysts and copper(I) salts. The reaction scope is broad and a series of substrates can be efficiently cyclized with high yields and enantioselectivities. Herein, we present a detailed mechanistic study based on experimental considerations and quantum mechanical calculations. Several variables, such as the nature of the organic pre-catalyst and the metal-ion source, have been thoroughly investigated. Kinetic studies, as well as kinetic isotope effects and deuterium labeling experiments have been used to gain further insights into the mechanism and prove the cooperative nature of the catalytic system. Our studies suggest that the rate-limiting step for the reaction involves the β-ketoester deprotonation and that the active species responsible for the enantiodeterming step is monomeric in amino-urea pre-catalyst. Computational studies provide a quantitative understanding of the observed stereoinduction and identify hydrogen bonding from the urea group as a crucial factor in determining the observed enantioselectivity.

  11. Fast preparation of a highly efficient organic monolith via photo-initiated thiol-ene click polymerization for capillary liquid chromatography.

    PubMed

    Chen, Lianfang; Ou, Junjie; Liu, Zhongshan; Lin, Hui; Wang, Hongwei; Dong, Jing; Zou, Hanfa

    2015-05-15

    A novel organic monolith was firstly prepared in a UV-transparent fused-silica capillary by a single-step approach via photo-initiated thiol-ene click polymerization reaction of 1,2,4-trivinylcyclohexane (TVCH) and pentaerythriol tetra(3-mercaptopropionate) (4SH) within 10min. The effects of both composition of prepolymerization solution and polymerization time on the morphology and permeability of monolithic column were investigated in detail. Then, the optimal condition was acquired to fabricate a homogeneous and permeable organic monolith. The chemical groups of the monolithic column were confirmed by Fourier transform infrared spectroscopy (FT-IR). The SEM graphs showed the organic monolith possessed a uniform porous structure, which promotes the highest column efficiency of ∼133,000 plates per meter for alkylbenzenes at the linear velocity of 0.65mm/s in reversed-phase liquid chromatography. Finally, the organic monolithic column was further applied for separation of basic compounds, pesticides and EPA610, indicating satisfactory separation ability.

  12. Facile "one-pot" synthesis of poly(methacrylic acid)-based hybrid monolith via thiol-ene click reaction for hydrophilic interaction chromatography.

    PubMed

    Lv, Xumei; Tan, Wangming; Chen, Ye; Chen, Yingzhuang; Ma, Ming; Chen, Bo; Yao, Shouzhuo

    2016-07-01

    A novel sol-gel "one-pot" approach in tandem with a radical-mediated thiol-ene reaction for the synthesis of a methacrylic acid-based hybrid monolith was developed. The polymerization monomers, tetramethoxysilane (TMOS) and 3-mercaptopropyl trimethoxysilane (MPTS), were hydrolyzed in high-concentration methacrylic acid solution that also served as a hydrophilic functional monomer. The resulting solution was then mixed with initiator (2, 2'-azobis (2-methylpropionamide) dihydrochloride) and porogen (urea, polyethylene glycol 20,000) in a capillary column and polymerized in water bath. The column had a uniform porous structure and a good permeability. The evaluation of the monolith was performed by separation of small molecules including nucleosides, phenols, amides, bases and Triton X-100. The calibration curves for uridine, inosine, adenosine and cytidine were determined. All the calibration curves exhibited good linear regressions (R(2)≥0.995) within the test ranges of 0.5-40μg/mL for four nucleosides. Additionaliy, atypical hydrophilic mechanism was proved by elution order from low to high according to polarity retention time increased with increases in the content of the organic solvent in the mobile phase. Further studies indicated that hydrogen bond and electrostatic interactions existed between the polar analytes and the stationary phase. This was the mechanism of retention. The excellent separation of the BSA digest showed good hydrophility of the column and indicated the potential in separation of complex biological samples.

  13. Reaction of singlet-excited 2,3-diazabicyclo[2.2.2]oct-2-ene and tert-butoxyl radicals with aryl-substituted benzofuranones.

    PubMed

    Lundgren, Cecilia Vannesjö; Koner, Apurba L; Tinkl, Michael; Pischel, Uwe; Nau, Werner M

    2006-03-01

    5,7-Di-tert-butyl-3-aryl-3H-benzofuran-2-ones are lactones with potential antioxidant activity, owing to their abstractable benzylic C-H hydrogens. The fluorescence quenching of the azoalkane 2,3-diazabicyclo[2.2.2]oct-2-ene (DBO), an established probe for the hydrogen-donor propensity of chain-breaking antioxidants, was investigated for 16 aryl-substituted benzofuranone derivatives [m,m-(CF3)2, p-CN, m-CN, p-CF3, p-COOCH3, m-CF3, p-Cl, p-F, H, m-CH3, p-CH3, m,p-(CH3)2, p-OCH3, o-CH3, o-CF3, o,m-(CH3)2]. Analysis of the rate data in terms of a linear free energy relationship yielded a reaction constant of rho = +0.35. This implies that n,pi*-excited DBO acts as nucleophilic species. In contrast, hydrogen abstraction of tert-butoxyl radicals from the benzofuranones was accelerated by electron-donating substituents (rho = -0.23), in conformity with the electrophilic character of oxygen-centered alkoxyl radicals. Possible implications for the optimization of the hydrogen-donor propensity of antioxidants through structural variation are discussed.

  14. Facile "one-pot" synthesis of poly(methacrylic acid)-based hybrid monolith via thiol-ene click reaction for hydrophilic interaction chromatography.

    PubMed

    Lv, Xumei; Tan, Wangming; Chen, Ye; Chen, Yingzhuang; Ma, Ming; Chen, Bo; Yao, Shouzhuo

    2016-07-01

    A novel sol-gel "one-pot" approach in tandem with a radical-mediated thiol-ene reaction for the synthesis of a methacrylic acid-based hybrid monolith was developed. The polymerization monomers, tetramethoxysilane (TMOS) and 3-mercaptopropyl trimethoxysilane (MPTS), were hydrolyzed in high-concentration methacrylic acid solution that also served as a hydrophilic functional monomer. The resulting solution was then mixed with initiator (2, 2'-azobis (2-methylpropionamide) dihydrochloride) and porogen (urea, polyethylene glycol 20,000) in a capillary column and polymerized in water bath. The column had a uniform porous structure and a good permeability. The evaluation of the monolith was performed by separation of small molecules including nucleosides, phenols, amides, bases and Triton X-100. The calibration curves for uridine, inosine, adenosine and cytidine were determined. All the calibration curves exhibited good linear regressions (R(2)≥0.995) within the test ranges of 0.5-40μg/mL for four nucleosides. Additionaliy, atypical hydrophilic mechanism was proved by elution order from low to high according to polarity retention time increased with increases in the content of the organic solvent in the mobile phase. Further studies indicated that hydrogen bond and electrostatic interactions existed between the polar analytes and the stationary phase. This was the mechanism of retention. The excellent separation of the BSA digest showed good hydrophility of the column and indicated the potential in separation of complex biological samples. PMID:27264742

  15. Biocomposites from Natural Rubber: Synergistic Effects of Functionalized Cellulose Nanocrystals as Both Reinforcing and Cross-Linking Agents via Free-Radical Thiol-ene Chemistry.

    PubMed

    Parambath Kanoth, Bipinbal; Claudino, Mauro; Johansson, Mats; Berglund, Lars A; Zhou, Qi

    2015-08-01

    Natural rubber/cellulose nanocrystals (NR/CNCs) form true biocomposites from renewable resources and are demonstrated to show significantly improved thermo-mechanical properties and reduced stress-softening. The nanocomposites were prepared from chemically functionalized CNCs bearing thiols. CNCs served as both reinforcing and cross-linking agents in the NR matrix, and the study was designed to prove the cross-linking function of modified CNCs. CNCs were prepared from cotton, and the cross-linkable mercapto-groups were introduced onto the surface of CNCs by esterification. Nanocomposite films were prepared by dispersing the modified CNCs (m-CNCs) in NR matrix by solution casting. The cross-links at the filler-matrix (m-CNCs-NR) interface were generated by photochemically initiated thiol-ene reactions as monitored by real-time FTIR analysis. The synergistic effects of reinforcement and chemical cross-linking at the m-CNCs-NR interface on structure, thermo-mechanical, and stress-softening behavior were investigated. Methods included field emission scanning electron microscopy (FE-SEM), swelling tests, dynamic mechanical analysis, and tensile tests. Compared to biocomposites from NR with unmodified CNCs, the NR/m-CNCs nanocomposites showed 2.4-fold increase in tensile strength, 1.6-fold increase in strain-to-failure, and 2.9-fold increase in work-of-fracture at 10 wt % of m-CNCs in NR. PMID:26151647

  16. Thiol-ene Michael-type formation of gelatin/poly(ethylene glycol) biomatrices for three-dimensional mesenchymal stromal/stem cell administration to cutaneous wounds

    PubMed Central

    Xu, Kedi; Cantu, David Antonio; Fu, Yao; Kim, Jaehyup; Zheng, Xiaoxiang; Hematti, Peiman; Kao, W. John

    2013-01-01

    Mesenchymal stromal/stem cells (MSCs) are considered promising cellular therapeutics in the fields of tissue engineering and regenerative medicine. MSCs secrete high concentrations of immunomodulatory cytokines and growth factors, which exert paracrine effects on infiltrating immune and resident cells of the wound microenvironment that could favorably promote healing after acute injury. However, better spatial delivery and improved retention at the site of injury are two factors that could improve the clinical application of MSCs. In this study, we utilized thiol-ene Michael-type addition for rapid encapsulation of MSCs within a gelatin/poly(ethylene glycol) biomatrix; this biomatrix was also applied as a provisional dressing to full-thickness wounds in Sprague-Dawley rats. The three-way interaction of MSCs, gelatin/poly(ethylene glycol) biomatrices, and host immune cells and adjacent resident cells of the wound microenvironment favorably modulated wound progression and host response. In this model we observed attenuated immune cell infiltration, lack of foreign giant cell (FBGC) formation, accelerated wound closure and re-epithelialization, as well as enhanced neovascularization and granulation tissue formation by 7 days. The MSC-entrapped gelatin/poly(ethylene glycol) biomatrix localized the presentation of MSCs adjacent to the wound microenvironment and thus, mediated early resolution of inflammatory events and facilitated proliferative phases in wound healing. PMID:23811217

  17. Engineering an anaerobic metabolic regime in Pseudomonas putida KT2440 for the anoxic biodegradation of 1,3-dichloroprop-1-ene.

    PubMed

    Nikel, Pablo I; de Lorenzo, Víctor

    2013-01-01

    Pseudomonas putida KT2440, a microbial cell factory of reference for industrial whole-cell biocatalysis, is unable to support biochemical reactions that occur under anoxic conditions, limiting its utility for a large number of relevant biotransformations. Unlike (facultative) anaerobes, P. putida resorts to NADH oxidation via an oxic respiratory chain and completely lacks a true fermentation metabolism. Therefore, it cannot achieve the correct balances of energy and redox couples (i.e., ATP/ADP and NADH/NAD(+)) that are required to sustain an O(2)-free lifestyle. To overcome this state of affairs, the acetate kinase (ackA) gene of the facultative anaerobe Escherichia coli and the pyruvate decarboxylase (pdc) and alcohol dehydrogenase II (adhB) genes of the aerotolerant Zymomonas mobilis were knocked-in to a wild-type P. putida strain. Biochemical and genetic assays showed that conditional expression of the entire enzyme set allowed the engineered bacteria to adopt an anoxic regime that maintained considerable metabolic activity. The resulting strain was exploited as a host for the heterologous expression of a 1,3-dichloroprop-1-ene degradation pathway recruited from Pseudomonas pavonaceae 170, enabling the recombinants to degrade this recalcitrant chlorinated compound anoxically. These results underscore the value of P. putida as a versatile agent for biotransformations able to function at progressively lower redox statuses.

  18. Thiol-ene Michael-type formation of gelatin/poly(ethylene glycol) biomatrices for three-dimensional mesenchymal stromal/stem cell administration to cutaneous wounds.

    PubMed

    Xu, Kedi; Cantu, David Antonio; Fu, Yao; Kim, Jaehyup; Zheng, Xiaoxiang; Hematti, Peiman; Kao, W John

    2013-11-01

    Mesenchymal stromal/stem cells (MSCs) are considered promising cellular therapeutics in the fields of tissue engineering and regenerative medicine. MSCs secrete high concentrations of immunomodulatory cytokines and growth factors, which exert paracrine effects on infiltrating immune and resident cells in the wound microenvironment that could favorably promote healing after acute injury. However, better spatial delivery and improved retention at the site of injury are two factors that could improve the clinical application of MSCs. In this study, we utilized thiol-ene Michael-type addition for rapid encapsulation of MSCs within a gelatin/poly(ethylene glycol) biomatrix. This biomatrix was also applied as a provisional dressing to full thickness wounds in Sprague-Dawley rats. The three-way interaction of MSCs, gelatin/poly(ethylene glycol) biomatrices, and host immune cells and adjacent resident cells in the wound microenvironment favorably modulated wound progression and host response. In this model we observed attenuated immune cell infiltration, lack of foreign giant cell (FBGC) formation, accelerated wound closure and re-epithelialization, as well as enhanced neovascularization and granulation tissue formation by 7 days. The MSC entrapped in the gelatin/poly(ethylene glycol) biomatrix localized cell presentation adjacent to the wound microenvironment and thus mediated the early resolution of inflammatory events and facilitated the proliferative phases in wound healing. PMID:23811217

  19. Stereoselective rhodium-catalysed [2+2+2] cycloaddition of linear allene-ene/yne-allene substrates: reactivity and theoretical mechanistic studies.

    PubMed

    Haraburda, Ewelina; Torres, Óscar; Parella, Teodor; Solà, Miquel; Pla-Quintana, Anna

    2014-04-22

    Allene-ene-allene (2 and 5) and allene-yne-allene (3 and 7) N-tosyl and O-linked substrates were satisfactorily synthesised. The [2+2+2] cycloaddition reaction catalysed by the Wilkinson catalyst [RhCl(PPh3 )3 ] was evaluated. Substrates 2 and 5, which bear a double bond in the central position, gave a tricyclic structure in a reaction in which four contiguous stereogenic centres were formed as a single diastereomer. The reaction of substrates 3 and 7, which bear a triple bond in the central position, gave a tricyclic structure with a cyclohexenic ring core, again in a diastereoselective manner. All cycloadducts were formed by a regioselective reaction of the inner allene double bond and, therefore, feature an exocyclic diene motif. A Diels-Alder reaction on N-tosyl linked cycloadducts 8 and 10 allowed pentacyclic scaffolds to be diastereoselectively constructed. The reactivity of the allenes on [2+2+2] cycloaddition reactions was studied for the first time by density functional theory calculations. This mechanistic study rationalizes the order in which the unsaturations take part in the catalytic cycle, the reactivity of the two double bonds of the allene towards the [2+2+2] cycloaddition reaction, and the diastereoselectivity of the reaction.

  20. Mechanistic investigations into the enantioselective Conia-ene reaction catalyzed by cinchona-derived amino urea pre-catalysts and Cu(I).

    PubMed

    Sladojevich, Filippo; Fuentes de Arriba, Ángel L; Ortín, Irene; Yang, Ting; Ferrali, Alessandro; Paton, Robert S; Dixon, Darren J

    2013-10-11

    The enantioselective Conia-ene cyclization of alkyne-tethered β-ketoesters is efficiently catalyzed by the combination of cinchona-derived amino-urea pre-catalysts and copper(I) salts. The reaction scope is broad and a series of substrates can be efficiently cyclized with high yields and enantioselectivities. Herein, we present a detailed mechanistic study based on experimental considerations and quantum mechanical calculations. Several variables, such as the nature of the organic pre-catalyst and the metal-ion source, have been thoroughly investigated. Kinetic studies, as well as kinetic isotope effects and deuterium labeling experiments have been used to gain further insights into the mechanism and prove the cooperative nature of the catalytic system. Our studies suggest that the rate-limiting step for the reaction involves the β-ketoester deprotonation and that the active species responsible for the enantiodeterming step is monomeric in amino-urea pre-catalyst. Computational studies provide a quantitative understanding of the observed stereoinduction and identify hydrogen bonding from the urea group as a crucial factor in determining the observed enantioselectivity. PMID:24009075

  1. C(8) substituted 1-azabicyclo[3.3.1]non-3-enes and C(8) substituted 1-azabicyclo[3.3.1]nonan-4-ones: novel muscarinic receptor antagonists.

    PubMed

    Kim, Myoung Goo; Bodor, Erik T; Wang, Chen; Harden, T Kendall; Kohn, Harold

    2003-05-22

    Expedient syntheses of C(8) substituted 1-azabicyclo[3.3.1]non-3-enes and C(8) substituted 1-azabicyclo[3.3.1]nonan-4-ones are reported to begin with 2,5-disubstituted pyridines. Catalytic reduction of the pyridine to the piperidine followed by treatment with ethyl acrylate and Dieckmann cyclization gave diastereomeric mixtures of C(8) substituted 3-ethoxycarbonyl-4-hydroxy-1-azabicyclo[3.3.1]non-3-enes, which were separable by chromatography. We found that the catalytic reduction (PtO2, H2) procedure provided the cis-substituted piperidine but that pyridine reduction was accompanied by competitive cleavage of the C(2) pyridyl substituent. Accordingly, an alternative route was devised that afforded a diastereomeric mixture of the cis- and trans-2,5-disubstituted piperidine. Treatment of the substituted pyridine with m-CPBA gave the pyridine N-oxide, which was reduced to the piperidine by sequential reduction with ammonium formate in the presence of Pd-C followed by NaBH3CN. Addition of ethyl acrylate completed the synthesis of the substituted piperidine. The overall four-step reaction gave higher yields (57%) than the two-step procedure (13%) with little cleavage of the C(2) pyridyl substituent. Acid decarboxylation of the bicyclo[3.3.1]non-3-enes provided the C(8) substituted 1-azabicyclo[3.3.1]nonan-4-ones. Structural studies revealed diagnostic 13C NMR signals that permit assignment of the orientation of the C(8) substituent. Pharmacological investigations documented that 3-ethoxycarbonyl-4-hydroxy-1-azabicyclo[3.3.1]non-3-enes efficiently bind to the human M1-M5 muscarinic receptors and function as antagonists. We observed that exo-8-benzyloxymethyl-3-ethoxycarbonyl-4-hydroxy-1-azabicyclo[3.3.1]non-3-ene (3) displayed the highest affinity, exhibiting Ki values at all five muscarinic receptors that were approximately 10-50 times lower than carbachol and approximately 30-230 times lower than arecoline. Receptor selectivity was observed for 3. Compound 3 contained

  2. Harnessing entropic and enthalpic contributions to create a negative tone chemically amplified molecular resist for high-resolution lithography

    NASA Astrophysics Data System (ADS)

    Kulshreshtha, Prashant K.; Maruyama, Ken; Kiani, Sara; Blackwell, James; Olynick, Deirdre L.; Ashby, Paul D.

    2014-08-01

    Here we present a new resist design concept. By adding dilute cross-linkers to a chemically amplified molecular resist, we synergize entropic and enthalpic contributions to dissolution by harnessing both changes to molecular weight and changes in intermolecular bonding to create a system that outperforms resists that emphasize one contribution over the other. We study patterning performance, resist modulus, solubility kinetics and material redistribution as a function of cross-linker concentration. Cross-linking varies from dilute oligomerization to creating a highly networked system. The addition of small amounts of cross-linker improves resist performance by reducing material diffusion and redistribution during development and stiffening the features to avoid pattern collapse. The new dilute cross-linking system achieves the highest resolution of a sensitive molecular glass resist at 20 nm half-pitch and line-edge roughness (LER) of 4.3 nm and can inform new resist design towards patterned feature control at the molecular level.

  3. Which one is preferred: Myers-Saito cyclization of ene-yne-allene or Garratt-Braverman cyclization of conjugated bisallenic sulfone? A theoretical and experimental study.

    PubMed

    Basak, Amit; Das, Sanket; Mallick, Dibyendu; Jemmis, Eluvathingal D

    2009-11-01

    A competitive scenario between Myers-Saito (MS) and Garratt-Braverman (GB) cyclization has been created in a molecule. High-level computations indicate a preference for GB over MS cyclization. The activation energies for the rate-determining steps of the GB and MS cyclizations were found to be the same (24.4 kcal/mol) at the B3LYP/6-31G* level of theory; thus, from the kinetic point of view, both reactions are feasible. However, the main biradical intermediate GB2 of the GB reaction is 6.2 kcal/mol lower in energy than the biradical MS2, which is the main intermediate of MS reaction, so GB cyclization is thermodynamically favored over MS cyclization. To verify the prediction by computational techniques, bisenediynyl sulfones 1-4 and bisenediynyl sulfoxide 17 were synthesized. Under basic conditions, these molecules isomerized to a system possessing both the ene-yne-allene and the bisallenic sulfone. The isolation of only one product, identified as the corresponding naphthalene- or benzene-fused sulfone 8-11, indicated the occurrence of GB cyclization as the sole reaction pathway. No product corresponding to the MS cyclization pathway could be isolated. Though the theoretical prediction showed a preference for the GB pathway over the MS pathway, the exclusive preference for GB over MS cyclization is very striking. Further analysis showed that the intramolecular self-quenching nature of the GB pathway may play an important role in the complete preference for this reaction. Apart from the mechanistic studies, these sulfones showed DNA cleavage activity that had an inverse relation with the reactivity order. Our findings are important for the design of artificial DNA-cleaving agents.

  4. Design of peptide substrates for nanosecond time-resolved fluorescence assays of proteases: 2,3-diazabicyclo[2.2.2]oct-2-ene as a noninvasive fluorophore.

    PubMed

    Hennig, Andreas; Florea, Mara; Roth, Doris; Enderle, Thilo; Nau, Werner M

    2007-01-15

    Fluorescence protease assays were investigated with peptide substrates containing a 2,3-diazabicyclo[2.2.2]oct-2-ene-labeled asparagine (Dbo) as a fluorescent amino acid. The special characteristic of the fluorophore Dbo is its exceedingly long fluorescence lifetime (ca. 300 ns in water under air), which allows the use of nanosecond time-resolved fluorescence (Nano-TRF) detection to efficiently suppress shorter-lived background emission. In addition, the natural amino acids tryptophan and tyrosine can be employed as intramolecular fluorescence quenchers, which facilitates substrate design. Fourteen synthetic peptide substrates (composed of 2-19 amino acids) and five enzymes (trypsin, pepsin, carboxypeptidase A, leucine aminopeptidase, and chymotrypsin) were investigated and, in all 28 examined combinations, enzymatic activity was detected by monitoring the increase in steady state fluorescence with time and determining the reaction rates as kcat/Km values, which ranged from 0.2 to 80x10(6) M-1 min-1. The results suggest an excellent compatibility of the very small and hydrophilic fluorescent probe Dbo with solid-phase peptide synthesis and the investigated proteases. For all 14 peptides the fluorescence lifetimes before and after enzymatic cleavage were measured and Nano-TRF measurements were performed in 384-well microplates. The fluorescence lifetimes of the different peptides provide the basis for the rational design of Dbo-based fluorescent substrates for protease assays. Measurements in Nano-TRF mode revealed, in addition to efficient suppression of background fluorescence, an increased differentiation between cleaved and uncleaved substrate. The Dbo-based assays can be adapted for high-throughput screening.

  5. Refractive index effects on the oscillator strength and radiative decay rate of 2,3-diazabicyclo[2.2.2]oct-2-ene.

    PubMed

    Mohanty, Jyotirmayee; Nau, Werner M

    2004-01-01

    The photophysical properties of 2,3-diazabicyclo[2.2.2]oct-2-ene (DBO) were determined in 15 solvents, two supramolecular hosts (cucurbit[7]uril and beta-cyclodextrin) as well as in the gas phase. The oscillator strength and radiative decay rate of DBO as a function of refractive index i.e. polarizability have been analyzed. The oscillator strength increases by a factor of 10 upon going from the gas phase to the most polarizable carbon disulfide, while the corresponding radiative decay rates increase by a factor of 40. There is a good empirical correlation between the oscillator strength of the weakly allowed n,pi* transition of DBO and the reciprocal bulk polarizability, which can be employed to assess the polarizability of unknown microheterogeneous environments. A satisfactory correlation between the radiative decay rate and the square of the refractive index is also found, as previously documented for chromophores with allowed transitions. However, the correlation improves significantly when the oscillator strength is included in the correlation, which demonstrates the importance of this factor in the Strickler-Berg equation for chromophores with forbidden or weakly allowed transitions, for which the oscillator strength may be strongly solvent dependent. The radiative decay rate of DBO in two supramolecular assemblies has been determined, confirming the very low polarizability inside the cucurbituril cavity, in between perfluorohexane and the gas phase. The fluorescence quantum yield of DBO in the gas phase has been remeasured (5.1 +/- 0.5%) and was found to fall one full order of magnitude below a previously reported value.

  6. The new low calcemic vitamin D analog 22-ene-25-oxa-vitamin D prominently ameliorates T helper cell type 1-mediated colitis in mice.

    PubMed

    Daniel, Carolin; Radeke, Heinfried H; Sartory, Nico A; Zahn, Nadine; Zuegel, Ulrich; Steinmeyer, Andreas; Stein, Jürgen

    2006-11-01

    In addition to its well defined role as a key regulator of calcium and bone metabolism, 1,25-dihydroxyvitamin D(3) (calcitriol) has been established as a potent modulator of immune cell function. Still, because of the hypercalcemic toxicity occurring after systemic application of the parent compound, its clinical application as an immunosuppressant has been hampered. Recently, we described 22-ene-25-oxa-vitamin D (ZK156979) as a representative of a novel class of low calcemic vitamin D analogs with well preserved immunosuppressive activity in vitro. Here, in vivo colitis was induced by applying a rectal enema of 2,4,6-trinitrobenzene sulfonic acid (TNBS) to male BALB/c mice, and calcitriol (0.2 microg/kg) or ZK156979 (0.1-2.0 microg/kg) was given i.p. from days 0 to 3 or 3 to 5. Body mass and clinical activity score of colitis were recorded daily. Colon tissue was analyzed macroscopically and microscopically, myeloperoxidase activity and cytokine levels [tumor necrosis factor (TNF)-alpha, interferon (IFN)-gamma, interleukin (IL)-10, and IL-4] were determined by enzyme-linked immunosorbent assay, and T-box transcription factor (T-bet) expression was determined by immunoblot analysis. We found that treatment with ZK156979 clearly reduced the severity of TNBS-induced colitis without exhibiting calcemic effects. Both early and late treatment abrogated body weight loss, diarrhea, and macroscopic intestinal inflammation with a potency comparable with that of calcitriol. The therapeutic effect of ZK156979 was accompanied by a down-regulation of myeloperoxidase activity, TNF-alpha, IFN-gamma, and T-bet expression decreased, whereas local tissue IL-10 and IL-4 protein levels increased. To conclude, our data provide the first clear evidence that ZK156979 exhibits a beneficial prophylactic as well as therapeutic profile in T helper cell type 1-like experimental colitis, offering new therapeutic options for the treatment of human inflammatory bowel diseases.

  7. Occurrence of (Z)-3,4-Dideoxyglucoson-3-ene in Different Types of Beer and Malt Beer as a Result of 3-Deoxyhexosone Interconversion.

    PubMed

    Hellwig, Michael; Nobis, Arndt; Witte, Sophia; Henle, Thomas

    2016-04-01

    In beer, 3-deoxyglucosone (3-DG) and 3-deoxygalactosone (3-DGal) are important sugar degradation products, but little is known about the relevance of the interconversion reaction between these compounds in different types of beer. In the present study, 3-DG was quantitated at concentrations of 12.9-52.7 mg/L and 3-DGal at concentrations of 6.0-26.4 mg/L in different types of beer (pilsner, wheat, bock, dark, and alcohol-free beers). The concentrations in malt beer tended to be higher. Largely overlapping concentration ranges precluded a classification of beers by their 3-deoxyglycosone contents. 3,4-Dideoxyglucoson-3-ene (3,4-DGE) was identified as an important intermediate and quantitated in beer and malt beer for the first time. The E and Z isomers of the corresponding quinoxaline were synthesized by a new synthetic approach and isolated by semipreparative HPLC. An assay was developed for quantitation of (E)- and (Z)-3,4-DGE by HPLC-MS/MS, and the Z isomer was determined at concentrations of 0.3-1.7 mg/L in beer and 0.5-4.8 mg/L in malt beer samples. The E isomer was shown to be of little importance. Concentrations of 5-hydroxymethylfurfural (HMF) were twice as high as those of (Z)-3,4-DGE in beer samples (0.4-3.7 mg/L) but much higher in malt beer samples (1.6-336 mg/L). PMID:26984557

  8. Microbes at Surface-Air Interfaces: The Metabolic Harnessing of Relative Humidity, Surface Hygroscopicity, and Oligotrophy for Resilience

    PubMed Central

    Stone, Wendy; Kroukamp, Otini; Korber, Darren R.; McKelvie, Jennifer; Wolfaardt, Gideon M.

    2016-01-01

    The human environment is predominantly not aqueous, and microbes are ubiquitous at the surface-air interfaces with which we interact. Yet microbial studies at surface-air interfaces are largely survival-oriented, whilst microbial metabolism has overwhelmingly been investigated from the perspective of liquid saturation. This study explored microbial survival and metabolism under desiccation, particularly the influence of relative humidity (RH), surface hygroscopicity, and nutrient availability on the interchange between these two phenomena. The combination of a hygroscopic matrix (i.e., clay or 4,000 MW polyethylene glycol) and high RH resulted in persistent measurable microbial metabolism during desiccation. In contrast, no microbial metabolism was detected at (a) hygroscopic interfaces at low RH, and (b) less hygroscopic interfaces (i.e., sand and plastic/glass) at high or low RH. Cell survival was conversely inhibited at high RH and promoted at low RH, irrespective of surface hygroscopicity. Based on this demonstration of metabolic persistence and survival inhibition at high RH, it was proposed that biofilm metabolic rates might inversely influence whole-biofilm resilience, with ‘resilience’ defined in this study as a biofilm’s capacity to recover from desiccation. The concept of whole-biofilm resilience being promoted by oligotrophy was supported in desiccation-tolerant Arthrobacter spp. biofilms, but not in desiccation-sensitive Pseudomonas aeruginosa biofilms. The ability of microbes to interact with surfaces to harness water vapor during desiccation was demonstrated, and potentially to harness oligotrophy (the most ubiquitous natural condition facing microbes) for adaptation to desiccation. PMID:27746774

  9. Design of thiol–ene photoclick hydrogels using facile techniques for cell culture applications† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c4bm00187g Click here for additional data file.

    PubMed Central

    Sawicki, Lisa A.

    2014-01-01

    Thiol–ene ‘click’ chemistries have been widely used in biomaterials applications, including drug delivery, tissue engineering, and controlled cell culture, owing to their rapid, cytocompatible, and often orthogonal reactivity. In particular, hydrogel-based biomaterials formed by photoinitiated thiol–ene reactions afford spatiotemporal control over the biochemical and biomechanical properties of the network for creating synthetic materials that mimic the extracellular matrix or enable controlled drug release. However, the use of charged peptides functionalized with cysteines, which can form disulfides prior to reaction, and vinyl monomers that require multistep syntheses and contain ester bonds, may lead to undesired inhomogeneity or degradation under cell culture conditions. Here, we designed a thiol–ene hydrogel formed by the reaction of allyloxycarbonyl-functionalized peptides and thiol-functionalized poly(ethylene glycol). Hydrogels were polymerized by free radical initiation under cytocompatible doses of long wavelength ultraviolet light in the presence of water-soluble photoinitiators (lithium acylphosphinate, LAP, and 2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methyl-1-propanone, Irgacure 2959). Mechanical properties of these hydrogels were controlled by varying the monomer concentration to mimic a range of soft tissue environments, and hydrogel stability in cell culture medium was observed over weeks. Patterns of biochemical cues were created within the hydrogels post-formation and confirmed through the incorporation of fluorescently-labeled peptides and Ellman's assay to detect free thiols. Human mesenchymal stem cells remained viable after encapsulation and subsequent photopatterning, demonstrating the utility of the monomers and hydrogels for three-dimensional cell culture. This facile approach enables the formation and characterization of hydrogels with well-defined, spatially-specific properties and expands the suite of monomers available for

  10. Harness: Heterogeneous Adaptable Reconfigurable Networked Systems -- U.S. Department of Energy Grant DE-FG02-99ER25379 Final Project Report

    SciTech Connect

    Vaidy Sunderam

    2003-07-02

    Issues in reconfigurability and adaptability in heterogeneous distributed systems for high-performance computing are the focus of the work funded by this grant. Our efforts are part of an ongoing research project in metacomputing and are a follow on to the DOE funded PVM system that has witnessed over a decade of use at numerous institutions worldwide. The current project, termed Harness, investigates novel methodologies and tools for distributed metacomputing, focusing on dynamically reconfigurable software frameworks. During the first phase, we defined the metacomputing architecture embodied in Harness and developed prototype subsystems as proof of concept exercises. Subsequently, we designed and developed a complete software framework manifesting the Harness architecture, and also developed several tools and subsystems that demonstrated the viability and effectiveness of our proposed model for next generation metacomputing. We then used this substrate to emulate multiple programming environments on Harness, and conducted performance evaluation and tuning exercises. The main research results from these efforts include the establishment of software metacomputing systems as viable and cost-effective alternatives to MPPs; the demonstration of dynamic and reconfigurable platforms as effective methods of tailoring parallel computing environments; the development of methodologies to construct plugin modules for component-based distributed systems; contributions to performance modeling and optimization in emulated software environments; and software architectures for multi- and mixed-paradigm parallel distributed computing. Details and specifics on these and other results have been reported in numerous publications, and are manifested in software systems, all of which may be accessed at or via the website http://www.mathcs.emory.edu/harness/

  11. Ring-closing metathesis-based synthesis of (3R,4R,5S)-4-acetylamino-5-amino-3-hydroxy- cyclohex-1-ene-carboxylic acid ethyl ester: a functionalized cycloalkene skeleton of GS4104.

    PubMed

    Cong, Xin; Yao, Zhu-Jun

    2006-07-01

    (3R,4R,5S)-4-Acetylamino-5-amino-3-hydroxy-cyclohex-1-ene-carboxylic acid ethyl ester, a functionalized cyclohexene skeleton of GS4104, was diastereoselectively synthesized. A major advantage of this synthesis is the use of readily available L-serine to replace frequently used (-)-shikimic acid or (-)-quinic acid as the starting material. Ring-closing metathesis and diastereoselective Grignard reactions successfully served as the key steps. Absolute configurations of the key intermediates were confirmed by corresponding two-dimensional NMR studies.

  12. rac-12,14-Dicyclo-propyl-5,8,13,18,21-penta-oxapenta-cyclo-[13.8.0.0.0.0]tricosa-1(15),2(11),3,9(10),16,22(23)-hexa-ene.

    PubMed

    Tafeenko, Viktor A; Aslanov, Leonid A; Puretskiy, Nikolay A; Fedotov, Aleksander N; Mochalov, Sergei S

    2011-05-01

    The mol-ecule of the title compound, C(24)H(24)O(5), has crystallographic twofold symmetry, with the central O atom lying on the rotation axis. The dihedral angle between the best planes of the benzene rings fused to the oxepine fragment is 38.5 (1)°. The dioxine ring adopts a twist form with the ethyl-ene group C atoms deviating by 0.472 (5) and -0.248 (6) Å from the plane defined by the remaining ring atoms. PMID:21754483

  13. Composite materials with improved properties in compression. Appendix 1. Cyclopropanation of poly(1-methyl-1-phenyl-1-sila-cis-pent-3-ene). Synthesis and characterization of poly(1-methyl-3,4-methylene-1-phenyl-1-sila-cis-pent-3-ene). Interim report

    SciTech Connect

    Liao, X.; Lee, H.S.; Weber, W.P.

    1990-05-09

    There is considerable interest in the chemical modification of polymers. While it has been possible to stereo specifically quantitatively add dichlorocarbene to the C-C double bonds of 1,4-polybutadiene as well as to those of poly(1,1-dimethyl-1-sila-cis-pent-3-ene) (II), it has not been possible to achieve complete cyclopropanation of the C-C double bonds of either 1,4-polybutadiene or II by use of the Simmons-Smith reaction. NMR spectra were obtained either on a Brucker AM-360 or an IBM Brucker WP-270-SY spectrometer operating in the Fourier transform mode. Five to ten percent weight/volume solutions of polymers C12C-I and H2C-I in chloroform-d were used to obtain NMR spectra, whereas ten to fifteen percent solutions were utilized for {sup 13}C and {sup 29}Si NMR spectra. BC NMR spectra were run with broad band proton decoupling. Chloroform was used as an internal standard for 1H and 13C NMR spectra.

  14. Inspiration in the harness of daily labor. Darwin, botany, and the triumph of evolution, 1859-1868.

    PubMed

    Bellon, Richard

    2011-09-01

    Charles Darwin hoped that a large body of working naturalists would embrace evolution after the Origin of Species appeared in late 1859. He was disappointed. His evolutionary ideas at first made painfully little progress in the scientific community. But by 1863 the tide had turned dramatically, and within five years evolution became scientific orthodoxy in Britain. The Origin's reception followed this peculiar trajectory because Darwin had not initially tied its theory to productive original scientific investigation, which left him vulnerable to charges of reckless speculation. The debate changed with his successful application of evolution to original problems, most notably orchid fertilization, the subject of a well-received book in 1862. Most of Darwin's colleagues found the argument of the Origin convincing when they realized that it functioned productively in the day-to-day work of science-and not before. The conceptual force of the Origin, however outwardly persuasive, acquired full scientific legitimacy only when placed "in the harness of daily labour". PMID:22073768

  15. An isotropic suspension system for a biaxial accelerometer using electroplated thick metal with a HAR SU-8 mold

    NASA Astrophysics Data System (ADS)

    Lee, Jin Seung; Lee, Seung S.

    2008-02-01

    In this paper, a novel approach is developed to design an isotropic suspension system using thick metal freestanding micro-structures combining bulk micro-machining with electroplating based on a HAR SU-8 mold. An omega-shape isotropic suspension system composed of circular curved beams that have free switching of imaginary boundary conditions is proposed. This novel isotropic suspension design is not affected by geometric dimensional parameters and always achieves matching stiffness along the principle axes of elasticity. Using the finite element method, the isotropic suspension system was compared with an S-shaped meandering suspension system. In order to realize the suggested isotropic suspension system, a cost-effective fabrication process using electroplating with the SU-8 mold was developed to avoid expensive equipment and materials such as deep reactive-ion etching (DRIE) or a silicon-on-insulator (SOI) wafer. The fabricated isotropic suspension system was verified by electromagnetic actuation experiments. Finally, a biaxial accelerometer with isotropic suspension system was realized and tested using a vibration generator system. The proposed isotropic suspension system and the modified surface micro-machining technique based on electroplating with an SU-8 mold can contribute towards minimizing the system size, simplifying the system configuration, reducing the system price of and facilitating mass production of various types of low-cost sensors and actuators.

  16. Labeling viral envelope lipids with quantum dots by harnessing the biotinylated lipid-self-inserted cellular membrane.

    PubMed

    Lv, Cheng; Lin, Yi; Liu, An-An; Hong, Zheng-Yuan; Wen, Li; Zhang, Zhenfeng; Zhang, Zhi-Ling; Wang, Hanzhong; Pang, Dai-Wen

    2016-11-01

    Highly efficient labeling of viruses with quantum dots (QDs) is the prerequisite for the long-term tracking of virus invasion at the single virus level to reveal mechanisms of virus infection. As one of the structural components of viruses, viral envelope lipids are hard to be labeled with QDs due to the lack of efficient methods to modify viral envelope lipids. Moreover, it is still a challenge to maintain the intactness and infectivity of labeled viruses. Herein, a mild method has been developed to label viral envelope lipids with QDs by harnessing the biotinylated lipid-self-inserted cellular membrane. Biotinylated lipids can spontaneously insert in cellular membranes of host cells during culture and then be naturally assembled on progeny Pseudorabies virus (PrV) via propagation. The biotinylated PrV can be labeled with streptavidin-conjugated QDs, with a labeling efficiency of ∼90%. Such a strategy to label lipids with QDs can retain the intactness and infectivity of labeled viruses to the largest extent, facilitating the study of mechanisms of virus infection at the single virus level. PMID:27552317

  17. Harnessing microbial gene pools to remediate persistent organic pollutants using genetically modified plants--a viable technology?

    PubMed

    Rylott, Elizabeth L; Johnston, Emily J; Bruce, Neil C

    2015-11-01

    It has been 14 years since the international community came together to legislate the Stockholm Convention on Persistent Organic Pollutants (POPs), restricting the production and use of specific chemicals that were found to be environmentally stable, often bioaccumulating, with long-term toxic effects. Efforts are continuing to remove these pollutants from the environment. While incineration and chemical treatment can be successful, these methods require the removal of tonnes of soil, at high cost, and are damaging to soil structure and microbial communities. The engineering of plants for in situ POP remediation has had highly promising results, and could be a more environmentally-friendly alternative. This review discusses the characterization of POP-degrading bacterial pathways, and how the genes responsible have been harnessed using genetic modification (GM) to introduce these same abilities into plants. Recent advances in multi-gene cloning, genome editing technologies and expression in monocot species are accelerating progress with remediation-applicable species. Examples include plants developed to degrade 2,4,6-trinitrotoluene (TNT), hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), trichloroethylene (TCE), and polychlorinated biphenyls (PCBs). However, the costs and timescales needed to gain regulatory approval, along with continued public opposition, are considerable. The benefits and challenges in this rapidly developing and promising field are discussed. PMID:26283045

  18. Inspiration in the harness of daily labor. Darwin, botany, and the triumph of evolution, 1859-1868.

    PubMed

    Bellon, Richard

    2011-09-01

    Charles Darwin hoped that a large body of working naturalists would embrace evolution after the Origin of Species appeared in late 1859. He was disappointed. His evolutionary ideas at first made painfully little progress in the scientific community. But by 1863 the tide had turned dramatically, and within five years evolution became scientific orthodoxy in Britain. The Origin's reception followed this peculiar trajectory because Darwin had not initially tied its theory to productive original scientific investigation, which left him vulnerable to charges of reckless speculation. The debate changed with his successful application of evolution to original problems, most notably orchid fertilization, the subject of a well-received book in 1862. Most of Darwin's colleagues found the argument of the Origin convincing when they realized that it functioned productively in the day-to-day work of science-and not before. The conceptual force of the Origin, however outwardly persuasive, acquired full scientific legitimacy only when placed "in the harness of daily labour".

  19. Cycloart-24-ene-26-ol-3-one, a New Cycloartane Isolated from Leaves of Aglaia exima Triggers Tumour Necrosis Factor-Receptor 1-Mediated Caspase-Dependent Apoptosis in Colon Cancer Cell Line

    PubMed Central

    Loong, Xe-Min; Cheah, Foo Kit; Supratman, Unang; Litaudon, Marc; Mustafa, Mohd Rais; Awang, Khalijah

    2016-01-01

    Plants in the Meliaceae family are known to possess interesting biological activities, such as antimalaral, antihypertensive and antitumour activities. Previously, our group reported the plant-derived compound cycloart-24-ene-26-ol-3-one isolated from the hexane extracts of Aglaia exima leaves, which shows cytotoxicity towards various cancer cell lines, in particular, colon cancer cell lines. In this report, we further demonstrate that cycloart-24-ene-26-ol-3-one, from here forth known as cycloartane, reduces the viability of the colon cancer cell lines HT-29 and CaCO-2 in a dose- and time-dependent manner. Further elucidation of the compound’s mechanism showed that it binds to tumour necrosis factor-receptor 1 (TNF-R1) leading to the initiation of caspase-8 and, through the activation of Bid, in the activation of caspase-9. This activity causes a reduction in mitochondrial membrane potential (MMP) and the release of cytochrome-C. The activation of caspase-8 and -9 both act to commit the cancer cells to apoptosis through downstream caspase-3/7 activation, PARP cleavage and the lack of NFkB translocation into the nucleus. A molecular docking study showed that the cycloartane binds to the receptor through a hydrophobic interaction with cysteine-96 and hydrogen bonds with lysine-75 and -132. The results show that further development of the cycloartane as an anti-cancer drug is worthwhile. PMID:27070314

  20. Application of 2,4-Dinitrophenylhydrazine (DNPH) in High-Throughput Screening for Microorganism Mutants Accumulating 9α-Hydroxyandrost-4-ene-3,17-dione (9α-OH-AD)

    PubMed Central

    Liu, Yang; Cao, Fei; Xiong, Hui; Shen, Yanbing; Wang, Min

    2016-01-01

    To develop a quick method for the preliminarily screening of mutant strains that can accumulate 9α-hydroxyandrost-4-ene-3,17-dione (9α-OH-AD), a high-throughput screening method was presented by applying the principle that 2,4-dinitrophenylhydrazine (DNPH) can react with ketones to produce precipitation. The optimal color assay conditions were the substrate androst-4-ene-3,17-dione (AD) concentration at 2.0 g/L, the ratio of AD to DNPH solution at 1:4, and the sulfuric acid and ethanol solution percentages in DNPH solution at 2% and 35%, respectively. This method was used to preliminarily screen the mutants of Rhodococcus rhodochrous DSM43269, from which the three ones obtained could produce more 9α-OH-AD. This DNPH color assay method not only broadens screening methods and increases screening efficiency in microbial mutation breeding but also establishes a good foundation for obtaining strains for industrial application. PMID:27706217

  1. Cycloart-24-ene-26-ol-3-one, a New Cycloartane Isolated from Leaves of Aglaia exima Triggers Tumour Necrosis Factor-Receptor 1-Mediated Caspase-Dependent Apoptosis in Colon Cancer Cell Line.

    PubMed

    Leong, Kok Hoong; Looi, Chung Yeng; Loong, Xe-Min; Cheah, Foo Kit; Supratman, Unang; Litaudon, Marc; Mustafa, Mohd Rais; Awang, Khalijah

    2016-01-01

    Plants in the Meliaceae family are known to possess interesting biological activities, such as antimalaral, antihypertensive and antitumour activities. Previously, our group reported the plant-derived compound cycloart-24-ene-26-ol-3-one isolated from the hexane extracts of Aglaia exima leaves, which shows cytotoxicity towards various cancer cell lines, in particular, colon cancer cell lines. In this report, we further demonstrate that cycloart-24-ene-26-ol-3-one, from here forth known as cycloartane, reduces the viability of the colon cancer cell lines HT-29 and CaCO-2 in a dose- and time-dependent manner. Further elucidation of the compound's mechanism showed that it binds to tumour necrosis factor-receptor 1 (TNF-R1) leading to the initiation of caspase-8 and, through the activation of Bid, in the activation of caspase-9. This activity causes a reduction in mitochondrial membrane potential (MMP) and the release of cytochrome-C. The activation of caspase-8 and -9 both act to commit the cancer cells to apoptosis through downstream caspase-3/7 activation, PARP cleavage and the lack of NFkB translocation into the nucleus. A molecular docking study showed that the cycloartane binds to the receptor through a hydrophobic interaction with cysteine-96 and hydrogen bonds with lysine-75 and -132. The results show that further development of the cycloartane as an anti-cancer drug is worthwhile. PMID:27070314

  2. Sea floor topography and backscatter intensity of the Historic Area Remediation Site (HARS), offshore of New York, based on multibeam surveys conducted in 1996, 1998, and 2000

    USGS Publications Warehouse

    Butman, Bradford; Danforth, W.W.; Knowles, S.C.; May, Brian; Serrett, Laurie

    2000-01-01

    An area offshore of Sandy Hook, New Jersey, has been used extensively for disposal of dredged and other materials, derived from the New York/New Jersey Harbor and surrounding areas, since the late 1800's (Figure 1). Between 1976 and 1995, the New York Bight Dredged Material Disposal Site, also known as the Mud Dump Site (Figure 2), received on average about 6 million cubic yards of material each year from federal and private maintenance dredging and from harbor deepening activities (Massa and others, 1996). In September 1997 the Mud Dump Site (MDS) was closed as an official ocean disposal site by the U.S. Environmental Protection Agency (http://www.epa.gov/), and the MDS and surrounding areas were designated as the Historic Area Remediation Site (HARS). The HARS is subdivided into a Primary Remediation Area (PRA, subdivided into 9 cells), a Buffer Zone, and a No-Discharge Zone (Figure 2). The sea floor of the HARS, approximately 9 square nautical miles in area, is being remediated by placing at least a one-meter cap of Category I (clean) dredged material on top of the existing surface sediments that exhibit varying degrees of degradation. (See http://www.nan.usace.army.mil/business/prjlinks/dmmp/benefic/hars.htm)(Category I sediments have no potential short or long-term impacts and are acceptable for unrestricted ocean disposal (EPA, 1996)). About 1.1 million cubic yards of dredged material for remediation was placed in the HARS in 1999, and 2.5 million cubic yards in 2000. Three multibeam echosounder surveys were carried out to map the topography and surficial geology of the HARS. The surveys were conducted November 23 - December 3, 1996, October 26 - November 11, 1998, and April 6 - 30, 2000. The surveys were carried out as part of a larger survey of the Hudson Shelf Valley and adjacent shelf (Butman and others, 1998, (http://pubs.usgs.gov/openfile/of98-616/). This report presents maps showing topography, shaded relief, and backscatter intensity (a measure of sea

  3. Comparability of echographic and tomographic assessments of body fat changes related to the HIV associated adipose redistribution syndrome (HARS) in antiretroviral treated patients.

    PubMed

    Gulizia, Rosario; Vercelli, Alessandro; Gervasoni, Cristina; Uglietti, Alessia; Ortu, Massimiliano; Ferraioli, Giovanna; Galli, Massimo; Filice, Carlo

    2008-07-01

    To assess the comparability of ultrasonographic (US) subcutaneous fat thickness (SFT) measurements in comparison with computed tomography (CT) at reference points (RPs) representative of HIV related adipose redistribution syndrome (HARS) in patients treated with antiretrovirals. US and CT measurements were compared in nine patients with clinical reports of HARS. We obtained the best resolution of facial (at deepest point of Bichat pad), brachial (in the dorsal face of arm) and crural SFT (at mid thigh) by means of minimal transducer pressures avoiding potential biases such as stand off pads pressure on the skin and artefacts due to too abundant quantity of gel. CT scans were obtained in the same RP where US measurements were performed such as identified by means of metallic skin markers. Median US measurement of facial SFT was 8.8 mm (95% CI: 3.1 to 13.4), 3.95 mm (95% CI: 2.62 to 5.84) for brachial SFT and 4 mm (95% CI: 3.4 to 9.4) for crural SFT. Median CT assessments of facial SFT was 8.7 mm (95% CI: 3.5 to 13.5), 4.2 mm (95% CI: 2.6 to 5.88) for brachial SFT and 5 mm (95% CI: 3.9 to 10.3) for crural SFT, with no significant difference at each RP. A linear regression showed good CT/US comparability at each RP, with no significant deviation from linearity (p > 0.10). US shows to be highly comparable with CT, excluding invaliding biases as the transducer pressure on the skin. Given the proven efficacy on the HARS assessments, if well standardized, US could be a reliable method, simpler than CT in the management of body fat changes related to HARS.

  4. Paleoenvironmental significance of aluminum phosphate-sulfate minerals in the upper Cretaceous ooidal ironstones, E-NE Aswan area, southern Egypt

    NASA Astrophysics Data System (ADS)

    Salama, Walid

    2014-09-01

    Aluminum phosphate-sulfate (APS) minerals are present as small, disseminated crystals in the upper Cretaceous shallow marine ooidal ironstones, E-NE Aswan area, southern Egypt. Their association with the ironstones is considered as a proxy of subaerial weathering and post-diagenetic meteoric water alteration. The mineralogical composition of the ooidal ironstones was investigated by optical and scanning electron microscopes, X-ray diffraction, Fourier transform infrared and Raman spectroscopy. The ooidal ironstones are composed mainly of ooids and groundmass, both of which consist of a mixture of detrital (quartz) and diagenetic (fluorapatite, chamosite and pyrite) mineral assemblages. These mineral assemblages are destabilized under acidic and oxidizing, continental conditions. These conditions resulted from the oxidation of pyrite and probably organic matter under warm and humid, tropical climate followed the Santonian Sea regression and subaerial exposure. These pedogenic conditions promoted corrosion of quartz, dissolution of chamosite and apatite and hydrolysis of feldspars of the nearby exposed granitoids. The released Si, Al and Sr from quartz, chamosite and feldspars; Fe and S from pyrite and P, Ca and light rare earth elements (LREE) from apatite are reprecipitated as hematite, kaolinite, apatite and APS minerals from the pore fluids or along fractures. The paragenetic sequence and textural relationships of this post-diagenetic mineral assemblage indicate that hematite was formed by replacement of chamosite followed by formation of a secondary generation of pore filling chlorapatite and APS minerals and finally the precipitation of kaolinite in the remaining pore spaces. The formation of APS minerals and chlorapatite is simultaneous, but APS minerals are stable at shallow depths under acidic to neutral pH conditions, whereas chlorapatite is stable under alkaline pH conditions. Alkaline conditions were maintained at greater depths when the infiltrated

  5. Harnessing Online Peer Education (HOPE): Integrating C-POL and Social Media to Train Peer Leaders in HIV Prevention

    PubMed Central

    Jaganath, Devan; Gill, Harkiran K.; Cohen, Adam Carl; Young, Sean D.

    2011-01-01

    Novel methods, such as Internet-based interventions, are needed to combat the spread of HIV. While past initiatives have used the Internet to promote HIV prevention, the growing popularity, decreasing digital divide, and multi-functionality of social networking sites, such as Facebook, make this an ideal time to develop innovative ways to use online social networking sites to scale HIV prevention interventions among high-risk groups. The UCLA HOPE [Harnessing Online Peer Education] study is a longitudinal experimental study to evaluate the feasibility, acceptability, and preliminary effectiveness of using social media for peer-led HIV prevention, specifically among African American and Latino Men who have Sex with Men (MSM). No curriculum currently exists to train peer leaders in delivering culturally aware HIV prevention messages using social media. Training was created that adapted the Community Popular Opinion Leader (C-POL) model, for use on social networking sites. Peer leaders are recruited who represent the target population and have experience with both social media and community outreach. The curriculum contains the following elements: discussion and role playing exercises to integrate basic knowledge of HIV/AIDS, awareness of sociocultural HIV/AIDS issues in the age of technology, and communication methods for training peer leaders in effective, interactive social media-based HIV prevention. Ethical issues related to Facebook and health interventions are integrated throughout the sessions. Training outcomes have been developed for long-term assessment of retention and efficacy. This is the first C-POL curriculum that has been adapted for use on social networking websites. Although this curriculum has been used to target African American and Latino MSM, it has been created to allow generalization to other high-risk groups. PMID:22149081

  6. Biological inspiration in optics and photonics: harnessing nature's light manipulation strategies for multifunctional optical materials (Conference Presentation)

    NASA Astrophysics Data System (ADS)

    Kolle, Mathias; Sandt, Joseph D.; Nagelberg, Sara N.; Zarzar, Lauren D.; Kreysing, Moritz; Vukusic, Peter

    2016-03-01

    The precise control of light-matter interactions is crucial for the majority of known biological organisms in their struggle to survive. Many species have evolved unique methods to manipulate light in their environment using a variety of physical effects including pigment-induced, spectrally selective absorption or light interference in photonic structures that consist of micro- and nano-periodic material morphologies. In their optical performance, many of the known biological photonic systems are subject to selection criteria not unlike the requirements faced in the development of novel optical technology. For this reason, biological light manipulation strategies provide inspiration for the creation of tunable, stimuli-responsive, adaptive material platforms that will contribute to the development of multifunctional surfaces and innovative optical technology. Biomimetic and bio-inspired approaches for the manufacture of photonic systems rely on self-assembly and bottom-up growth techniques often combined with conventional top-down manufacturing. In this regard, we can benefit in several ways from highly sophisticated material solutions that have convergently evolved in various organisms. We explore design concepts found in biological photonic architectures, seek to understand the mechanisms underlying morphogenesis of bio-optical systems, aim to devise viable manufacturing strategies that can benefit from insight in biological formation processes and the use of established synthetic routines alike, and ultimately strive to realize new photonic materials with tailor-made optical properties. This talk is focused on the identification of biological role model photonic architectures, a brief discussion of recently developed bio-inspired photonic structures, including mechano-sensitive color-tunable photonic fibers and reconfigurable fluid micro-lenses. Potentially, early-stage results in studying and harnessing the structure-forming capabilities of living cells that

  7. Harnessing Fluorine–Sulfur Contacts and Multipolar Interactions for the Design of p53 Mutant Y220C Rescue Drugs

    PubMed Central

    2016-01-01

    Many oncogenic mutants of the tumor suppressor p53 are conformationally unstable, including the frequently occurring Y220C mutant. We have previously developed several small-molecule stabilizers of this mutant. One of these molecules, PhiKan083, 1-(9-ethyl-9H-carbazole-3-yl)-N-methylmethanamine, binds to a mutation-induced surface crevice with a KD = 150 μM, thereby increasing the melting temperature of the protein and slowing its rate of aggregation. Incorporation of fluorine atoms into small molecule ligands can substantially improve binding affinity to their protein targets. We have, therefore, harnessed fluorine–protein interactions to improve the affinity of this ligand. Step-wise introduction of fluorines at the carbazole ethyl anchor, which is deeply buried within the binding site in the Y220C–PhiKan083 complex, led to a 5-fold increase in affinity for a 2,2,2-trifluoroethyl anchor (ligand efficiency of 0.3 kcal mol–1 atom–1). High-resolution crystal structures of the Y220C–ligand complexes combined with quantum chemical calculations revealed favorable interactions of the fluorines with protein backbone carbonyl groups (Leu145 and Trp146) and the sulfur of Cys220 at the mutation site. Affinity gains were, however, only achieved upon trifluorination, despite favorable interactions of the mono- and difluorinated anchors with the binding pocket, indicating a trade-off between energetically favorable protein–fluorine interactions and increased desolvation penalties. Taken together, the optimized carbazole scaffold provides a promising starting point for the development of high-affinity ligands to reactivate the tumor suppressor function of the p53 mutant Y220C in cancer cells. PMID:27267810

  8. Harnessing and storing visible light using a heterojunction of WO3 and CdS for sunlight-free catalysis.

    PubMed

    Kim, Seonghun; Park, Yiseul; Kim, Wooyul; Park, Hyunwoong

    2016-08-01

    CdS and WO3 (CdS/WO3) bilayer film electrodes are fabricated to harness solar visible light (λ > 420 nm) and store photogenerated electrons for possible use during periods of unavailable sunlight. The overall film thickness is approximately 50-60 μm, while the CdS underlayer is slightly thinner than WO3 owing to a packing effect. The energetics of CdS and WO3 determined by optical and electrochemical analyses enables cascaded electron transfer from CdS to WO3. The open circuit potential (EOCP) of CdS/WO3 under visible light (approximately -0.35 V vs. SCE) is nearly maintained even in the absence of light, with a marginal decrease (∼0.15 V) in ∼20 h of darkness. Neither CdS nor WO3 alone exhibits such behavior. The electron lifetimes (τ) of CdS and WO3 are each less than 100 s, whereas coupling of the two increases τ to ∼2500 s at the EOCP. In the absence of dissolved O2, τ further increases, suggesting that O2 is the primary electron acceptor. In spite of oxic conditions, CdS/WO3 is capable of continuously reducing Cr(6+) to Cr(3+) and Ag(+) to Ag(0) after removal of visible light. The number of utilized (i.e., stored) electrons in the reductions of Cr(6+) and Ag(+) are estimated to be ∼1.08 × 10(17) and ∼0.87 × 10(17), respectively. The primary role of CdS is to be a visible-light absorber in the 420-565 nm wavelength range, transferring the photogenerated electrons to WO3. The electrons stored in WO3 are gradually released to electron acceptors with suitable redox potentials. PMID:27411566

  9. Harnessing the Risk-Related Data Supply Chain: An Information Architecture Approach to Enriching Human System Research and Operations Knowledge

    NASA Technical Reports Server (NTRS)

    Buquo, Lynn; Johnson-Throop, Kathy

    2010-01-01

    NASA's Human Research Program (HRP) and Space Life Sciences Directorate (SLSD), not unlike many NASA organizations today, struggle with the inherent inefficiencies caused by dependencies on heterogeneous data systems and silos of data and information spread across decentralized discipline domains. The capture of operational and research-based data/information (both in-flight and ground-based) in disparate IT systems impedes the extent to which that data/information can be efficiently and securely shared, analyzed, and enriched into knowledge that directly and more rapidly supports HRP's research-focused human system risk mitigation efforts and SLSD s operationally oriented risk management efforts. As a result, an integrated effort is underway to more fully understand and document how specific sets of risk-related data/information are generated and used and in what IT systems that data/information currently resides. By mapping the risk-related data flow from raw data to useable information and knowledge (think of it as the data supply chain), HRP and SLSD are building an information architecture plan to leverage their existing, shared IT infrastructure. In addition, it is important to create a centralized structured tool to represent risks including attributes such as likelihood, consequence, contributing factors, and the evidence supporting the information in all these fields. Representing the risks in this way enables reasoning about the risks, e.g. revisiting a risk assessment when a mitigation strategy is unavailable, updating a risk assessment when new information becomes available, etc. Such a system also provides a concise way to communicate the risks both within the organization as well as with collaborators. Understanding and, hence, harnessing the human system risk-related data supply chain enhances both organizations' abilities to securely collect, integrate, and share data assets that improve human system research and operations.

  10. Harnessing data structure for recovery of randomly missing structural vibration responses time history: Sparse representation versus low-rank structure

    NASA Astrophysics Data System (ADS)

    Yang, Yongchao; Nagarajaiah, Satish

    2016-06-01

    Randomly missing data of structural vibration responses time history often occurs in structural dynamics and health monitoring. For example, structural vibration responses are often corrupted by outliers or erroneous measurements due to sensor malfunction; in wireless sensing platforms, data loss during wireless communication is a common issue. Besides, to alleviate the wireless data sampling or communication burden, certain accounts of data are often discarded during sampling or before transmission. In these and other applications, recovery of the randomly missing structural vibration responses from the available, incomplete data, is essential for system identification and structural health monitoring; it is an ill-posed inverse problem, however. This paper explicitly harnesses the data structure itself-of the structural vibration responses-to address this (inverse) problem. What is relevant is an empirical, but often practically true, observation, that is, typically there are only few modes active in the structural vibration responses; hence a sparse representation (in frequency domain) of the single-channel data vector, or, a low-rank structure (by singular value decomposition) of the multi-channel data matrix. Exploiting such prior knowledge of data structure (intra-channel sparse or inter-channel low-rank), the new theories of ℓ1-minimization sparse recovery and nuclear-norm-minimization low-rank matrix completion enable recovery of the randomly missing or corrupted structural vibration response data. The performance of these two alternatives, in terms of recovery accuracy and computational time under different data missing rates, is investigated on a few structural vibration response data sets-the seismic responses of the super high-rise Canton Tower and the structural health monitoring accelerations of a real large-scale cable-stayed bridge. Encouraging results are obtained and the applicability and limitation of the presented methods are discussed.

  11. Harnessing Online Peer Education (HOPE): integrating C-POL and social media to train peer leaders in HIV prevention.

    PubMed

    Jaganath, Devan; Gill, Harkiran K; Cohen, Adam Carl; Young, Sean D

    2012-01-01

    Novel methods, such as Internet-based interventions, are needed to combat the spread of HIV. While past initiatives have used the Internet to promote HIV prevention, the growing popularity, decreasing digital divide, and multi-functionality of social networking sites, such as Facebook, make this an ideal time to develop innovative ways to use online social networking sites to scale HIV prevention interventions among high-risk groups. The UCLA Harnessing Online Peer Education study is a longitudinal experimental study to evaluate the feasibility, acceptability, and preliminary effectiveness of using social media for peer-led HIV prevention, specifically among African American and Latino Men who have Sex with Men (MSM). No curriculum currently exists to train peer leaders in delivering culturally aware HIV prevention messages using social media. Training was created that adapted the Community Popular Opinion Leader (C-POL) model, for use on social networking sites. Peer leaders are recruited who represent the target population and have experience with both social media and community outreach. The curriculum contains the following elements: discussion and role playing exercises to integrate basic knowledge of HIV/AIDS, awareness of sociocultural HIV/AIDS issues in the age of technology, and communication methods for training peer leaders in effective, interactive social media-based HIV prevention. Ethical issues related to Facebook and health interventions are integrated throughout the sessions. Training outcomes have been developed for long-term assessment of retention and efficacy. This is the first C-POL curriculum that has been adapted for use on social networking websites. Although this curriculum has been used to target African-American and Latino MSM, it has been created to allow generalization to other high-risk groups.

  12. A new series of bis(ene-1,2-dithiolato)tungsten(IV), -(V), -(VI) complexes as reaction centre models of tungsten enzymes: preparation, crystal structures and spectroscopic properties.

    PubMed

    Sugimoto, Hideki; Hatakeda, Kohei; Toyota, Kazuo; Tatemoto, Susumu; Kubo, Minoru; Ogura, Takashi; Itoh, Shinobu

    2013-03-01

    The carbomethoxy substituted dithiolene ligand (L(COOMe)) enabled us to develop a series of new bis(ene-1,2-dithiolato)tungsten complexes including W(IV)O, W(IV)(OSiBuPh(2)), W(VI)O(2), W(VI)O(OSiBuPh(2)) and W(VI)O(S) core structures. By using these tungsten complexes, a systematic study of the terminal monodentate ligand effects has been performed on the structural, spectroscopic properties and reactivity. The structure and spectroscopic properties of the tungsten complexes have also been compared to those of the molybdenum complexes coordinated by the same ligand to investigate the effects of the metal ion (W vs. Mo). X-ray crystallographic analyses of the tungsten(IV) complexes have revealed that the tungsten centres adopt a distorted square pyramidal geometry with a dithiolene ligand having an ene-1,2-dithiolate form. On the other hand, the dioxotungsten(VI) complex exhibits an octahedral structure consisting of the bidentate L(COOMe) and two oxo groups, in which π-delocalization was observed between the W(VI)O(2) and ene-1,2-dithiolate units. The tungsten(IV) and dioxotungsten(VI) complexes are isostructural with the molybdenum counter parts. DFT calculation study of the W(VI)O(S) complex has indicated that the W=S bond of 2.2 Å is close to the bond length between the tungsten centre and ambiguously assigned terminal monodentate atom in aldehyde oxidoreductase of the tungsten enzyme. Resonance Raman (rR) spectrum of the W(VI)O(S) complex has shown the two inequivalent L(COOMe) ligands with respect to their bonding interactions with the tungsten centre, reproducing the appearance of two ν(C=C) stretches in the rR spectrum of aldehyde oxidoreductase. Sulfur atom transfer reaction from the W(VI)O(S) complex to triphenylphosphines has also been studied kinetically to demonstrate that the tungsten complex has a lower reactivity by about one-order of magnitude, when compared with its molybdenum counterpart.

  13. Harnessing wind power

    NASA Astrophysics Data System (ADS)

    Fagenbaum, J.

    1982-04-01

    The design goals, test results, operating mechanisms, and ultimate limits of large wind energy conversion systems (WECS) are explored. NASA is currently managing and monitoring the performance of the Mod O, Mod OA, Mod 1, and Mod 2 wind turbines, which produce from 100 kW-2.5 MWe for grid interconnection. The Mod 2 machines have a 300 ft diam rotor, begin producing at 14 mph and achieve the rated output at 20 mph. Testing has shown the necessity of incorporating partial span pitch control, a flexible shaft, yaw control, microprocessor monitored wind condition sensors, and a soft-shell tower to lower vibration hazards with WECS. Large WECS have proved to be relatively nonpolluting, although some television and radio interference is present. Institutional issues for the protection of land, of aircraft flight paths, and for utility interconnect are outlined, and large WECS development programs in Denmark, Sweden, Spain, and Germany are described.

  14. Synthesis and pharmacological profile of bicyclo[2.2.2]octane derivatives: N-(1-aryl-4-piperazinyl-butyl) derivatives of 7-isopropyl-6-methyl- and 1-isopropyl-4-methylbicyclo[2.2.2]oct-5-ene-2,3-dicarboxyimide.

    PubMed

    Zawadowski, T; Skowron, A A; Suski, S; Rump, S; Jakowicz, I

    1995-01-01

    The new class of compounds characterized by anxiolytic or antidepressive properties, including a number of N-(1-aryl-4-piperazinylbutyl) derivatives of the two isomers: 7-isopropyl-6-methyl- and 1-isopropyl-4-methylbicyclo [2.2.2]oct-5-ene-2,3-dicarboxyimide was synthesized. Two compounds were selected for further pharmacological study.

  15. Crystal structure of 5''-benzyl-idene-1'-methyl-4'-phenyl-tri-spiro-[ace-naphthyl-ene-1,2'-pyrrolidine-3',1''-cyclo-hexane-3'',2'''-[1,3]dioxane]-2,6''-dione.

    PubMed

    Chandralekha, Kuppan; Gavaskar, Deivasigamani; Sureshbabu, Adukamparai Rajukrishnan; Lakshmi, Srinivasakannan

    2016-03-01

    In the title compound, C36H31NO4, two spiro links connect the methyl-substituted pyrrolidine ring to the ace-naphthyl-ene and cyclo-hexa-none rings. The cyclo-hexa-none ring is further connected to the dioxalane ring by a third spiro junction. The five-membered ring of the ace-naphthylen-1-one ring system adopts a flattened envelope conformation with the ketonic C atom as flap, whereas the dioxalane and pyrrolidine rings each have a twist conformation. The cyclo-hexa-none ring assumes a boat conformation. Three intra-molecular C-H⋯O hydrogen bonds involving both ketonic O atoms as acceptors are present. In the crystal, C-H⋯O hydrogen bonds connect centrosymmetrically related mol-ecule into chains parallel to the b axis, forming rings of R 2 (2)(10)and R 2 (2)(8) graph-set motifs. PMID:27006814

  16. catena-Poly[[tetra­aqua­cadmium]-μ-5,5′-(1,4-phenyl­ene)di(tetra­zol-2-ido)-κ2 N 2:N 2′

    PubMed Central

    Dang, Qinqin; Caiyun, Han

    2013-01-01

    In the title compound, [Cd(C8H4N8)(H2O)4]n, 5,5′-(1,4-phenyl­ene)di(tetra­zol-2-ide) (L) ligands bridge CdII atoms into polymeric chains along [201]. The CdII atom is situated on an inversion centre and is coordinated by two N atoms from two L ligands and by four water O atoms in a distorted octa­hedral geometry. In the L ligand, the benzene ring resides on an inversion centre and the tetra­zole rings are twisted from its plane by 22.3 (1)°. An extensive hydrogen-bonding network formed by classical O—H⋯N and O—H⋯O inter­actions consolidates the crystal packing, linking the poymeric chains into a three-dimensional structure. PMID:23723784

  17. Chlorido(10,11,12,13-tetra­hydro-4,5,9,14-tetra­aza­benzo[b]triphenyl­ene-κ2 N 4,N 5)copper(I)

    PubMed Central

    Hong, Jun; Li, Xiu-Ying; Ng, Seik Weng

    2011-01-01

    The CuI atom in the title compound, [CuCl(C18H14N4)], is N,N′-chelated by the N-heterocyclic ligand and coordinated by one Cl− anion in a distorted trigonal geometry. In the crystal, the CuI atom is disordered over two positions in a 0.667 (6):0.333 (6) ratio. The deviation of the Cu atom from the N/N/Cl coordination plane is 0.013 (3) Å for the major component and 0.073 (6) Å for the minor component. Two methyl­ene C atoms are also disordered over two positions in a 0.667 (6):0.333 (6) ratio. PMID:22065705

  18. Theoretical prediction of a perepoxide intermediate for the reaction of singlet oxygen with trans-cyclooctene contrasts with the two-step no-intermediate ene reaction for acyclic alkenes.

    PubMed

    Leach, Andrew G; Houk, K N; Foote, Christopher S

    2008-11-01

    B3LYP/6-31G* and CASMP2 calculations have been employed to study the ene reaction of singlet oxygen with trans-cyclooctene. These methods predict that the reaction involves a perepoxide intermediate, whereas alkenes such as tetramethylethylene are predicted by the same methods to occur by a two-step no-intermediate mechanism, with no perepoxide intermediate. The change in mechanism arises because the trans-cyclooctene imposes a substantial strain in the transition state for hydrogen abstraction. The perepoxide is formed through a polarized diradical intermediate that can lead to the observation of alkene isomerization. The polarized diradical also becomes a minimum because of the barrier to abstraction.

  19. 6 alpha-Fluoro- and 6 alpha,9 alpha-difluoro-11 beta,21-dihydroxy-16 alpha,17 alpha-propylmethylenedioxypregn-4-ene-3,20-dione: synthesis and evaluation of activity and kinetics of their C-22 epimers.

    PubMed

    Thalén, B A; Axelsson, B I; Andersson, P H; Brattsand, R L; Nylander, B; Wickström, L I

    1998-01-01

    It is generally accepted that the anti-inflammatory effect of glucocorticosteroids cannot be separated from their adverse effects at the receptor level. However, modification of the pharmacokinetics through structural alterations could provide steroids with a better therapeutic index than those currently used. Thus, new 16 alpha,17 alpha-acetals between butyraldehyde and 6 alpha-fluoro- or 6 alpha,9 alpha-difluoro-16 alpha-hydroxycortisol were synthesized and studied. Acetalization of the corresponding 16 alpha,17 alpha-diols or transacetalization of their 16 alpha,17 alpha-acetonides in dioxane produced mixtures of C-22 epimers, which were resolved by preparative chromatography. Alternatively, an efficient method was used to produce the 22R-epimer stereoselectively through performing the acetalization and transacetalization in a hydrocarbon with an inert material present. The C-22 configuration of (22R)-6 alpha,9 alpha-difluoro-11 beta,21-dihydroxy-16 alpha,17 alpha-propylmethylenedioxypregn-4-ene-3,20-dione was unambiguously established by single crystal X-ray diffraction. The present compounds, especially the 22R-epimer just mentioned, bind to the rat thymus glucocorticoid receptor with high potency. The C-22 epimers of the 6 alpha,9 alpha-difluoro derivatives showed a 10-fold higher biotransformation rate than the budesonide 22R-epimer when incubated with human liver S9 subcellular fraction. The high receptor affinity in combination with the high biotransformation rate indicates that (22R)-6 alpha,9 alpha-difluoro-11 beta,21-dihydroxy-16 alpha,17 alpha-propylmethylenedioxypregn-4-ene-3,20-dione may be an improved 16 alpha,17 alpha-acetal glucocorticosteroid for therapy of inflammatory diseases, in which the mucous membranes are involved, such as those in the intestinal tract as well in the respiratory tract. PMID:9437793

  20. Cryogenic on-orbit liquid depot storage acquisition and transfer (COLD-SAT) experiment subsystem instrumentation and wire harness design report

    NASA Technical Reports Server (NTRS)

    Edwards, Lawrence G.

    1994-01-01

    Subcritical cryogens such as liquid hydrogen (LH2) and liquid oxygen (LO2) are required for space based transportation propellant, reactant, and life support systems. Future long-duration space missions will require on-orbit systems capable of long-term cryogen storage and efficient fluid transfer capabilities. COLD-SAT, which stands for cryogenic orbiting liquid depot-storage acquisition and transfer, is a free-flying liquid hydrogen management flight experiment. Experiments to determine optimum methods of fluid storage and transfer will be performed on the COLD-SAT mission. The success of the mission is directly related to the type and accuracy of measurements made. The instrumentation and measurement techniques used are therefore critical to the success of the mission. This paper presents the results of the COLD-SAT experiment subsystem instrumentation and wire harness design effort. Candidate transducers capable of fulfilling the COLD-SAT experiment measurement requirements are identified. Signal conditioning techniques, data acquisition requirements, and measurement uncertainty analysis are presented. Electrical harnessing materials and wiring techniques for the instrumentation designed to minimize heat conduction to the cryogenic tanks and provide optimum measurement accuracy are listed.