Sample records for strongly absorbing c-h

  1. Catalog of strong MgII absorbers (Lawther+, 2012)

    DEFF Research Database (Denmark)

    Lawther, D.; Paarup, Troels; Schmidt, Morten L.


    Here we present a catalog of strong (rest equivalent width Wr> intervening Mg II absorbers in the SDSS Data Release 7 quasar catalog (2010AJ....139.2360S, Cat. VII/260). The intervening absorbers were found by a semi-automatic algorithm written in IDL - for details of the algorithm see section 2...... of our paper. A subset of the absorbers have been visually inspected - see the MAN_OK flag in the catalog. The number of sightlines searched, tabulated by absorber redshift, i.e. g(z), is available as an ASCII table (for S/N>8 and S/N>15). All analysis in our paper is based on the SNR>8 coverage......, and considers only sight-lines towards non-BAL quasars. Any questions regarding the catalog should be sent to Daniel Lawther (unclellama(at) (3 data files)....

  2. Improvement of discontinuity factor for strong absorber region

    Energy Technology Data Exchange (ETDEWEB)

    Guo, Jiong, E-mail:; Li, Fu, E-mail:; Zhang, Han; Zhou, Xiafeng; Fan, Kai; Wang, Lidong; Lu, Jianan


    At Institute of Nuclear and New Energy Technology (INET) the discontinuity factor corrected diffusion method with the homogenization technology was developed and applied in the control rod worth calculation of the pebble bed high temperature gas cooled reactor. But the result with the normal procedure is not accurate enough for a strong absorber. The numerical analysis shows that the strong absorber still has great influence on the flux distribution in the nearby graphite region, so that the flux distribution obtained by the normal diffusion method does not agree with the transport result. Thus, two improvements were proposed in this paper. First, instead of the neutron flux in the middle of the fine mesh, the surface flux of the absorber region was calculated through the net current in the boundary of the region; and then, while the discontinuity factor of the homogenized absorber region should be calculated, the discontinuity factor of the neighboring graphite region on the other side of the interface should also be calculated to eliminate the influence of the strong absorber. The numerical results demonstrate that, based on the improved method, the accuracy of heterogeneous transport calculation can be achieved by a diffusion calculation.

  3. A transformation technique to treat strong vibrating absorbers

    International Nuclear Information System (INIS)

    Sahni, D.C.; Garis, N.S.; Pazsit, I.


    Calculation of the neutron noise, induced by small amplitude vibrations of a strong absorber, is a difficult task because the traditional linearization technique cannot be applied. Two methods, based on two different representations of the absorber, were developed earlier to solve the problem. In both methods the rod displacements are described by a Taylor expansion, such that the boundary condition needs only to be considered at the surface of a static rod. Only one of the methods is applicable in two dimensions. In this paper an alternative method is developed and used for the solution of the problem. The essence of the method is a variable transformation by which the moving boundary is transformed into a static one without Taylor expansion. The corresponding equations are solved in a linear manner and the solution is transformed back to the original parameter space. The method is equally applicable in one and two dimensions. The solutions are in complete agreement with those of the previous methods

  4. Solving the conundrum of intervening strong Mg II absorbers towards gamma-ray bursts and quasars (United States)

    Christensen, L.; Vergani, S. D.; Schulze, S.; Annau, N.; Selsing, J.; Fynbo, J. P. U.; de Ugarte Postigo, A.; Cañameras, R.; Lopez, S.; Passi, D.; Cortés-Zuleta, P.; Ellison, S. L.; D'Odorico, V.; Becker, G.; Berg, T. A. M.; Cano, Z.; Covino, S.; Cupani, G.; D'Elia, V.; Goldoni, P.; Gomboc, A.; Hammer, F.; Heintz, K. E.; Jakobsson, P.; Japelj, J.; Kaper, L.; Malesani, D.; Møller, P.; Petitjean, P.; Pugliese, V.; Sánchez-Ramírez, R.; Tanvir, N. R.; Thöne, C. C.; Vestergaard, M.; Wiersema, K.; Worseck, G.


    Previous studies have shown that the incidence rate of intervening strong Mg II absorbers towards gamma-ray bursts (GRBs) were a factor of 2-4 higher than towards quasars. Exploring the similar sized and uniformly selected legacy data sets XQ-100 and XSGRB, each consisting of 100 quasar and 81 GRB afterglow spectra obtained with a single instrument (VLT/X-shooter), we demonstrate that there is no disagreement in the number density of strong Mg II absorbers with rest-frame equivalent widths W_rλ2796>1 Å towardsGRBs and quasars in the redshift range 0.1 ≲ z ≲ 5. With large and similar sample sizes, and path length coverages of Δz = 57.8 and 254.4 for GRBs and quasars, respectively, the incidences of intervening absorbers are consistent within 1σ uncertainty levels at all redshifts. For absorbers at z Digital Sky Survey (SDSS) quasar spectra, while for quasar absorbers observed with X-shooter we find an excess factor of 1.4 ± 0.2 relative to SDSS quasars. Conversely, the incidence rates agree at all redshifts with reported high-spectral-resolution quasar data, and no excess is found. The only remaining discrepancy in incidences is between SDSS Mg II catalogues and high-spectral-resolution studies. The rest-frame equivalent-width distribution also agrees to within 1σ uncertainty levels between the GRB and quasar samples. Intervening strong Mg II absorbers towards GRBs are therefore neither unusually frequent, nor unusually strong. Based on observations collected at the European Southern Observatory, Paranal, Chile, Program ID: 098.A-0055, 097.A-0036, 096.A-0079, 095.B-0811(B), 095.A-0045, 094.A-0134, 093.A-0069, 092.A-0124, 0091.C-0934, 090.A-0088, 089.A-0067, 088.A-0051, 087.A-0055, 086.A-0073, 085.A-0009 and 084.A-0260. XQ-100: 189.A-0424.

  5. Critical experiments on an enriched uranium solution system containing periodically distributed strong thermal neutron absorbers

    International Nuclear Information System (INIS)

    Rothe, R.E.


    A series of 62 critical and critical approach experiments were performed to evaluate a possible novel means of storing large volumes of fissile solution in a critically safe configuration. This study is intended to increase safety and economy through use of such a system in commercial plants which handle fissionable materials in liquid form. The fissile solution's concentration may equal or slightly exceed the minimum-critical-volume concentration; and experiments were performed for high-enriched uranium solution. Results should be generally applicable in a wide variety of plant situations. The method is called the 'Poisoned Tube Tank' because strong neutron absorbers (neutron poisons) are placed inside periodically spaced stainless steel tubes which separate absorber material from solution, keeping the former free of contamination. Eight absorbers are investigated. Both square and triangular pitched lattice patterns are studied. Ancillary topics which closely model typical plant situations are also reported. They include the effect of removing small bundles of absorbers as might occur during inspections in a production plant. Not taking the tank out of service for these inspections would be an economic advantage. Another ancillary topic studies the effect of the presence of a significant volume of unpoisoned solution close to the Poisoned Tube Tank on the critical height. A summary of the experimental findings is that boron compounds were excellent absorbers, as expected. This was true for granular materials such as Gerstley Borate and Borax; but it was also true for the flexible solid composed of boron carbide and rubber, even though only thin sheets were used. Experiments with small bundles of absorbers intentionally removed reveal that quite reasonable tanks could be constructed that would allow a few tubes at a time to be removed from the tank for inspection without removing the tank from production service

  6. Characterization of weak, fair and strong neutron absorbing materials by means of neutron transmission: Beam hardening effect

    International Nuclear Information System (INIS)

    Kharfi, F.; Bastuerk, M.; Boucenna, A.


    The characterization of neutron absorbing materials as well as quantification of neutron attenuation through matter is very essential in various fields, namely in shielding calculation. The objective of this work is to describe an experimental procedure to be used for the determination of neutron transmission through different materials. The proposed method is based on the relation between the gray value measured on neutron radiography image and the corresponding inducing neutron beam. For such a purpose, three kinds of materials (in shape of plate) were investigated using thermal neutrons: (1) boron-alloyed stainless steel as strong absorber; (2) copper and steel as fair absorbers and (3) aluminum as weak absorber. This work is not limited to the determination of neutron transmission through matters; it is also spread out to the measure of the surface density of the neutron absorbing elements (ρ s ) as a function of thickness of neutron absorbing material such as boron-alloyed stainless steel. The beam hardening effect depending on material thickness was also studied using the neutron transmission measurements. A theoretical approach was used to interpret the experimental results. The neutron transmission measurements were performed at the Neutron Radiography and Tomography facility of the Atomic Institute of the Austrian Universities in Vienna. Finally, a Maxwellian neutron distribution of incident neutron beam was used in the theoretical calculations of neutron energy shift in order to compare with experiments results. The obtained experimental results are in a good agreement with the developed theoretical approach

  7. Characterization of weak, fair and strong neutron absorbing materials by means of neutron transmission: Beam hardening effect (United States)

    Kharfi, F.; Bastuerk, M.; Boucenna, A.


    The characterization of neutron absorbing materials as well as quantification of neutron attenuation through matter is very essential in various fields, namely in shielding calculation. The objective of this work is to describe an experimental procedure to be used for the determination of neutron transmission through different materials. The proposed method is based on the relation between the gray value measured on neutron radiography image and the corresponding inducing neutron beam. For such a purpose, three kinds of materials (in shape of plate) were investigated using thermal neutrons: (1) boron-alloyed stainless steel as strong absorber; (2) copper and steel as fair absorbers and (3) aluminum as weak absorber. This work is not limited to the determination of neutron transmission through matters; it is also spread out to the measure of the surface density of the neutron absorbing elements (ρs) as a function of thickness of neutron absorbing material such as boron-alloyed stainless steel. The beam hardening effect depending on material thickness was also studied using the neutron transmission measurements. A theoretical approach was used to interpret the experimental results. The neutron transmission measurements were performed at the Neutron Radiography and Tomography facility of the Atomic Institute of the Austrian Universities in Vienna. Finally, a Maxwellian neutron distribution of incident neutron beam was used in the theoretical calculations of neutron energy shift in order to compare with experiments results. The obtained experimental results are in a good agreement with the developed theoretical approach.

  8. Isolating Weakly and Strongly-Absorbing Classes of Carbonaceous Aerosol: Optical Properties, Abundance and Lifecycle

    Energy Technology Data Exchange (ETDEWEB)

    Bond, Tami C. [Univ. of Illinois, Urbana-Champaign, IL (United States); Rood, Mark J. [Univ. of Illinois, Urbana-Champaign, IL (United States); Riemer, Nicole [Univ. of Illinois, Urbana-Champaign, IL (United States)


    absorption. Aging by NH3 produces a mild increase in the hygroscopicity of BrC, and a greater increase in cloud condensation nucleus activity. Therefore, reactions with NH3 form compounds that absorb more light than the original aerosol and act as surfactants, increasing the likelihood that these particles will participate in cloud formation. The particle-resolved model PartMC was enhanced to include additional physical processes. It was calibrated against chamber results, and we needed to account for the non-spherical structure of particle agglomerates, even for ammonium sulfate. We implemented the “volatility basis set” (VBS) framework in the model. The updated PartMC-MOSAIC model was able to simulate gas and aerosol concentrations from the CARES campaign at levels similar to observations. The PartMC model was used to evaluate plume dynamics affecting CCN activity of biomass burning aerosols early in a plume. Coagulation limits emission of CCN to about 1016 per kg of fuel. Co-emitted, semi-volatile organic compounds or emission at small particle sizes can homogenize composition before plume exit, and SVOC co-emission can be the main factor determining plume-exit CCN for hydrophobic or small particles. When externally-mixed, accumulation-mode particles are emitted in the absence of SVOCs, CCN can be overestimated by up to a factor of two. This means that measurements made on aerosol from all phases of combustion gathered into a single chamber may incorrectly estimate CCN properties. Based on the findings here, we make some recommendations for use in large-scale models: (1) inventories should represent “internally” versus “externally” mixed under certain combustion conditions; (2) consideration of non-spherical particles when coagulation is important for climate-relevant properties near sources; (3) designating organic biomass particles as weakly absorbing; (4) “inherent absorption” and hygroscopicity are not altered with aging by ozone

  9. Rigidly linking cyclometallated Ir(iii) and Pt(ii) centres: an efficient approach to strongly absorbing and highly phosphorescent red emitters. (United States)

    Turnbull, Graeme; Williams, J A Gareth; Kozhevnikov, Valery N


    The synthesis and photophysical properties of an unprecedented tetranuclear complex are described, in which a fac-tris-cyclometallated Ir(iii) centre is rigidly connected to three cyclometallated Pt(ii) centres. The complex absorbs strongly up to ∼600 nm and emits red light with unusually high efficiency.

  10. Semiconducting polymer-based nanoparticles with strong absorbance in NIR-II window for in vivo photothermal therapy and photoacoustic imaging. (United States)

    Cao, Ziyang; Feng, Liangzhu; Zhang, Guobing; Wang, Junxia; Shen, Song; Li, Dongdong; Yang, Xianzhu


    Near-infrared (NIR) light-induced photothermal therapy (PTT) has attracted much interest in recent years. In the NIR region, tissue penetration ability of the second biological near-infrared window (1000-1350 nm) is recognized to be stronger than that of the first window (650-950 nm). However, NIR light absorbers in the second NIR region (NIR-II) have been scant even though various NIR light absorbers in the first NIR region (NIR-I) have been widely explored. In this work, a thieno-isoindigo derivative-based semiconducting polymer, PBTPBF-BT, were formulated into PEGylated nanoparticles. The obtained nanoparticle NP PBTPBF-BT exhibited strong absorption in NIR-II region, inherent high photothermal conversion efficacy, and excellent photostability. The in vitro and in vivo PTT study employing 1064 nm laser in NIR-II window revealed that NP PBTPBF-BT could efficiently ablate tumor cell at a power density of 0.42 W/cm 2 (the skin tolerance threshold value). Moreover, NP PBTPBF-BT with excellent photostability exhibited enhanced photoacoustic (PA) imaging of tumor in living mice, suggesting the great probability of using NP PBTPBF-BT for in vivo PA imaging-guided PTT in the NIR-II window. Copyright © 2017 Elsevier Ltd. All rights reserved.

  11. Palladium-catalysed electrophilic aromatic C-H fluorination (United States)

    Yamamoto, Kumiko; Li, Jiakun; Garber, Jeffrey A. O.; Rolfes, Julian D.; Boursalian, Gregory B.; Borghs, Jannik C.; Genicot, Christophe; Jacq, Jérôme; van Gastel, Maurice; Neese, Frank; Ritter, Tobias


    Aryl fluorides are widely used in the pharmaceutical and agrochemical industries, and recent advances have enabled their synthesis through the conversion of various functional groups. However, there is a lack of general methods for direct aromatic carbon-hydrogen (C-H) fluorination. Conventional methods require the use of either strong fluorinating reagents, which are often unselective and difficult to handle, such as elemental fluorine, or less reactive reagents that attack only the most activated arenes, which reduces the substrate scope. A method for the direct fluorination of aromatic C-H bonds could facilitate access to fluorinated derivatives of functional molecules that would otherwise be difficult to produce. For example, drug candidates with improved properties, such as increased metabolic stability or better blood-brain-barrier penetration, may become available. Here we describe an approach to catalysis and the resulting development of an undirected, palladium-catalysed method for aromatic C-H fluorination using mild electrophilic fluorinating reagents. The reaction involves a mode of catalysis that is unusual in aromatic C-H functionalization because no organometallic intermediate is formed; instead, a reactive transition-metal-fluoride electrophile is generated catalytically for the fluorination of arenes that do not otherwise react with mild fluorinating reagents. The scope and functional-group tolerance of this reaction could provide access to functional fluorinated molecules in pharmaceutical and agrochemical development that would otherwise not be readily accessible.

  12. Decorative a-C:H coatings

    Czech Academy of Sciences Publication Activity Database

    Černý, F.; Jech, V.; Štěpánek, I.; Macková, Anna; Konvičková, S.

    roč. 256, 3 s. 1 (2009), s77-s81 ISSN 0169-4332 Institutional research plan: CEZ:AV0Z10480505 Keywords : a-C:H films * decorative coatings * adhesion Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.616, year: 2009

  13. Palladium Catalyzed Allylic C-H Alkylation

    DEFF Research Database (Denmark)

    Engelin, Casper Junker; Fristrup, Peter


    an acetate ion coordinated to Pd. Several of the reported systems rely on benzoquinone for re-oxidation of the active catalyst. The scope for nucleophilic addition in allylic C-H alkylation is currently limited, due to demands on pKa of the nucleophile. This limitation could be due to the pH dependence...

  14. Study of the strongly ionized medium in active galactic n ('Warm Absorber'): multi-wavelength modelling and plasma diagnostics in the X-ray spectral range

    International Nuclear Information System (INIS)

    Porquet, Delphine


    The so-called 'Warm Absorber' medium is observed in the central region of Active Galactic Nuclei and particularly in Seyfert l galaxies. lt is mainly characterized by O(VII) and O(VIII) absorption edges detected in the soft X-rays. Its study (modelization and observation) is an important key tool to understand Active Galactic Nuclei. The work presented here consists in modelling the Warm Absorber, and in developing X-ray spectroscopy diagnostics to constrain the physical parameters of any hot medium such as the Warm Absorber. The physical parameters of the Warm Absorber (density, temperature, ionization processes..) are difficult to determine only on the basis of present X-ray data. In particular, the value of the density cannot be derived only from the modelling of the resonance lines and of the soft X-ray absorption edges since there are almost insensitive to the density in the range of values expected for the Warm Absorber. lt is why we have developed diagnostic methods based on a multi-wavelength approach. The modelling is made with two complementary computational codes: PEGAS, and IRIS which takes into account the most accurate atomic data. With these two codes, we have modelled several types of plasma ionisation processes (photoionized plasmas and/or collisional). Results for the Warm Absorber were compared to multi-wavelength observations (mainly the optical iron coronal lines [Fe X] 6375 Angstroms, [Fe XI] 7892 Angstroms, and [Fe XIV] 5303 Angstroms). The proposed method has allowed to show that the Warm Absorber could be responsible of the emission of these lines totally or partially. All models of the Warm Absorber producing coronal line equivalent widths larger than observed were ruled out. This strongly constrains the physical parameters of the Warm Absorber, and particularly its density (n H ≥10 10 cm -3 ). The new generation of X-ray satellites (Chandra/AXAF, XMM...) will produce spectra at high spectral resolution and high sensitivity

  15. Study of the hydrogen behavior in amorphous hydrogenated materials of type a - C:H and a - SiC:H facing fusion reactor plasma

    International Nuclear Information System (INIS)

    Barbier, G.


    Plasma facing components of controlled fusion test devices (tokamaks) are submitted to several constraints (irradiation, high temperatures). The erosion (physical sputtering and chemical erosion) and the hydrogen recycling (retention and desorption) of these materials influence many plasma parameters and thus affect drastically the tokamak running. First, we will describe the different plasma-material interactions. It will be pointed out, how erosion and hydrogen recycling are strongly related to both chemical and physical properties of the material. In order to reduce these interactions, we have selected two amorphous hydrogenated materials (a-C:H and a-SiC:H), which are known for their good thermal and chemical qualities. Some samples have been then implanted with lithium ions at different fluences. Our materials have been then irradiated with deuterium ions at low energy. From our results, it is shown that both the lithium implantation and the use of an a - SiC:H substrate can be beneficial in enhancing the hydrogen retention. These results were completed with thermal desorption studies of these materials. It was evidenced that the hydrogen fixation was more efficient in a-SiC:H than in a-C:H substrate. Results in good agreement with those described above have been obtained by exposing a - C:H and a - SiC:H samples to the scrape off layer of the tokamak of Varennes (TdeV, Canada). A modelling of hydrogen diffusion under irradiation has been also proposed. (author)

  16. Shock absorber

    International Nuclear Information System (INIS)

    Housman, J.J.


    A shock absorber is described for use in a hostile environment at the end of a blind passage for absorbing impact loads. The shock absorber includes at least one element which occupies the passage and which is comprised of a porous brittle material which is substantially non-degradable in the hostile environment. A void volume is provided in the element to enable the element to absorb a predetermined level of energy upon being crushed due to impact loading

  17. The I{sub c}(H)-T{sub c}(H) phase boundary of superconducting Nb thin films with periodic and quasiperiodic antidot arrays

    Energy Technology Data Exchange (ETDEWEB)

    Bothner, D.; Kemmler, M.; Cozma, R.; Kleiner, R.; Koelle, D. [Physikalisches Institut and Center for Collective Quantum Phenomena, Universitaet Tuebingen (Germany); Misko, V.; Peeters, F. [Departement Fysica, Universiteit Antwerpen (Belgium); Nori, F. [Advanced Science Institute, RIKEN (Japan)


    The magnetic field dependent critical current I{sub c}(H) of superconducting thin films with artificial defects strongly depends on the symmetry of the defect arrangement. Likewise the critical temperature T{sub c}(H) of superconducting wire networks is heavily influenced by the symmetry of the system. Here we present experimental data on the I{sub c}(H)-T{sub c}(H) phase boundary of Nb thin films with artificial defect lattices of different symmetries. For this purpose we fabricated 60 nm thick Nb films with antidots in periodic (triangular) and five different quasiperiodic arrangements. The parameters of the antidot arrays were varied to investigate the influence of antidot diameter and array density. Experiments were performed with high temperature stability ({delta}T<1 mK) at 0.5{<=}T/T{sub c}{<=}1. From the I-V-characteristics at variable H and T we extract I{sub c}(H) and T{sub c}(H) for different voltage and resistance criteria. The experimental data for the critical current density are compared with results from numerical molecular dynamics simulations.

  18. Study of the hydrogen behavior in amorphous hydrogenated materials of type a - C:H and a - SiC:H facing fusion reactor plasma; Etude du comportament de l`hydrogene dans des materiaux amorphes hydrogenes de type a - C:H et a - SiC:H devant faire face au plasma des reacteurs a fusion

    Energy Technology Data Exchange (ETDEWEB)

    Barbier, G. [Lyon-1 Univ., 69 - Villeurbanne (France). Inst. de Physique Nucleaire


    Plasma facing components of controlled fusion test devices (tokamaks) are submitted to several constraints (irradiation, high temperatures). The erosion (physical sputtering and chemical erosion) and the hydrogen recycling (retention and desorption) of these materials influence many plasma parameters and thus affect drastically the tokamak running. First, we will describe the different plasma-material interactions. It will be pointed out, how erosion and hydrogen recycling are strongly related to both chemical and physical properties of the material. In order to reduce these interactions, we have selected two amorphous hydrogenated materials (a-C:H and a-SiC:H), which are known for their good thermal and chemical qualities. Some samples have been then implanted with lithium ions at different fluences. Our materials have been then irradiated with deuterium ions at low energy. From our results, it is shown that both the lithium implantation and the use of an a - SiC:H substrate can be beneficial in enhancing the hydrogen retention. These results were completed with thermal desorption studies of these materials. It was evidenced that the hydrogen fixation was more efficient in a-SiC:H than in a-C:H substrate. Results in good agreement with those described above have been obtained by exposing a - C:H and a - SiC:H samples to the scrape off layer of the tokamak of Varennes (TdeV, Canada). A modelling of hydrogen diffusion under irradiation has been also proposed. (author) 176 refs.

  19. Deposition and characterisation of multilayer hard coatings. Ti/TiNδ/TiCxNy/(TiC) a-C:H/(Ti) a-C:H

    International Nuclear Information System (INIS)

    Burinprakhon, T.


    Multilayer hard coatings containing Ti, TiNδ, TiC x N y , (TiC m ) a-C:H, (TiC n ) a-C:H, and (Ti) a-C:H were deposited on commercially pure titanium substrates by using an asymmetric bipolar pulsed-dc reactive magnetron sputtering of a titanium target, with Ar, Ar+N 2 , Ar+N 2 +CH 4 , and Ar+CH 4 gas mixtures. The microstructures, elemental compositions and bonding states of the interlayers and the coating surfaces were studied by using cross-sectional transmission electron microscopy (XTEM), electron energy loss spectroscopy (EELS), X-ray diffraction (XRD), Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS). The microstructure development of the multilayer coating was strongly influenced by target poisoning. As a result of the complete poisoning of the titanium target during the deposition of TiNδ and TiC x N y interlayers, the a-C:H interlayers containing graded titanium and nitrogen contents were found to develop successively to the TiC x N y interlayer without the formation of near-stoichiometric TiC. The (TiC m ) a-C:H interlayer consisted of nano-particles of distorted fcc crystal structure embedded in the a-C:H matrix. The (TiC n ) a-C:H and (Ti) a-C:H top layers were found to be a-C:H matrix without nano-particles. In the (Ti) a-C:H top layer there was no measurable amount of Ti observed, regardless of the variation of CH 4 concentration between 37.5 and 60 % flow rate in Ar+-CH4 gas mixture. The top layer (Ti) a-C:H was found to contain approximately 10 atomic % nitrogen, due to N 2 contamination during deposition caused by low conductance of N 2 through the nominally closed valve of the mass flow controller. The change of the CH 4 concentration during deposition of the top layer (Ti) a-C:H, however, showed a strong influence on the hydrogen content. The comparison of the fluorescence background of the Raman spectra revealed that hydrogen-less (Ti) a-C:H was deposited at a CH 4 concentration of less than 50 % flow rate in Ar. The hardness

  20. Structure and Friction Behavior of CrNx/a-C:H Nanocomposite Films

    Directory of Open Access Journals (Sweden)

    Lunlin Shang


    Full Text Available CrN and CrNx/a-C:H nanocomposite films were deposited on Si substrates by the magnetron sputtering technique. The structure, chemical state, and friction behavior of the CrNx/a-C:H films prepared at various CH4 content were studied systematically. The CrN film shows strong (111 and (220 orientation, while the CrNx/a-C:H films consist of the nanocrystalline CrNx or Cr particles embedded in an amorphous hydrocarbon (a-C:H matrix and show weak diffraction peaks, which is in accordance with the XPS analysis results. The typical Raman D and G peaks are observed, indicating that the separated amorphous carbon or CNx phase appears in the CrNx/a-C:H films. However, no chromium carbide was observed in all the as-deposited samples. From the SEM graphs, all the deposited films depicted a dense and compact microstructure with well-attached interface with the substrate. The average friction coefficient of the CrNx/a-C:H films largely decreased with increasing CH4 content.

  1. Electrooxidative Rhodium-Catalyzed C-H/C-H Activation: Electricity as Oxidant for Cross-Dehydrogenative Alkenylation. (United States)

    Qiu, Youai; Kong, Wei-Jun; Struwe, Julia; Sauermann, Nicolas; Rogge, Torben; Scheremetjew, Alexej; Ackermann, Lutz


    Rhodium(III) catalysis has enabled a plethora of oxidative C-H functionalizations, which predominantly employ stoichiometric amounts of toxic and/or expensive metal oxidants. In contrast, we describe the first electrochemical C-H activation by rhodium catalysis that avoids hazardous chemical oxidants. Thus, environmentally-benign twofold C-H/C-H functionalizations were accomplished with weakly-coordinating benzoic acids and benzamides, employing electricity as the terminal oxidant with H2 as the sole byproduct. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Ir-catalyzed C-H silylations of phenyldeazapurines

    Czech Academy of Sciences Publication Activity Database

    Sabat, Nazarii; Poštová Slavětínská, Lenka; Hocek, Michal


    Roč. 56, č. 49 (2015), s. 6860-6862 ISSN 0040-4039 Institutional support: RVO:61388963 Keywords : C-H silylation * deazapurines * iridium catalysis * C-H activations Subject RIV: CC - Organic Chemistry Impact factor: 2.347, year: 2015

  3. Solution and solid-phase halogen and C-H hydrogen bonding to perrhenate. (United States)

    Massena, Casey J; Riel, Asia Marie S; Neuhaus, George F; Decato, Daniel A; Berryman, Orion B


    (1)H NMR spectroscopic and X-ray crystallographic investigations of a 1,3-bis(4-ethynyl-3-iodopyridinium)benzene scaffold with perrhenate reveal strong halogen bonding in solution, and bidentate association in the solid state. A nearly isostructural host molecule demonstrates significant C-H hydrogen bonding to perrhenate in the same phases.

  4. Sound Absorbers (United States)

    Fuchs, H. V.; Möser, M.

    Sound absorption indicates the transformation of sound energy into heat. It is, for instance, employed to design the acoustics in rooms. The noise emitted by machinery and plants shall be reduced before arriving at a workplace; auditoria such as lecture rooms or concert halls require a certain reverberation time. Such design goals are realised by installing absorbing components at the walls with well-defined absorption characteristics, which are adjusted for corresponding demands. Sound absorbers also play an important role in acoustic capsules, ducts and screens to avoid sound immission from noise intensive environments into the neighbourhood.

  5. Measurement of the C / H ratio using neutrons

    International Nuclear Information System (INIS)

    Martinelli, P.


    A probe made up of a Ra (α, n) Be neutron source and a proportional counter filled with boron trifluoride has been used to measure the C/H ratio in hydrocarbons. The intensity of the thermal neutron flux in the neighbourhood of the detector increases with the concentration of the hydrocarbon hydrogen surrounding it. By measuring the density it is possible to deduce the C/H ratio. It is thus possible to evaluate the C/H ratio with a precision equal to that given by the β-ray transmission method. The errors arising from the chemical nature of the hydrocarbon can be reduced to a minimum. This method has the advantage of allowing the measurement of the C/H ratio of hydrocarbons contained in recipients or thick steel tubing by means an independent portable apparatus. (author) [fr

  6. Oxidative esterification via photocatalytic C-H activation (United States)

    Direct oxidative esterification of alcohol via photocatalytic C-H activation has been developed using VO@g-C3N4 catalyst; an expeditious esterification of alcohols occurs under neutral conditions using visible light as the source of energy.

  7. Toward Efficient Palladium-Catalyzed Allylic C-H Alkylation

    DEFF Research Database (Denmark)

    Jensen, Thomas; Fristrup, Peter


    Recent breakthroughs have proved that direct palladium (II)-catalyzed allylic C-H alkylation can be achieved. This new procedure shows that the inherent requirement for a leaving group in the Tsuji-Trost palladium-catalyzed allylic alkylation can be lifted. These initial reports hold great promise...... for the development of allylic C-H alkylation into a widely applicable methodology, thus providing a means to enhance synthetic efficiency in these reactions....

  8. General allylic C-H alkylation with tertiary nucleophiles. (United States)

    Howell, Jennifer M; Liu, Wei; Young, Andrew J; White, M Christina


    A general method for intermolecular allylic C-H alkylation of terminal olefins with tertiary nucleophiles has been accomplished employing palladium(II)/bis(sulfoxide) catalysis. Allylic C-H alkylation furnishes products in good yields (avg. 64%) with excellent regio- and stereoselectivity (>20:1 linear:branched, >20:1 E:Z). For the first time, the olefin scope encompasses unactivated aliphatic olefins as well as activated aromatic/heteroaromatic olefins and 1,4-dienes. The ease of appending allyl moieties onto complex scaffolds is leveraged to enable this mild and selective allylic C-H alkylation to rapidly diversify phenolic natural products. The tertiary nucleophile scope is broad and includes latent functionality for further elaboration (e.g., aliphatic alcohols, α,β-unsaturated esters). The opportunities to effect synthetic streamlining with such general C-H reactivity are illustrated in an allylic C-H alkylation/Diels-Alder reaction cascade: a reactive diene is generated via intermolecular allylic C-H alkylation and approximated to a dienophile contained within the tertiary nucleophile to furnish a common tricyclic core found in the class I galbulimima alkaloids.

  9. C-H activation on platinum, a mechanistic study

    International Nuclear Information System (INIS)

    Lebrilla, C.B.; Maier, W.F.


    C-H activation on heterogeneous Pt catalysts is found to be most facile at low Pt dispersion and surface structure insensitive at dispersions above 10%. Two distinct processes have been identified which lead to the formation of mono- and polydeuterated products, respectively. The ratio of mono-/polydeuteration processes increases with increasing dispersion. Evidence is provided for the formation of π-intermediates as the initiator of polydeuteration. The most facile mechanism of exchange propagation in a single molecule is through a π-allyl-type interconversion. The deuterium in monodeuterated n-hexane is located at the terminal position by high-resolution deuterium NMR. NMR spectroscopy also provides evidence for steric effects which prevent significant H/D exchange at positions close to quaternary centers. C-H activation appears to be sensitive to steric hindrance, the C-H bond energy, and the partial pressure of the substrate

  10. Rhodium(0) metalloradicals in binuclear C-H activation

    NARCIS (Netherlands)

    Puschmann, F.F.; Grützmacher, H.; de Bruin, B.


    A reactive rhodium(0) metalloradical capable of binuclear activation of an aromatic C-H bond of PPh3 is disclosed. Kinetic measurements and density functional theory calculations reveal a binuclear mechanism: two metalloradicals add to a 'double bond' of the aromatic substrate while approaching the

  11. Enzyme catalysis: C-H activation is a Reiske business (United States)

    Bruner, Steven D.


    Enzymes that selectively oxidize unactivated C-H bonds are capable of constructing complex molecules with high efficiency. A new member of this enzyme family is RedG, a Reiske-type oxygenase that catalyses chemically challenging cyclizations in the biosynthesis of prodiginine natural products.

  12. Elaboration of copper-oxygen mediated C-H activation chemistry in consideration of future fuel and feedstock generation. (United States)

    Lee, Jung Yoon; Karlin, Kenneth D


    To contribute solutions to current energy concerns, improvements in the efficiency of dioxygen mediated C-H bond cleavage chemistry, for example, selective oxidation of methane to methanol, could minimize losses in natural gas usage or produce feedstocks for fuels. Oxidative C-H activation is also a component of polysaccharide degradation, potentially affording alternative biofuels from abundant biomass. Thus, an understanding of active-site chemistry in copper monooxygenases, those activating strong C-H bonds is briefly reviewed. Then, recent advances in the synthesis-generation and study of various copper-oxygen intermediates are highlighted. Of special interest are cupric-superoxide, Cu-hydroperoxo and Cu-oxy complexes. Such investigations can contribute to an enhanced future application of C-H oxidation or oxygenation processes using air, as concerning societal energy goals. Copyright © 2015 Elsevier Ltd. All rights reserved.

  13. Iterative maximum a posteriori (IMAP-DOAS for retrieval of strongly absorbing trace gases: Model studies for CH4 and CO2 retrieval from near infrared spectra of SCIAMACHY onboard ENVISAT

    Directory of Open Access Journals (Sweden)

    C. Frankenberg


    Full Text Available In the past, differential optical absorption spectroscopy (DOAS has mostly been employed for atmospheric trace gas retrieval in the UV/Vis spectral region. New spectrometers such as SCIAMACHY onboard ENVISAT also provide near infrared channels and thus allow for the detection of greenhouse gases like CH4, CO2, or N2O. However, modifications of the classical DOAS algorithm are necessary to account for the idiosyncrasies of this spectral region, i.e. the temperature and pressure dependence of the high resolution absorption lines. Furthermore, understanding the sensitivity of the measurement of these high resolution, strong absorption lines by means of a non-ideal device, i.e. having finite spectral resolution, is of special importance. This applies not only in the NIR, but can also prove to be an issue for the UV/Vis spectral region. This paper presents a modified iterative maximum a posteriori-DOAS (IMAP-DOAS algorithm based on optimal estimation theory introduced to the remote sensing community by rodgers76. This method directly iterates the vertical column densities of the absorbers of interest until the modeled total optical density fits the measurement. Although the discussion in this paper lays emphasis on satellite retrieval, the basic principles of the algorithm also hold for arbitrary measurement geometries. This new approach is applied to modeled spectra based on a comprehensive set of atmospheric temperature and pressure profiles. This analysis reveals that the sensitivity of measurement strongly depends on the prevailing pressure-height. The IMAP-DOAS algorithm properly accounts for the sensitivity of measurement on pressure due to pressure broadening of the absorption lines. Thus, biases in the retrieved vertical columns that would arise in classical algorithms, are obviated. Here, we analyse and quantify these systematic biases as well as errors due to variations in the temperature and pressure profiles, which is indispensable for

  14. Enhancing Reactivity and Site-Selectivity in Hydrogen Atom Transfer from Amino Acid C-H Bonds via Deprotonation. (United States)

    Pipitone, Luca Maria; Carboni, Giulia; Sorrentino, Daniela; Galeotti, Marco; Salamone, Michela; Bietti, Massimo


    A kinetic study on the reactions of the cumyloxyl radical (CumO • ) with N-Boc-protected amino acids in the presence of the strong organic base DBU has been carried out. CO 2 H deprotonation increases the electron density at the α-C-H bonds activating these bonds toward HAT to the electrophilic CumO • strongly influencing the intramolecular selectivity. The implications of these results are discussed in the framework of HAT-based aliphatic C-H bond functionalization of amino acids and peptides.

  15. Catalytic alkylation of remote C-H bonds enabled by proton-coupled electron transfer. (United States)

    Choi, Gilbert J; Zhu, Qilei; Miller, David C; Gu, Carol J; Knowles, Robert R


    Despite advances in hydrogen atom transfer (HAT) catalysis, there are currently no molecular HAT catalysts that are capable of homolysing the strong nitrogen-hydrogen (N-H) bonds of N-alkyl amides. The motivation to develop amide homolysis protocols stems from the utility of the resultant amidyl radicals, which are involved in various synthetically useful transformations, including olefin amination and directed carbon-hydrogen (C-H) bond functionalization. In the latter process-a subset of the classical Hofmann-Löffler-Freytag reaction-amidyl radicals remove hydrogen atoms from unactivated aliphatic C-H bonds. Although powerful, these transformations typically require oxidative N-prefunctionalization of the amide starting materials to achieve efficient amidyl generation. Moreover, because these N-activating groups are often incorporated into the final products, these methods are generally not amenable to the direct construction of carbon-carbon (C-C) bonds. Here we report an approach that overcomes these limitations by homolysing the N-H bonds of N-alkyl amides via proton-coupled electron transfer. In this protocol, an excited-state iridium photocatalyst and a weak phosphate base cooperatively serve to remove both a proton and an electron from an amide substrate in a concerted elementary step. The resultant amidyl radical intermediates are shown to promote subsequent C-H abstraction and radical alkylation steps. This C-H alkylation represents a catalytic variant of the Hofmann-Löffler-Freytag reaction, using simple, unfunctionalized amides to direct the formation of new C-C bonds. Given the prevalence of amides in pharmaceuticals and natural products, we anticipate that this method will simplify the synthesis and structural elaboration of amine-containing targets. Moreover, this study demonstrates that concerted proton-coupled electron transfer can enable homolytic activation of common organic functional groups that are energetically inaccessible using

  16. Carbon dioxide utilization via carbonate-promoted C-H carboxylation. (United States)

    Banerjee, Aanindeeta; Dick, Graham R; Yoshino, Tatsuhiko; Kanan, Matthew W


    Using carbon dioxide (CO2) as a feedstock for commodity synthesis is an attractive means of reducing greenhouse gas emissions and a possible stepping-stone towards renewable synthetic fuels. A major impediment to synthesizing compounds from CO2 is the difficulty of forming carbon-carbon (C-C) bonds efficiently: although CO2 reacts readily with carbon-centred nucleophiles, generating these intermediates requires high-energy reagents (such as highly reducing metals or strong organic bases), carbon-heteroatom bonds or relatively acidic carbon-hydrogen (C-H) bonds. These requirements negate the environmental benefit of using CO2 as a substrate and limit the chemistry to low-volume targets. Here we show that intermediate-temperature (200 to 350 degrees Celsius) molten salts containing caesium or potassium cations enable carbonate ions (CO3(2-)) to deprotonate very weakly acidic C-H bonds (pKa > 40), generating carbon-centred nucleophiles that react with CO2 to form carboxylates. To illustrate a potential application, we use C-H carboxylation followed by protonation to convert 2-furoic acid into furan-2,5-dicarboxylic acid (FDCA)--a highly desirable bio-based feedstock with numerous applications, including the synthesis of polyethylene furandicarboxylate (PEF), which is a potential large-scale substitute for petroleum-derived polyethylene terephthalate (PET). Since 2-furoic acid can readily be made from lignocellulose, CO3(2-)-promoted C-H carboxylation thus reveals a way to transform inedible biomass and CO2 into a valuable feedstock chemical. Our results provide a new strategy for using CO2 in the synthesis of multi-carbon compounds.

  17. Direct Electrophilic C-H Alkynylation of Unprotected 2-Vinylanilines. (United States)

    Caspers, Lucien D; Finkbeiner, Peter; Nachtsheim, Boris J


    Unprotected aromatic amines can be used as directing groups in metal-catalyzed C-H alkynylations of alkenes. By using low amounts of an Ir III catalyst in combination with alkynylbenziodoxolones as electrophilic alkyne-transfer reagents, highly desirable 1,3-enynes were isolated in excellent yields of up to 98 % with Z stereoselectivity. A broad substrate scope as well as the high synthetic utility of the 1,3-enynes render this new method an efficient approach for the synthesis of five- and six-membered heterocycles. Further derivatizations of the 1,3-enynes to highly substituted quinolines through Au I - and N-bromosuccinimide-mediated exo-dig cyclizations were demonstrated. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Molecular Dynamics of Dimethyldioxirane C-H Oxidation. (United States)

    Yang, Zhongyue; Yu, Peiyuan; Houk, K N


    We report molecular dynamics simulations of the reaction of dimethyldioxirane (DMDO) with isobutane. The reaction involves hydrogen atom abstraction in the transition state, and trajectories branch to the oxygen rebound pathway, which gives tert-butanol and acetone, or a separated radical pair. In the gas phase, only 10% of the reactive trajectories undergo the oxygen rebound pathway, but this increases to 90% in simulations in an implicit acetone solvent (SMD) because the oxygen rebound becomes barrierless in solution. Short-lived diradical species were observed in the oxygen rebound trajectories. The time gap between C-H bond-breaking and C-O bond formation ranges from 30 to 150 fs, close to the <200 fs lifetime of radical pairs from DMDO hydroxylation of trans-1-phenyl-2-ethylcyclopropane measured by Newcomb.

  19. Magnetic field effects on microwave absorbing materials (United States)

    Goldberg, Ira; Hollingsworth, Charles S.; Mckinney, Ted M.


    The objective of this program was to gather information to formulate a microwave absorber that can work in the presence of strong constant direct current (DC) magnetic fields. The program was conducted in four steps. The first step was to investigate the electrical and magnetic properties of magnetic and ferrite microwave absorbers in the presence of strong magnetic fields. This included both experimental measurements and a literature survey of properties that may be applicable to finding an appropriate absorbing material. The second step was to identify those material properties that will produce desirable absorptive properties in the presence of intense magnetic fields and determine the range of magnetic field in which the absorbers remain effective. The third step was to establish ferrite absorber designs that will produce low reflection and adequate absorption in the presence of intense inhomogeneous static magnetic fields. The fourth and final step was to prepare and test samples of such magnetic microwave absorbers if such designs seem practical.

  20. C-H nickellation of phenol-derived phosphinites: regioselectivity and structures of cyclonickellated complexes. (United States)

    Mangin, Loïc P; Zargarian, Davit


    This report describes the results of a study on the ortho-C-H nickellation of the aryl phosphinites i-Pr 2 P(OAr) derived from the following four groups of substituted phenols: 3-R-C 6 H 4 OH (R = F (b), Me (c), MeO (d), Cl (e)); 3,5-R 2 -C 6 H 3 OH (R = F (f), Me (g), Cl (h), OMe (i)); 2-R-C 6 H 4 OH (R = Me (j), Ph(k)); and 2,6-R 2 -C 6 H 3 OH (R = Me (l), Ph (m)). No nickellation was observed with the phosphinites derived from the 3,5-disubstituted phenols g and h, and the 2,6-disubstituted phenols l and m; in all other cases nickellation occurred at an ortho-C-H to generate either the Br-bridged dimers [{κ P ,κ C -(i-Pr) 2 POAr}Ni(μ-Br)] 2 (1b-1f, 1j, and 1k) or the monomeric acetonitrile adduct {κ P ,κ C -ArOP(i-Pr) 2 }Ni(Br)(NCMe) (1i-NCMe). Analysis of C-H nickellation regioselectivity with 3-R-C 6 H 4 OH pointed to the importance of substituent sterics, not electronics: nickellation occurred at the least hindered position either exclusively (for R = Me (c), MeO(d), and Cl (e)) or predominantly (for R = F (b); 6 : 1). This conclusion is also consistent with the observation that C-H nickellation is possible with the 3,5-disubstituted aryl phosphinites bearing F and OMe, but not with the more bulky substituents Me or Cl. For the 2-substituted aryl phosphinites, C-H nickellation occurs at the unsubstituted ortho-C-H and not on the R substituent, regardless of whether the alternative C-H moiety of the substituent is sp 3 (R = Me (j)) or sp 2 (R = Ph (k)). The system thus reveals a strong preference for formation of 5-membered metallacycles. Consistent with this reactivity, no nickellation occurs with (2,6-R 2 -C 6 H 3 O)P(i-Pr) 2 . Tests with the parent dimer derived from i-Pr 2 P(OPh) showed that conversion to the monomeric acetonitrile adduct is highly favored, going to completion with only a small excess of MeCN. All new cyclonickellated complexes reported in this study were fully characterized, including by single crystal X-ray diffraction studies

  1. Bend-absorbing clamp (United States)

    Abbott, J. R.; Valencia, B., Jr.


    Compact, inexpensive clamp for flexible cables or rigid tubes absorbs vibrations and other motion. It accomodates wide range of dimensions, and saves space by eliminating pigtails or bellows commonly used to absorb linear movement or vibrations

  2. Metal-free oxidative olefination of primary amines with benzylic C-H bonds through direct deamination and C-H bond activation. (United States)

    Gong, Liang; Xing, Li-Juan; Xu, Tong; Zhu, Xue-Ping; Zhou, Wen; Kang, Ning; Wang, Bin


    An oxidative olefination reaction between aliphatic primary amines and benzylic sp(3) C-H bonds has been achieved using N-bromosuccinimide as catalyst and tert-butyl hydroperoxide as oxidant. The olefination proceeds under mild metal-free conditions through direct deamination and benzylic C-H bond activation, and provides easy access to biologically active 2-styrylquinolines with (E)-configuration.

  3. Tribological Performance of Hydrogenated Amorphous Carbon (a-C: H DLC Coating when Lubricated with Biodegradable Vegetal Canola Oil

    Directory of Open Access Journals (Sweden)

    H.M. Mobarak


    Full Text Available Increasing environmental awareness and demands for lowering energy consumptions are strong driving forces behind the development of the vehicles of tomorrow. Without the advances of lubricant chemistry and adequate lubricant formulation, expansion of modern engines would not have been possible. Considering environmental awareness factors as compared to mineral oils, vegetal oil based biolubricants are renewable, biodegradable, non-toxic and have a least amount of greenhouse gases. Furthermore, improvement in engine performance and transmission components, which were impossible to achieve by applying only lubricants design, is now possible through diamond like carbon (DLC coatings. DLC coatings exhibit brilliant tribological properties, such as good wear resistance and low friction. In this regard, tribological performance of a-C: H DLC coating when lubricated with Canola vegetal oil has been investigated by the help of a ball-on-flat geometry. Experimental results demonstrated that the a-C: H DLC coating exhibited better performance with Canola oil in terms of friction and wear as compared to the uncoated materials. Large amount of polar components in the Canola oil significantly improved the tribological properties of the a-C:H coating. Thus, usage of a-C: H DLC coating with Canola oil in the long run may have a positive impact on engine life.

  4. Recoverable neutron absorbers

    International Nuclear Information System (INIS)

    Keay, R.T.; Williams, J.A.


    In the reprocessing of irradiated nuclear fuel elements the nuclear fuel material is separated from the material which forms the remainder of the elements by dissolving the nuclear fuel material in nitric acid. Neutron absorbers are added to control criticality. The neutron absorbers comprise pellets each having a core of neutron absorbing material encased in a sheath of a material which is resistant to attack by acid, the core or sheath being magnetic. The sheath protects the core of neutron absorbing material from attack by the acid and the magnetic content of the core or sheath enables the absorbers to be recovered for reuse by magnetic separation techniques. (author)

  5. Enzyme-controlled nitrogen-atom transfer enables regiodivergent C-H amination. (United States)

    Hyster, Todd K; Farwell, Christopher C; Buller, Andrew R; McIntosh, John A; Arnold, Frances H


    We recently demonstrated that variants of cytochrome P450BM3 (CYP102A1) catalyze the insertion of nitrogen species into benzylic C-H bonds to form new C-N bonds. An outstanding challenge in the field of C-H amination is catalyst-controlled regioselectivity. Here, we report two engineered variants of P450BM3 that provide divergent regioselectivity for C-H amination-one favoring amination of benzylic C-H bonds and the other favoring homo-benzylic C-H bonds. The two variants provide nearly identical kinetic isotope effect values (2.8-3.0), suggesting that C-H abstraction is rate-limiting. The 2.66-Å crystal structure of the most active enzyme suggests that the engineered active site can preorganize the substrate for reactivity. We hypothesize that the enzyme controls regioselectivity through localization of a single C-H bond close to the iron nitrenoid.

  6. Cobalt-Catalyzed Tandem C-H Activation/C-C Cleavage/C-H Cyclization of Aromatic Amides with Alkylidenecyclopropanes. (United States)

    Li, Mingliang; Kwong, Fuk Yee


    A cobalt-catalyzed chelation-assisted tandem C-H activation/C-C cleavage/C-H cyclization of aromatic amides with alkylidenecyclopropanes (ACPs) is reported. This process allows the sequential formation of two C-C bonds, in which it is in sharp contrast to previous report of using Rh catalyst for the formation of C-N bond. Here the inexpensive catalyst system exhibits good functional group compatibility and relatively broad substrate scope. The desired products can be easily transformed into polycyclic lactones with m-CPBA. Mechanistic studies revealed that the tandem reaction proceeds through a sequential C-H cobaltation, β-carbon elimination and intramolecular C-H cobaltation pathway. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Ligand-controlled, tunable silver-catalyzed C-H amination. (United States)

    Alderson, Juliet M; Phelps, Alicia M; Scamp, Ryan J; Dolan, Nicholas S; Schomaker, Jennifer M


    The development of readily tunable and regioselective C-H functionalization reactions that operate solely through catalyst control remains a challenge in modern organic synthesis. Herein, we report that simple silver catalysts supported by common nitrogenated ligands can be used to tune a nitrene transfer reaction between two different types of C-H bonds. The results reported herein represent the first example of ligand-controlled and site-selective silver-promoted C-H amination.

  8. Selective Palladium(II)-Catalyzed Carbonylation of Methylene β-C-H Bonds in Aliphatic Amines. (United States)

    Cabrera-Pardo, Jaime R; Trowbridge, Aaron; Nappi, Manuel; Ozaki, Kyohei; Gaunt, Matthew J


    Palladium(II)-catalyzed C-H carbonylation reactions of methylene C-H bonds in secondary aliphatic amines lead to the formation of trans-disubstituted β-lactams in excellent yields and selectivities. The generality of the C-H carbonylation process is aided by the action of xantphos-based ligands and is important in securing good yields for the β-lactam products. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Conformation-induced remote meta-C-H activation of amines (United States)

    Tang, Ri-Yuan; Li, Gang; Yu, Jin-Quan


    Achieving site selectivity in carbon-hydrogen (C-H) functionalization reactions is a long-standing challenge in organic chemistry. The small differences in intrinsic reactivity of C-H bonds in any given organic molecule can lead to the activation of undesired C-H bonds by a non-selective catalyst. One solution to this problem is to distinguish C-H bonds on the basis of their location in the molecule relative to a specific functional group. In this context, the activation of C-H bonds five or six bonds away from a functional group by cyclometallation has been extensively studied. However, the directed activation of C-H bonds that are distal to (more than six bonds away) functional groups has remained challenging, especially when the target C-H bond is geometrically inaccessible to directed metallation owing to the ring strain encountered in cyclometallation. Here we report a recyclable template that directs the olefination and acetoxylation of distal meta-C-H bonds--as far as 11 bonds away--of anilines and benzylic amines. This template is able to direct the meta-selective C-H functionalization of bicyclic heterocycles via a highly strained, tricyclic-cyclophane-like palladated intermediate. X-ray and nuclear magnetic resonance studies reveal that the conformational biases induced by a single fluorine substitution in the template can be enhanced by using a ligand to switch from ortho- to meta-selectivity.

  10. Reactively co-sputter deposited a-C:H/Cr thin films: Material characteristics and optical properties

    International Nuclear Information System (INIS)

    Cheng, Hsin-Yen; Chiou, Jau-Wern; Ting, Jyh-Ming; Tzeng, Yonhua


    Various chromium-containing amorphous hydrogenated carbon (a-C:H/Cr) coatings were deposited on oxygen-free copper and silicon substrates for use as solar selective absorber coatings. The deposition was performed using a magnetron co-sputter deposition method under various methane/Ar ratios, ranging from 0 to 8%. The obtained films were characterized using glazing incident X-ray diffraction, scanning electron microscopy, high-resolution transmission electron microscopy, secondary ion mass spectrometer, and X-ray photoelectron spectroscopy. The optical absorptance and emittance at 100 °C were determined using UV–vis-NIR spectroscopy and Fourier transform infrared spectrometry, respectively. Effects of the material characteristics on the optical properties are reported and discussed. - Highlights: ► a-C:H/Cr coatings were prepared using reactive magnetron co-sputtering deposition. ► Cr exists as crystallites having diameters in between 1 to 2 nm. ► Coating prepared with 3% methane in the gas fed exhibits the best optical absorptance

  11. Reactively co-sputter deposited a-C:H/Cr thin films: Material characteristics and optical properties

    Energy Technology Data Exchange (ETDEWEB)

    Cheng, Hsin-Yen [Department of Materials Science and Engineering, National Cheng Kung University, 1 University Road, Tainan 701, Taiwan (China); Chiou, Jau-Wern [Department of Applied Physics, National University of Kaohsiung, Kaohsiung University Rd., Nanzih District, Kaohsiung 811, Taiwan (China); Ting, Jyh-Ming, E-mail: [Department of Materials Science and Engineering, National Cheng Kung University, 1 University Road, Tainan 701, Taiwan (China); Institute of Nanotechnology and Microsystems Engineer, National Cheng Kung University, 1 University Road, Tainan 701, Taiwan (China); Center for Micro/Nano Science and Technology, National Cheng Kung University, 1 University Road, Tainan 701, Taiwan (China); Tzeng, Yonhua [Institute of Nanotechnology and Microsystems Engineer, National Cheng Kung University, 1 University Road, Tainan 701, Taiwan (China); Center for Micro/Nano Science and Technology, National Cheng Kung University, 1 University Road, Tainan 701, Taiwan (China); Department of Electrical Engineering, National Cheng Kung University, 1 University Road, Tainan 701, Taiwan (China)


    Various chromium-containing amorphous hydrogenated carbon (a-C:H/Cr) coatings were deposited on oxygen-free copper and silicon substrates for use as solar selective absorber coatings. The deposition was performed using a magnetron co-sputter deposition method under various methane/Ar ratios, ranging from 0 to 8%. The obtained films were characterized using glazing incident X-ray diffraction, scanning electron microscopy, high-resolution transmission electron microscopy, secondary ion mass spectrometer, and X-ray photoelectron spectroscopy. The optical absorptance and emittance at 100 °C were determined using UV–vis-NIR spectroscopy and Fourier transform infrared spectrometry, respectively. Effects of the material characteristics on the optical properties are reported and discussed. - Highlights: ► a-C:H/Cr coatings were prepared using reactive magnetron co-sputtering deposition. ► Cr exists as crystallites having diameters in between 1 to 2 nm. ► Coating prepared with 3% methane in the gas fed exhibits the best optical absorptance.

  12. Deposition and characterisation of multilayer hard coatings. Ti/TiN delta/TiC sub x N sub y /(TiC) a-C H/(Ti) a-C H

    CERN Document Server

    Burinprakhon, T


    mixture. The top layer (Ti) a-C:H was found to contain approximately 10 atomic % nitrogen, due to N sub 2 contamination during deposition caused by low conductance of N sub 2 through the nominally closed valve of the mass flow controller. The change of the CH sub 4 concentration during deposition of the top layer (Ti) a-C:H, however, showed a strong influence on the hydrogen content. The comparison of the fluorescence background of the Raman spectra revealed that hydrogen-less (Ti) a-C:H was deposited at a CH sub 4 concentration of less than 50 % flow rate in Ar. The hardness and adhesion of the multilayer coated titanium substrates were assessed by using microindentation hardness and scratch tests, respectively. A simple hardness model containing parameters that assess the contributions from the coating and the substrate to the measured hardness was developed to describe hardness variation as a function of indentation size. This model allowed the determination of a coating hardness and an effective substrate...

  13. Semiconductor saturable absorbers for ultrafast terahertz signals

    DEFF Research Database (Denmark)

    Hoffmann, Matthias C.; Turchinovich, Dmitry


    We demonstrate saturable absorber behavior of n-type semiconductors GaAs, GaP, and Ge in the terahertz THz frequency range at room temperature using nonlinear THz spectroscopy. The saturation mechanism is based on a decrease in electron conductivity of semiconductors at high electron momentum...... states, due to conduction band onparabolicity and scattering into satellite valleys in strong THz fields. Saturable absorber parameters, such as linear and nonsaturable transmission, and saturation fluence, are extracted by fits to a classic saturable absorber model. Further, we observe THz pulse...

  14. Thermodynamic design of a high temperature chemical vapor deposition process to synthesize α-SiC in Si-C-H and Si-C-H-Cl systems (United States)

    Kang, Yura; Yoo, Chang-Hyoung; Nam, Deok-Hui; Lee, Myung-Hyun; Seo, Won-Seon; Hong, Suklyun; Jeong, Seong-Min


    In this study, we thermodynamically reviewed the suitable growth process conditions of α-SiC in the Si-C-H system using tetramethylsilane (TMS) and in the Si-C-H-Cl system using methyltrichlorosilane (MTS). In the Si-C-H-Cl system, pure solid SiC was obtained at high temperatures under a larger range of hydrogen dilution ratios than that tolerated in the Si-C-H system. X-ray diffraction and micro-Raman analysis of the products obtained at 1900, 2000, and 2100 °C showed that the α-SiC becomes more dominant with increasing temperature in the Si-C-H-Cl system. While TMS was unsuitable for high temperature processing due to its high C/Si ratio, MTS was found to be appropriate for growing α-SiC crystals at high temperatures under a range of conditions. These results indicate that a novel method to grow α-SiC single crystals through HTCVD using MTS as a precursor could be established.

  15. Breakdown of the Coulomb friction law in TiC/a-C : H nanocomposite coatings

    NARCIS (Netherlands)

    Pei, Y.T.; Huizenga, P.; Galvan, D.; Hosson, J.Th.M. De


    Advanced TiC/a-C:H nanocomposite coatings have been produced via reactive deposition in a closed-field unbalanced magnetron sputtering system (Hauzer HTC-1000 or HTC 1200). In this paper, we report on the tribological behavior of TiC/a-C:H nanocomposite coatings in which ultralow friction is

  16. Influence of nitrogen doping on different properties of a-C : H

    NARCIS (Netherlands)

    Hauert, R.; Glisenti, A.; Metin, S.; Goitia, J.; Kaufman, J.H.; Loosdrecht, P.H.M. van; Kellock, A.J.; Hoffmann, P.; White, R.L.; Hermsmeier, B.D.


    Amorphous hydrogenated carbon (a-C:H) exhibits outstanding properties such as high hardness, low mechanical wear and friction, high thermal conductivity, etc. These properties are irreversibly altered above 400 °C. Doping the a-C:H films with nitrogen revealed the possibility to continuously tune

  17. Selective sp3 C-H alkylation via polarity-match-based cross-coupling (United States)

    Le, Chip; Liang, Yufan; Evans, Ryan W.; Li, Ximing; MacMillan, David W. C.


    The functionalization of carbon-hydrogen (C-H) bonds is one of the most attractive strategies for molecular construction in organic chemistry. The hydrogen atom is considered to be an ideal coupling handle, owing to its relative abundance in organic molecules and its availability for functionalization at almost any stage in a synthetic sequence. Although many C-H functionalization reactions involve C(sp3)-C(sp2) coupling, there is a growing demand for C-H alkylation reactions, wherein sp3 C-H bonds are replaced with sp3 C-alkyl groups. Here we describe a polarity-match-based selective sp3 C-H alkylation via the combination of photoredox, nickel and hydrogen-atom transfer catalysis. This methodology simultaneously uses three catalytic cycles to achieve hydridic C-H bond abstraction (enabled by polarity matching), alkyl halide oxidative addition, and reductive elimination to enable alkyl-alkyl fragment coupling. The sp3 C-H alkylation is highly selective for the α-C-H of amines, ethers and sulphides, which are commonly found in pharmaceutically relevant architectures. This cross-coupling protocol should enable broad synthetic applications in de novo synthesis and late-stage functionalization chemistry.

  18. Selective sp3 C-H alkylation via polarity-match-based cross-coupling. (United States)

    Le, Chip; Liang, Yufan; Evans, Ryan W; Li, Ximing; MacMillan, David W C


    The functionalization of carbon-hydrogen (C-H) bonds is one of the most attractive strategies for molecular construction in organic chemistry. The hydrogen atom is considered to be an ideal coupling handle, owing to its relative abundance in organic molecules and its availability for functionalization at almost any stage in a synthetic sequence. Although many C-H functionalization reactions involve C(sp 3 )-C(sp 2 ) coupling, there is a growing demand for C-H alkylation reactions, wherein sp 3 C-H bonds are replaced with sp 3 C-alkyl groups. Here we describe a polarity-match-based selective sp 3 C-H alkylation via the combination of photoredox, nickel and hydrogen-atom transfer catalysis. This methodology simultaneously uses three catalytic cycles to achieve hydridic C-H bond abstraction (enabled by polarity matching), alkyl halide oxidative addition, and reductive elimination to enable alkyl-alkyl fragment coupling. The sp 3 C-H alkylation is highly selective for the α-C-H of amines, ethers and sulphides, which are commonly found in pharmaceutically relevant architectures. This cross-coupling protocol should enable broad synthetic applications in de novo synthesis and late-stage functionalization chemistry.

  19. Pd(II)-Catalyzed Enantioselective C-H Olefination of Diphenylacetic Acids (United States)

    Shi, Bing-Feng; Zhang, Yang-Hui; Lam, Jonathan K.; Wang, Dong-Hui; Yu, Jin-Quan


    Pd(II)-catalyzed enantioselective C-H olefination of diphenylacetic acid substrates has been achieved through the use of mono-protected chiral amino acid ligands. The absolute configuration of the resulting olefinated products is consistent with that of a proposed C-H insertion intermediate. PMID:20017549

  20. S,O-Ligand-Promoted Palladium-Catalyzed C-H Functionalization Reactions of Nondirected Arenes

    NARCIS (Netherlands)

    Naksomboon, K.; Valderas, C.; Gomez-Martinez, M.; Alvarez-Casao, Y.; Fernández Ibáñez, M.A.

    Pd(II)-catalyzed C-H functionalization of non directed arenes has been realized using an inexpensive and easily accessible type of bidentate S,O-ligand. The catalytic system shows high efficiency in the C-H olefination reaction of electron-rich and electron-poor arenes. This methodology is

  1. Advanced TiC/a-C : H nanocomposite coatings deposited by magnetron sputtering

    NARCIS (Netherlands)

    Pei, Y.T.; Galvan, D.; Hosson, J.Th.M. De; Strondl, C.


    TiC/a-C:H nanocomposite coatings have been deposited by magnetron Sputtering. They consist of 2-5 nm TiC nanocrystallites embedded in the amorphous hydrocarbon (a-C:H) matrix. A transition from a Columnar to a glassy microstructure has been observed in the nanocomposite coatings with increasing

  2. Absorber manufacturing made easy

    Energy Technology Data Exchange (ETDEWEB)

    Berner, Joachim


    Whether by means of a laser source or an ultrasound head - automation technology is making progress in the solar thermal sector. S and WE presents news developments in welding technology in absorber manufacture. (orig.)

  3. PWR burnable absorber evaluation

    International Nuclear Information System (INIS)

    Cacciapouti, R.J.; Weader, R.J.; Malone, J.P.


    The purpose of the study was to evaluate the relative neurotic efficiency and fuel cycle cost benefits of PWR burnable absorbers. Establishment of reference low-leakage equilibrium in-core fuel management plans for 12-, 18- and 24-month cycles. Review of the fuel management impact of the integral fuel burnable absorber (IFBA), erbium and gadolinium. Calculation of the U 3 O 8 , UF 6 , SWU, fuel fabrication, and burnable absorber requirements for the defined fuel management plans. Estimation of fuel cycle costs of each fuel management plan at spot market and long-term market fuel prices. Estimation of the comparative savings of the different burnable absorbers in dollar equivalent per kgU of fabricated fuel. (author)

  4. TOMS Absorbing Aerosol Index (United States)

    Washington University St Louis — TOMS_AI_G is an aerosol related dataset derived from the Total Ozone Monitoring Satellite (TOMS) Sensor. The TOMS aerosol index arises from absorbing aerosols such...

  5. Adsorption of alcohols and fatty acids onto hydrogenated (a-C:H) DLC coatings (United States)

    Simič, R.; Kalin, M.; Kovač, J.; Jakša, G.


    Information about the interactions between lubricants and DLC coatings is scarce, despite there having been many studies over the years. In this investigation we used ToF-SIMS, XPS and contact-angle analyses to examine the adsorption ability and mechanisms with respect to two oiliness additives, i.e., hexadecanol and hexadecanoic acid, on an a-C:H coating. In addition, we analyzed the resistance of the adsorbed films to external influences like solvent cleaning. The results show that both molecules adsorb onto surface oxides and hydroxides present on the initial DLC surface and shield these structures with their hydrocarbon tails. This makes the surfaces less polar, which is manifested in a smaller polar component of the surface energy. We also showed that ultrasonic cleaning in heptane has no significant effect on the quantity of adsorbed molecules or on their chemical state. This not only shows the relatively strong adsorption of these molecules, but also provides useful information for future experimental work. Of the two examined molecules, the acid showed a greater adsorption ability than the alcohol, which explains some of the previously reported better tribological properties in the case of the acid with respect to the alcohol.

  6. Observation of Weak C-H...O Hydrogen Bonding by Unactivated Alkanes

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Xue B.; Woo, Hin-koon; Boggavarapu, Kiran; Wang, Lai S.


    Weak C-H...O hydrogen bonding has been recognized to play a major role in biological molecular structures and functions. A newly developed low-temperature photoelectron spectroscopy apparatus is used here to study the C-H...O hydrogen bonding between unactivated alkanes and the carboxylate functional group. We observed that gaseous linear carboxylates, CH3(CH2)nCO2-, assume folded structures at low temperatures due to weak C-H...O hydrogen bonding between the terminal CH3 and CO2- groups for n-5. Temperature-dependent studies showed that the folding transition depends on both the temperature and the aliphatic chain length. Theoretical calculations revealed that for n = 3-8, the folded conformations are more stable than the linear structures, but C-H...O hydrogen bonding only forms for species with n-5 due to steric constraint in the smaller species. One C-H...O hydrogen-bond is formed in the n = 5 and 6 species, whereas two C-H...O hydrogen-bonds are formed for n = 7 and 8. Comparison of the photoelectron spectral shifts for the folded relative to the linear conformations yielded lower limits for the strength of the C-H...O hydrogen-bonds in CH3(CH2)nCO2-, ranging from 1.2 kcal/mol for n = 5 to 4.4 kcal/mol for n = 8.

  7. Rhodium(III)-Catalyzed Imidoyl C-H Activation for Annulations to Azolopyrimidines. (United States)

    Halskov, Kim Søholm; Witten, Michael R; Hoang, Gia L; Mercado, Brandon Q; Ellman, Jonathan A


    Azolopyrimidines are efficiently prepared by direct imidoyl C-H bond activation. Annulations of N-azolo imines with sulfoxonium ylides and diazoketones under redox-neutral conditions and alkynes under oxidizing conditions provide products with various arrangements of nitrogen atoms and carbon substituents. We have also probed the mechanism of this first example of Rh(III)-catalyzed direct imidoyl C-H activation by structural characterization of a catalytically competent rhodacycle obtained after C-H activation and by kinetic isotope effects.

  8. Iridium/Bipyridine-Catalyzed ortho-Selective C-H Borylation of Phenol and Aniline Derivatives. (United States)

    Li, Hong-Liang; Kanai, Motomu; Kuninobu, Yoichiro


    An iridium-catalyzed ortho-selective C-H borylation of phenol and aniline derivatives has been successfully developed. Iridium/bipyridine-catalyzed C-H borylation generally occurred at the meta- and para-positions of aromatic substrates. Introduction of an electron-withdrawing substituent on the bipyridine-type ligand and a methylthiomethyl group on the hydroxy and amino groups of the phenol and aniline substrates, however, dramatically altered the regioselectivity, affording exclusively ortho-borylated products. The reaction proceeded in good to excellent yields with good functional group tolerance. C-H borylation was applied to the synthesis of a calcium receptor modulator.

  9. The preparation and mechanical properties of Al-containing a-C : H thin films

    International Nuclear Information System (INIS)

    Zhang Guangan; Yan Pengxun; Wang Peng; Chen Youming; Zhang Junyan


    Al-containing hydrogenated amorphous carbon (Al-C : H) films were deposited on silicon substrates using a mid frequency magnetron sputtering Al target in an argon and methane gas mixture. The composition, surface morphology, hardness and friction coefficient of the films were characterized using x-ray photoelectron spectroscopy, atomic force microscopy, nanoindentation and tribological tester. The Al-C : H films deposited at low CH 4 content show high surface roughness, low hardness and high friction coefficient, similar to metallic Al films; in contrast, the Al-C : H films prepared under high CH 4 content indicate low surface roughness, high hardness and low friction coefficient, close to that of hard a-C : H films as wear-resistance films

  10. Synthesis of Dihydropyridines and Pyridines from Imines and Alkynes via C-H Activation

    Energy Technology Data Exchange (ETDEWEB)

    Ellman, Jonathan A.; Colby, Denise; Bergman, Robert


    A convenient one-pot C-H alkenylation/electrocyclization/aromatization sequence has been developed for the synthesis of highly substituted pyridine derivatives from alkynes and {alpha},{beta}-unsaturated N-benzyl aldimines and ketimines that proceeds through dihydropyridine intermediates. A new class of ligands for C-H activation was developed, providing broader scope for the alkenylation step than could be achieved with previously reported ligands. Substantial information was obtained about the mechanism of the reaction. This included the isolation of a C-H activated complex and its structure determination by X-ray analysis; in addition, kinetic simulations using the Copasi software were employed to determine rate constants for this transformation, implicating facile C-H oxidative addition and slow reductive elimination steps.

  11. Pd-Catalyzed C-H Bond Functionalization on the Indole and Pyrrole Nucleus (United States)

    Beck, Elizabeth M.; Gaunt, Matthew J.

    This review details recent developments in the Pd-catalyzed C-H bond arylation and alkenylation of indoles and pyrroles, aromatic heterocycles that are frequently displayed in natural products and medicinal agents.

  12. Palladium-Catalyzed C-H Arylation of 1,2,3-Triazoles. (United States)

    Zhang, Chengwei; You, Lin; Chen, Chuo


    Palladium(II) acetate, in combination with triphenylphosphine, catalyzes direct arylation of 1,4-disubstituted 1,2,3-triazoles effectively. This C-H arylation reaction provides facile access to fully substituted triazoles with well-defined regiochemistry.

  13. Elemental (C, H, N) composition of zooplankton from north Arabian Sea

    Digital Repository Service at National Institute of Oceanography (India)

    Matondkar, S.G.P.; Bhat, K.L.; Ansari, Z.A.; Parulekar, A.H.

    Zooplankton samples collected from north Arabian Sea during March 1992 were analysed for elemental (C,H,N) composition. Estimated carbon, hydrogen and nitrogen concentrations displayed variations among different groups but their ratios were nearly...

  14. Site-selective and stereoselective functionalization of non-activated tertiary C-H bonds (United States)

    Liao, Kuangbiao; Pickel, Thomas C.; Boyarskikh, Vyacheslav; Bacsa, John; Musaev, Djamaladdin G.; Davies, Huw M. L.


    The synthesis of complex organic compounds usually relies on controlling the reactions of the functional groups. In recent years, it has become possible to carry out reactions directly on the C-H bonds, previously considered to be unreactive. One of the major challenges is to control the site-selectivity because most organic compounds have many similar C-H bonds. The most well developed procedures so far rely on the use of substrate control, in which the substrate has one inherently more reactive C-H bond or contains a directing group or the reaction is conducted intramolecularly so that a specific C-H bond is favoured. A more versatile but more challenging approach is to use catalysts to control which site in the substrate is functionalized. p450 enzymes exhibit C-H oxidation site-selectivity, in which the enzyme scaffold causes a specific C-H bond to be functionalized by placing it close to the iron-oxo haem complex. Several studies have aimed to emulate this enzymatic site-selectivity with designed transition-metal catalysts but it is difficult to achieve exceptionally high levels of site-selectivity. Recently, we reported a dirhodium catalyst for the site-selective functionalization of the most accessible non-activated (that is, not next to a functional group) secondary C-H bonds by means of rhodium-carbene-induced C-H insertion. Here we describe another dirhodium catalyst that has a very different reactivity profile. Instead of the secondary C-H bond, the new catalyst is capable of precise site-selectivity at the most accessible tertiary C-H bonds. Using this catalyst, we modify several natural products, including steroids and a vitamin E derivative, indicating the applicability of this method of synthesis to the late-stage functionalization of complex molecules. These studies show it is possible to achieve site-selectivity at different positions within a substrate simply by selecting the appropriate catalyst. We hope that this work will inspire the design of

  15. Synthesis of propargylic and allenic carbamates via the C-H amination of alkynes. (United States)

    Grigg, R David; Rigoli, Jared W; Pearce, Simon D; Schomaker, Jennifer M


    Propargylic amines are important intermediates for the synthesis of nitrogen-containing heterocycles. The insertion of a nitrene into a propargylic C-H bond has not been explored, despite the attention directed toward the Rh-catalyzed amination of other types of C-H bonds. In this communication, the conversion of a series of homopropargylic carbamates to propargylic carbamates and aminated allenes is described. © 2011 American Chemical Society

  16. Palladium-catalysed C-H activation of aliphatic amines to give strained nitrogen heterocycles (United States)

    McNally, Andrew; Haffemayer, Benjamin; Collins, Beatrice S. L.; Gaunt, Matthew J.


    The development of new chemical transformations based on catalytic functionalization of unactivated C-H bonds has the potential to simplify the synthesis of complex molecules dramatically. Transition metal catalysis has emerged as a powerful tool with which to convert these unreactive bonds into carbon-carbon and carbon-heteroatom bonds, but the selective transformation of aliphatic C-H bonds is still a challenge. The most successful approaches involve a `directing group', which positions the metal catalyst near a particular C-H bond, so that the C-H functionalization step occurs via cyclometallation. Most directed aliphatic C-H activation processes proceed through a five-membered-ring cyclometallated intermediate. Considering the number of new reactions that have arisen from such intermediates, it seems likely that identification of distinct cyclometallation pathways would lead to the development of other useful chemical transformations. Here we report a palladium-catalysed C-H bond activation mode that proceeds through a four-membered-ring cyclopalladation pathway. The chemistry described here leads to the selective transformation of a methyl group that is adjacent to an unprotected secondary amine into a synthetically versatile nitrogen heterocycle. The scope of this previously unknown bond disconnection is highlighted through the development of C-H amination and carbonylation processes, leading to the synthesis of aziridines and β-lactams (respectively), and is suggestive of a generic C-H functionalization platform that could simplify the synthesis of aliphatic secondary amines, a class of small molecules that are particularly important features of many pharmaceutical agents.

  17. Palladium catalyzed selective distal C-H olefination of biaryl systems. (United States)

    Maity, Soham; Hoque, Ehtasimul; Dhawa, Uttam; Maiti, Debabrata


    Palladium catalyzed selective distal C-H activation with nitrile based templates has been of significant research interest in recent times. In this report, we disclose the distal C-H olefination of biphenyl systems with high regio- and stereo-selectivity and useful synthetic yields. The utility of this method has been demonstrated through its wide olefin scope, its operation at the gram scale and the easy removal/recovery of the directing group.

  18. Advanced TiC/a-C: H nanocomposite coatings deposited by magnetron sputtering


    Pei, Y.T.; Galvan, D.; Hosson, J.Th.M. De; Strondl, C.


    TiC/a-C:H nanocomposite coatings have been deposited by magnetron Sputtering. They consist of 2-5 nm TiC nanocrystallites embedded in the amorphous hydrocarbon (a-C:H) matrix. A transition from a Columnar to a glassy microstructure has been observed in the nanocomposite coatings with increasing substrate bias or carbon content. Micro-cracks induced by nanoindentation or wear tests readily propagate through the column boundaries whereas the coatings without a columnar inicrostructure exhibit s...

  19. Neutron absorbing article

    International Nuclear Information System (INIS)

    Naum, R.G.; Owens, D.P.; Dooher, G.I.


    A neutron absorbing article, in flat plate form and suitable for use in a storage rack for spent fuel, includes boron carbide particles, diluent particles and a solid, irreversibly cured phenolic polymer cured to a continuous matrix binding the boron carbide and diluent particles. The total conent of boron carbide and diluent particles is a major proportion of the article and the content of cured phenolic polymer present is a minor proportion. By regulation of the ratio of boron carbide particles to diluent particles, normally within the range of 1:9 and 9:1 and preferably within the range of 1:5 to 5:1, the neutron absorbing activity of the product may be controlled, which facilitates the manufacture of articles of particular absorbing activities best suitable for specific applications

  20. Neutron absorbing article

    International Nuclear Information System (INIS)

    Naum, R.G.; Owens, D.P.; Dooker, G.I.


    A neutron-absorbing article suitable for use in spent fuel racks is described. It comprises boron carbide particles, diluent particles, and a phenolic polymer cured to a continuous matrix. The diluent may be silicon carbide, graphite, amorphous carbon, alumina, or silica. The combined boron carbide-diluent phase contains no more than 2 percent B 2 O 3 , and the neutron-absorbing article contains from 20 to 40 percent phenol resin. The ratio of boron carbide to diluent particles is in the range 1:9 to 9:1

  1. Inert C-H Bond Transformations Enabled by Organometallic Manganese Catalysis. (United States)

    Hu, Yuanyuan; Zhou, Bingwei; Wang, Congyang


    Traditional organic synthesis relies heavily on the transformations of various preinstalled functional groups, such as cross-coupling reactions using organohalides and organometallic reagents. The strategy of C-H activation enables the direct formation of C-C/C-X (X = heteroatom) bonds from inert C-H bonds, which can enhance the atom- and step-economy of organic synthesis. To date, precious metals have overwhelmingly dominated the C-H activation field; however, the rarity and high cost of these metals necessitate the development of more sustainable catalysts. In this regard, catalysts based on manganese are highly desirable owing to the abundant reserve of manganese in the earth's crust and its economic benefits, low toxicity, and potentially unique reactivity. Although the first stoichiometric manganese-mediated C-H activation reaction was reported as early as 1970, manganese-catalyzed C-H activation reactions are largely underdeveloped. How to construct an efficient catalytic cycle for manganese in C-H activation reactions remains as a key issue to be addressed. In this Account, we summarize our recent advances in the manganese-catalyzed transformations of inert C-H bonds. To overcome the challenges associated with building manganese-based catalytic cycles, we developed two novel strategies, namely, synergy between manganese catalysts and bases and between manganese catalysts (with or w/o bases) and acids. By implementing the former strategy, we developed cooperative manganese/base catalytic systems that facilitate a new mode of C-H bond activation by manganese via a redox-neutral base-assisted deprotonation mechanism. As such, the requirement for the tedious preparation of MnR(CO) 5 complexes (R = Me, Bn, Ph) in stoichiometric reactions was eliminated, and a series of manganese-catalyzed C-H activation reactions of arenes with various reaction partners having C≡C and C═C bonds were achieved. Through the latter strategy of synergy between manganese catalysts

  2. Behavior of rats treated with Rhus toxicodendron 200cH Conducta da ratones tratados con Rhus toxicodendron 200cH Conduta de ratos tratados com Rhus toxicodendron 200cH


    Leoni Villano Bonamin; Lucienne Colombo Martini; Fernanda Martins Soares; Marcos Paulo da Silva Rocha


    One of the main pathogenetic characteristics of Rhus toxicodendron (Rhus-t) is the presence of articular pain and aggravation on standing, which improve only by motion. The present study proposes an experimental model to evaluate the action of Rhus-t 200cH. Rats were divided into 3 groups according to treatment received (Rhus-t, diazepam and water); each group was further divided into two sub-groups according to the initial pattern of behavior (hyperactive and hypoactive) as assessed by open...

  3. Absorber for nuclear radiations

    International Nuclear Information System (INIS)

    Planchamp, C.


    Neutrons, gamma and x radiations are highly absorbed by an alloy of gadolinium and aluminium. Workability, thermal conductivity, mechanical properties, corrosion resistance of the alloy are good. Possible applications are transport or storage of radioactive wastes or nuclear fuels, fuel racks, shelters, etc [fr

  4. Low Absorbance Measurements (United States)

    Harris, T. D.; Williams, A. M.


    The application of low absorption measurements to dilute solute determination requires specific instrumental characteristics. The use of laser intracavity absorption and thermal lens calorimetry to measure concentration is shown. The specific operating parameters that determine sensitivity are delineated along with the limits different measurement strategies impose. Finally areas of improvement in components that would result in improve sensitivity, accuracy, and reliability are discussed. During the past decade, a large number of methods have been developed for measuring the light absorbed by transparent materials. These include measurements on gases, liquids, and solids. The activity has been prompted by a variety of applications and a similar variety of disciplines. In Table 1 some representative examples of these methods is shown along with their published detection limits.1 It is clear that extraordinarily small absorbances can be measured. Most of the methods can be conveniently divided into two groups. These groups are those that measure the transmission of the sample and those that measure the light absorbed by the sample. The light absorbed methods are calorimetric in character. The advantages and disadvantages of each method varies depending on the principal application for which they were developed. The most prevalent motivation has been to characterize the bulk optical properties of transparent materials. Two examples are the development of extremely transparent glasses for use as fiber optic materials and the development of substrates for high power laser operation.

  5. Absorbance and electrochemical properties of natural indigo dye (United States)

    Basuki, Suyitno, Kristiawan, Budi


    The objective of study is to investigate the absorbance and electrochemical properties of natural indigo dyes. The natural indigo dyes were extracted from Indigofera tinctoria leaves. The solution was kept in alkaline condition and the reductor used was Sodium dithionite (Na2S2O4). The absorbance and electrochemical properties were tested by ultraviolet-visible (UV-Vis) spectrophotometry, Fourier transform infrared (FTIR) spectroscopy, and cyclic voltammetry (CV). The results show that the absorbance spectrum of dyes was at a wavelength from 375 to 475. The dyes also have C=C, C-H, and C-N which important for anchoring in semiconductors. Moreover, the level energy of highest occupied molecular orbital and that of lowest unoccupied molecular orbital from indigo dyes were -4.89 eV and -4.035 eV, respectively. The findings show that the natural indigo dye has promising properties for dyeing of photo-anode in solar energy harvester.

  6. Ligand-accelerated non-directed C-H functionalization of arenes (United States)

    Wang, Peng; Verma, Pritha; Xia, Guoqin; Shi, Jun; Qiao, Jennifer X.; Tao, Shiwei; Cheng, Peter T. W.; Poss, Michael A.; Farmer, Marcus E.; Yeung, Kap-Sun; Yu, Jin-Quan


    The directed activation of carbon-hydrogen bonds (C-H) is important in the development of synthetically useful reactions, owing to the proximity-induced reactivity and selectivity that is enabled by coordinating functional groups. Palladium-catalysed non-directed C-H activation could potentially enable further useful reactions, because it can reach more distant sites and be applied to substrates that do not contain appropriate directing groups; however, its development has faced substantial challenges associated with the lack of sufficiently active palladium catalysts. Currently used palladium catalysts are reactive only with electron-rich arenes, unless an excess of arene is used, which limits synthetic applications. Here we report a 2-pyridone ligand that binds to palladium and accelerates non-directed C-H functionalization with arene as the limiting reagent. This protocol is compatible with a broad range of aromatic substrates and we demonstrate direct functionalization of advanced synthetic intermediates, drug molecules and natural products that cannot be used in excessive quantities. We also developed C-H olefination and carboxylation protocols, demonstrating the applicability of our methodology to other transformations. The site selectivity in these transformations is governed by a combination of steric and electronic effects, with the pyridone ligand enhancing the influence of sterics on the selectivity, thus providing complementary selectivity to directed C-H functionalization.

  7. Isotopic Effects on Stereodynamics of the C+ + H2 → CH+ + H Reaction (United States)

    Guo, Lu; Yang, Yun-Fan; Fan, Xiao-Xing; Ma, Feng-Cai; Li, Yong-Qing


    The effects of isotope substitution on stereodynamic properties for the reactions {C}++{H}2/{H D}/{H T}\\to {{C H}}++H/D/T have been studied applying a quasi classical trajectory method occurring on the new ground state {{C H}}2+ potential energy surface [J. Chem. Phys. 142 (2015) 124302]. In the center of mass coordinates applying the quasi classical trajectory method to investigate the orientation and the alignment of the product molecule. Differential cross section and three angle distribution functions P(θr), P(ϕr), P( {θ }r,{φ }r ) on the potential energy surface that fixed the collision energy with a value is 40 kcal/mol have been studied. The isotope effect becomes more and more important with the reagent molecules H 2 changing into HD and HT. P({θ }r,{φ }r) as the joint probability density function of both polar angles θ r and ϕ r , which can illustrate more detailed dynamics information. The isotope effect is obvious influence on the properties of stereodynamics in the reactions of {C}++{H}2/{H D}/{H T}\\to {{C H}}++H/D/T. Supported by the National Natural Science Foundation of China under Grant Nos. 11474141, 11274149, 11544015, the Program for Liaoning Excellent Talents in University under Grant No. LJQ2015040, and the Scientific Research Foundation for the Returned Overseas Chinese Scholars, State Education Ministry (2014-1685)

  8. Spectroscopic Study of Plasma Polymerized a-C:H Films Deposited by a Dielectric Barrier Discharge. (United States)

    Chandrashekaraiah, Thejaswini Halethimmanahally; Bogdanowicz, Robert; Rühl, Eckart; Danilov, Vladimir; Meichsner, Jürgen; Thierbach, Steffen; Hippler, Rainer


    Plasma polymerized a-C:H thin films have been deposited on Si (100) and aluminum coated glass substrates by a dielectric barrier discharge (DBD) operated at medium pressure using C₂H m /Ar ( m = 2, 4, 6) gas mixtures. The deposited films were characterized by Fourier transform infrared reflection absorption spectroscopy (FT-IRRAS), Raman spectroscopy, and ellipsometry. FT-IRRAS revealed the presence of sp ³ and sp ² C-H stretching and C-H bending vibrations of bonds in the films. The presence of D and G bands was confirmed by Raman spectroscopy. Thin films obtained from C₂H₄/Ar and C₂H₆/Ar gas mixtures have I D /I G ratios of 0.45 and 0.3, respectively. The refractive indices were 2.8 and 3.1 for C₂H₄/Ar and C₂H₆/Ar films, respectively, at a photon energy of 2 eV.

  9. Organocatalysis in cross-coupling: DMEDA-catalyzed direct C-H arylation of unactivated benzene. (United States)

    Liu, Wei; Cao, Hao; Zhang, Hua; Zhang, Heng; Chung, Kin Ho; He, Chuan; Wang, Haibo; Kwong, Fuk Yee; Lei, Aiwen


    A striking breakthrough to the frame of traditional cross-couplings/C-H functionalizations using an organocatalyst remains unprecedented. We uncovered a conceptually different approach toward the biaryl syntheses by using DMEDA as the catalyst to promote the direct C-H arylation of unactivated benzene in the presence of potassium tert-butoxide. The arylation of unactivated benzene with aryl iodides, or aryl bromides and even chlorides under the assistance of an iodo-group, could simply take place at 80 °C. The new methodology presumably involves an aryl radical anion as an intermediate. This finding offers an option toward establishing a new horizon for direct C-H/cross-coupling reactions.

  10. A steric tethering approach enables palladium-catalysed C-H activation of primary amino alcohols. (United States)

    Calleja, Jonas; Pla, Daniel; Gorman, Timothy W; Domingo, Victoriano; Haffemayer, Benjamin; Gaunt, Matthew J


    Aliphatic primary amines are a class of chemical feedstock essential to the synthesis of higher-order nitrogen-containing molecules, commonly found in biologically active compounds and pharmaceutical agents. New methods for the construction of complex amines remain a continuous challenge to synthetic chemists. Here, we outline a general palladium-catalysed strategy for the functionalization of aliphatic C-H bonds within amino alcohols, an important class of small molecule. Central to this strategy is the temporary conversion of catalytically incompatible primary amino alcohols into hindered secondary amines that are capable of undergoing a sterically promoted palladium-catalysed C-H activation. Furthermore, a hydrogen bond between amine and catalyst intensifies interactions around the palladium and orients the aliphatic amine substituents in an ideal geometry for C-H activation. This catalytic method directly transforms simple, easily accessible amines into highly substituted, functionally concentrated and structurally diverse products, and can streamline the synthesis of biologically important amine-containing molecules.

  11. Palladium-catalyzed aryl C-H olefination with unactivated, aliphatic alkenes. (United States)

    Deb, Arghya; Bag, Sukdev; Kancherla, Rajesh; Maiti, Debabrata


    Palladium-catalyzed coupling between aryl halides and alkenes (Mizoroki-Heck reaction) is one of the most popular reactions for synthesizing complex organic molecules. The limited availability, problematic synthesis, and higher cost of aryl halide precursors (or their equivalents) have encouraged exploration of direct olefination of aryl carbon-hydrogen (C-H) bonds (Fujiwara-Moritani reaction). Despite significant progress, the restricted substrate scope, in particular noncompliance of unactivated aliphatic olefins, has discouraged the use of this greener alternative. Overcoming this serious limitation, we report here a palladium-catalyzed chelation-assisted ortho C-H bond olefination of phenylacetic acid derivatives with unactivated, aliphatic alkenes in good to excellent yields with high regio- and stereoselectivities. The versatility of this operationally simple method has been demonstrated through drug diversification and sequential C-H olefination for synthesizing divinylbenzene derivatives.

  12. A steric tethering approach enables palladium-catalysed C-H activation of primary amino alcohols (United States)

    Calleja, Jonas; Pla, Daniel; Gorman, Timothy W.; Domingo, Victoriano; Haffemayer, Benjamin; Gaunt, Matthew J.


    Aliphatic primary amines are a class of chemical feedstock essential to the synthesis of higher-order nitrogen-containing molecules, commonly found in biologically active compounds and pharmaceutical agents. New methods for the construction of complex amines remain a continuous challenge to synthetic chemists. Here, we outline a general palladium-catalysed strategy for the functionalization of aliphatic C-H bonds within amino alcohols, an important class of small molecule. Central to this strategy is the temporary conversion of catalytically incompatible primary amino alcohols into hindered secondary amines that are capable of undergoing a sterically promoted palladium-catalysed C-H activation. Furthermore, a hydrogen bond between amine and catalyst intensifies interactions around the palladium and orients the aliphatic amine substituents in an ideal geometry for C-H activation. This catalytic method directly transforms simple, easily accessible amines into highly substituted, functionally concentrated and structurally diverse products, and can streamline the synthesis of biologically important amine-containing molecules.

  13. Kinetic energy absorbing pad

    International Nuclear Information System (INIS)

    Bricmont, R.J.; Hamilton, P.A.; Ming Long Ting, R.


    Reactors, fuel processing plants etc incorporate pipes and conduits for fluids under high pressure. Fractures, particularly adjacent to conduit elbows, produce a jet of liquid which whips the broken conduit at an extremely high velocity. An enormous impact load would be applied to any stationary object in the conduit's path. The design of cellular, corrugated metal impact pads to absorb the kinetic energy of the high velocity conduits is given. (U.K.)

  14. Absorbable and biodegradable polymers

    CERN Document Server

    Shalaby, Shalaby W


    INTRODUCTION NOTES: Absorbable/Biodegradable Polymers: Technology Evolution. DEVELOPMENT AND APPLICATIONOF NEW SYSTEMS: Segmented Copolyesters with Prolonged Strength Retention Profiles. Polyaxial Crystalline Fiber-Forming Copolyester. Polyethylene Glycol-Based Copolyesters. Cyanoacrylate-Based Systems as Tissue Adhesives. Chitosan-Based Systems. Hyaluronic Acid-Based Systems. DEVELOPMENTS IN PREPARATIVE, PROCESSING, AND EVALUATION METHODS: New Approaches to the Synthesis of Crystalline. Fiber-Forming Aliphatic Copolyesters. Advances in Morphological Development to Tailor the Performance of Me

  15. Burnable neutron absorbers

    International Nuclear Information System (INIS)

    Radford, K.C.; Carlson, W.G.


    This patent deals with the fabrication of pellets for neutron absorber rods. Such a pellet includes a matrix of a refractory material which may be aluminum or zirconium oxide, and a burnable poison distributed throughout the matrix. The neutron absorber material may consist of one or more elements or compounds of the metals boron, gadolinium, samarium, cadmium, europium, hafnium, dysprosium and indium. The method of fabricating pellets of these materials outlined in this patent is designed to produce pores or voids in the pellets that can be used to take up the expansion of the burnable poison and to absorb the helium gas generated. In the practice of this invention a slurry of Al 2 O 3 is produced. A hard binder is added and the slurry and binder are spray dried. This powder is mixed with dry B 4 C powder, forming a homogeneous mixture. This mixture is pressed into green tubes which are then sintered. During sintering the binder volatilizes leaving a ceramic with nearly spherical high-density regions of

  16. Effect of Bilirubin concentration on radiation absorbed dose ...

    African Journals Online (AJOL)

    Results indicate that at low concentrations (25 mol/L to 76 mol/L) absorbed doses decreased with increase in bilirubin concentration. At higher bilirubin concentrations (76 mol/L to 460 mol/L) and beyond, there was an increase in absorption with a strong positive correlation (r = 0.92) between dose absorbed and ...

  17. C-H and N-H bond dissociation energies of small aromatic hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Barckholtz, C.; Barckholtz, T.A.; Hadad, C.M.


    A survey of computational methods was undertaken to calculate the homolytic bond dissociation energies (BDEs) of the C-H and N-H bonds in monocyclic aromatic molecules that are representative of the functionalities present in coal. These include six-membered rings (benzene, pyridine, pyridazine, pyrimidine, pyrazine) and five-membered rings (furan, thiophene, pyrrole, oxazole). By comparison of the calculated C-H BDEs with the available experimental values for these aromatic molecules, the B3LYP/6-31G(d) level of theory was selected to calculate the BDEs of polycyclic aromatic hydrocarbons (PAHs), including carbonaceous PAHs (naphthalene, anthracene, pyrene, coronene) and heteroatomic PAHs (benzofuran, benzothiophene, indole, benzoxazole, quinoline, isoquinoline, dibenzofuran, carbazole). The cleavage of a C-H or a N-H bond generates a {sigma} radical that is, in general, localized at the site from which the hydrogen atom was removed. However, delocalization of the unpaired electron results in {approximately} 7 kcal {center{underscore}dot} mol{sup {minus}1} stabilization of the radical with respect to the formation of phenyl when the C-H bond is adjacent to a nitrogen atom in the azabenzenes. Radicals from five-membered rings are {approximately} 6 kcal {center{underscore}dot} mol{sup {minus}1} less stable than those formed from six-membered rings due to both localization of the spin density and geometric factors. The location of the heteroatoms in the aromatic ring affects the C-H bond strengths more significantly than does the size of the aromatic network. Therefore, in general, the monocyclic aromatic molecules can be used to predict the C-H BDE of the large PAHs within 1 kcal {center{underscore}dot} mol{sup {minus}1}.

  18. Synthesis of a Benzodiazepine-derived Rhodium NHC Complex by C-H Bond Activation

    Energy Technology Data Exchange (ETDEWEB)

    Bergman, Roberg G.; Gribble, Jr., Michael W.; Ellman, Jonathan A.


    The synthesis and characterization of a Rh(I)-NHC complex generated by C-H activation of 1,4-benzodiazepine heterocycle are reported. This complex constitutes a rare example of a carbene tautomer of a 1,4-benzodiazepine aldimine stabilized by transition metal coordination and demonstrates the ability of the catalytically relevant RhCl(PCy{sub 3}){sub 2} fragment to induce NHC-forming tautomerization of heterocycles possessing a single carbene-stabilizing heteroatom. Implications for the synthesis of benzodiazepines and related pharmacophores via C-H functionalization are discussed.

  19. Non-specificity of C-H bond rupture by γ radiolysis of 3-methylpentane glass

    International Nuclear Information System (INIS)

    Laet, M. de; Tilquin, B.


    Some authors using esr data claimed that there is a high selectivity for the rupture of a particular C-H bond after the radiolysis of solid branched alkanes. Using the identification of dimer isomers and very low total dose, we have established the identity of the trapped radical produced at 77 K by the radiolysis of 3-methylpentane, all the parent radicals are formed. If there is a different probability of breaking a particular C-H bond, the bond rupture is not much less selective in liquid than in the glassy state [fr

  20. Electrochemical C-H Amination by Cobalt Catalysis in a Renewable Solvent. (United States)

    Sauermann, Nicolas; Mei, Ruhuai; Ackermann, Lutz


    Syntheses of substituted anilines primarily rely on palladium-catalyzed coupling chemistry with prefunctionalized aryl electrophiles. While oxidative aminations have emerged as powerful alternatives, they largely produce undesired metal-containing by-products in stoichiometric quantities. In contrast, described herein is the unprecedented electrochemical C-H amination by cobalt-catalyzed C-H activation. The environmentally benign electrocatalysis avoids stoichiometric metal oxidants, can be conducted under ambient air, and employs a biomass-derived, renewable solvent for sustainable aminations in an atom- and step-economical manner with H 2 as the sole byproduct. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Photoredox ketone catalysis for the direct C-H imidation and acyloxylation of arenes. (United States)

    Tripathi, Chandra Bhushan; Ohtani, Tsuyoshi; Corbett, Michael T; Ooi, Takashi


    The photoexcited aryl ketone-catalyzed C-H imidation of arenes and heteroarenes is reported. Using 3,6-dimethoxy-9 H -thioxanthen-9-one as a catalyst in combination with a bench-stable imidating reagent, C-N bond formation proceeds with high efficiency and a broad substrate scope. A key part of this method is that the thioxanthone catalyst acts as an excited-state reductant, thus establishing an oxidative quenching cycle for radical aromatic substitution. The synthetic potential of this photoexcited ketone catalysis is further demonstrated by application to the direct C-H acyloxylation of arenes.

  2. Difluoroacetic Acid as a New Reagent for Direct C-H Difluoromethylation of Heteroaromatic Compounds

    DEFF Research Database (Denmark)

    Thanh Tung, Truong; Christensen, Søren Brøgger; Nielsen, John


    A technically simple procedure for direct C-H difluoromethylation of heteroaromatic compounds using off-the-shelf difluoroacetic acid as the difluoromethylating reagent has been developed. Mono-difluoromethylation versus bis-difluoromethylation is controlled as the result of the reaction temperat......A technically simple procedure for direct C-H difluoromethylation of heteroaromatic compounds using off-the-shelf difluoroacetic acid as the difluoromethylating reagent has been developed. Mono-difluoromethylation versus bis-difluoromethylation is controlled as the result of the reaction...

  3. Rh2(II)-catalyzed intramolecular aliphatic C-H bond amination reactions using aryl azides as the N-atom source. (United States)

    Nguyen, Quyen; Sun, Ke; Driver, Tom G


    Rhodium(II) dicarboxylate complexes were discovered to catalyze the intramolecular amination of unactivated primary, secondary, or tertiary aliphatic C-H bonds using aryl azides as the N-atom precursor. While a strong electron-withdrawing group on the nitrogen atom is typically required to achieve this reaction, we found that both electron-rich and electron-poor aryl azides are efficient sources for the metal nitrene reactive intermediate. © 2012 American Chemical Society

  4. A potential role of substrate as a base for deprotonation pathway in Rh-catalysed C-H amination of heteroArenes: DFT insights

    KAUST Repository

    Ajitha, Manjaly John


    The possibility of direct introduction of a new functionality through C–H bond activation is an attractive strategy in covalent synthesis. Here, we investigated the mechanism of Rh-catalysed C-H amination of the hetero-aryl substrate (2-phenylpyridine) using phenyl azide as nitrogen source by density functional theory (DFT). For the deprotocyclometallation and protodecyclometallation processes of the title reaction, we propose a stepwise base-assisted mechanism (pathway I) instead of previously reported concerted mechanism (pathway II). In the new mechanism proposed here, 2-phenylpyridine acts as a base in the initial deprotonation step (C-H bond cleavage) and transports the proton towards the final protonation step. In fact, the N-H bond of the strong conjugate acid (formed during initial C-H bond cleavage) considered in pathway I (via TS4) is more acidic than the C-H bond of the neutral substrate considered in pathway II (via TS5). The higher activation barrier of TS5 mainly originates from the ring strain of the four membered cyclic transition state. The vital role of base, as disclosed here, can potentially have broader mechanistic implications for the development of reaction conditions of transition metal catalysed reactions.

  5. Absorber for terahertz radiation management (United States)

    Biallas, George Herman; Apeldoorn, Cornelis; Williams, Gwyn P.; Benson, Stephen V.; Shinn, Michelle D.; Heckman, John D.


    A method and apparatus for minimizing the degradation of power in a free electron laser (FEL) generating terahertz (THz) radiation. The method includes inserting an absorber ring in the FEL beam path for absorbing any irregular THz radiation and thus minimizes the degradation of downstream optics and the resulting degradation of the FEL output power. The absorber ring includes an upstream side, a downstream side, and a plurality of wedges spaced radially around the absorber ring. The wedges form a scallop-like feature on the innermost edges of the absorber ring that acts as an apodizer, stopping diffractive focusing of the THz radiation that is not intercepted by the absorber. Spacing between the scallop-like features and the shape of the features approximates the Bartlett apodization function. The absorber ring provides a smooth intensity distribution, rather than one that is peaked on-center, thereby eliminating minor distortion downstream of the absorber.

  6. Corrosion resistant neutron absorbing coatings (United States)

    Choi, Jor-Shan [El Cerrito, CA; Farmer, Joseph C [Tracy, CA; Lee, Chuck K [Hayward, CA; Walker, Jeffrey [Gaithersburg, MD; Russell, Paige [Las Vegas, NV; Kirkwood, Jon [Saint Leonard, MD; Yang, Nancy [Lafayette, CA; Champagne, Victor [Oxford, PA


    A method of forming a corrosion resistant neutron absorbing coating comprising the steps of spray or deposition or sputtering or welding processing to form a composite material made of a spray or deposition or sputtering or welding material, and a neutron absorbing material. Also a corrosion resistant neutron absorbing coating comprising a composite material made of a spray or deposition or sputtering or welding material, and a neutron absorbing material.

  7. On the composition analysis of nc-TiC/a-C : H nanocomposite coatings

    NARCIS (Netherlands)

    Chechenin, N.G.; Chernykh, P.N.; Kulikauskas, V.S.; Pei, Y.T.; Vainshtein, D.; Hosson, J.Th.M. De


    Using a set of ion beam analysis (IBA) techniques the compositions of hydrogenated diamond-like carbon (DLC) nanocomposite coatings are scrutinized, including the hydrogen content. The coatings are composed of two constituents: amorphous hydrocarbon matrix (a-C : H) and nanocrystalline titanium

  8. Nanostructure and properties of TiC/a-C : H composite coatings

    NARCIS (Netherlands)

    Pei, Y.T.; Galvan, D.; Hosson, J.Th.M. De


    TiC/a-C:H nanocomposite coatings, deposited with closed-field unbalanced magnetron sputtering, have been scrutinized with atomic force, scanning and high-resolution transmission electron microscopy, nanoindentation and tribo-tests. These coatings consist of 2-5 nm TiC nanocrystallites embedded in an

  9. Ru(II)-catalyzed intermolecular ortho-C-H amidation of aromatic ketones with sulfonyl azides. (United States)

    Bhanuchandra, M; Yadav, M Ramu; Rit, Raja K; Rao Kuram, Malleswara; Sahoo, Akhila K


    Ru(II)-catalyzed intermolecular ortho-C-H amidation of weakly coordinating aromatic ketones with sulfonyl azides is reported. The developed reaction protocol can be extended to various substituted aromatic ketones to afford a wide range of desired C-N bond formation products in good yields.

  10. F. H. C h . J othmann , De Bijbel in de loop der eeuwen. Kampen, J ...

    African Journals Online (AJOL)


    F. H. C h . J othmann , De Bijbel in de loop der eeuwen. Kampen, J . H. Kok. N.V., 1954, 43 bis. Prys 95 cent. Hierdie werkie geskryf vir gebruik op skool, kategesasie en jeug- vereniging is besonder smakelik versorg met uiters insiggewende illu- strasies oor die geskiedenis van die Bybel as geskrif en boek. Die stof is.

  11. Penicillin resistant gonococci at Q.E.C.H. | Ward | Malawi Medical ...

    African Journals Online (AJOL)

    Malawi Medical Journal. Journal Home · ABOUT THIS JOURNAL · Advanced Search · Current Issue · Archives · Journal Home > Vol 3, No 2 (1986) >. Log in or Register to get access to full text downloads. Username, Password, Remember me, or Register. Penicillin resistant gonococci at Q.E.C.H.. JC Ward, JS ...

  12. Breakdown of the Coulomb friction law in TiC/a-C:H nanocomposite coatings

    International Nuclear Information System (INIS)

    Pei, Y. T.; Huizenga, P.; Galvan, D.; Hosson, J. Th. M. de


    Advanced TiC/a-C:H nanocomposite coatings have been produced via reactive deposition in a closed-field unbalanced magnetron sputtering system (Hauzer HTC-1000 or HTC 1200). In this paper, we report on the tribological behavior of TiC/a-C:H nanocomposite coatings in which ultralow friction is tailored with superior wear resistance, two properties often difficult to achieve simultaneously. Tribotests have been performed at room temperature with a ball-on-disk configuration. In situ monitoring of the wear depth of the coated disk together with the wear height of the ball counterpart at nanometer scale reveals that the self-lubricating effects are induced by the formation of transfer films on the surface of the ball counterpart. A remarkable finding is a breakdown of the Coulomb friction law in the TiC/a-C:H nanocomposite coatings. In addition, the coefficient of friction of TiC/a-C:H nanocomposite coatings decreases with decreasing relative humidity. A superior wear resistance of the coated disk at a level of 10 -17 m 3 /N m (per lap) has been achieved under the condition of superlow friction and high toughness, both of which require fine TiC nanoparticles (e.g., 2 nm) and a wide matrix separation that must be comparable to the dimensions of the nanoparticles

  13. References (Examples) Journals Desiraju G R 1991 The C-H...O ...

    Indian Academy of Sciences (India)


    References (Examples). Journals. Desiraju G R 1991 The C-H...O Hydrogen Bond in Crystals: What is it? Acc. Chem. Res. 24 290. Beer P D and Gale P A 2001 Anion Recognition and Sensing: The State of the Art and Future. Perspectives Angew. Chem. Int. Edit. 40 486. Chakraborty A, Kar S, Nath D N and Guchhait N ...

  14. High growth rate of a-SiC: H films using ethane carbon source by ...

    Indian Academy of Sciences (India)

    Home; Journals; Bulletin of Materials Science; Volume 36; Issue 7. High growth rate of a-SiC:H films using ethane carbon source by HW-CVD method. Mahesh M Kamble Vaishali S Waman Sanjay S Ghosh Azam Mayabadi Vasant G Sathe T Shripathi Habib M Pathan Sandesh R Jadkar. Volume 36 Issue 7 December 2013 ...

  15. Difluoroacetic Acid as a New Reagent for Direct C-H Difluoromethylation of Heteroaromatic Compounds

    DEFF Research Database (Denmark)

    Thanh Tung, Truong; Christensen, Søren Brøgger; Nielsen, John


    A technically simple procedure for direct C-H difluoromethylation of heteroaromatic compounds using off-the-shelf difluoroacetic acid as the difluoromethylating reagent has been developed. Mono-difluoromethylation versus bis-difluoromethylation is controlled as the result of the reaction temperat...

  16. C-H and H-H Activation in Transition Metal Complexes and on Surfaces. (United States)


    48) increases the *-xz overlap greatly. M-H becomes bonding, and :* significantly populated. The COOP curve shows increasing improvement in M-Ha...Activation, catalysis 20. ABSTRACT ’ Continuo an reverse od@ It necesary And Identily by Weeck num11ber) - .The breaking of the H-H bond in 142 and a C-H bond

  17. C-H activation on rhodium: reaction mechanism and the role of carbonaceous residues

    International Nuclear Information System (INIS)

    Cogen, J.M.; Maier, W.F.


    Evidence for two C-H activation mechanisms, the oxidative addition of a single C-H bond and the concerted oxidative addition of two adjacent C-H bonds, is presented. The two mechanisms show different sensitivity to surface structure or particle size. While the first process (E/sub a/ ∼ 21 kcal/mol) is insensitive to the hydrocarbon structure, the second process (E/sub a/ ∼ 5-9 kcal/mol) is sensitive to the hydrocarbon structure. C-H activation is found to be 0.6 order in hexane and zero order in deuterium, which is consistent with oxidative addition as the rate-determining step. The d 2 maximum obtained by H/D exchange of linear alkanes on Rh results from surface olefins, as indicated by high-resolution deuterium NMR. Evidence against the participation of carbonaceous residues in the H/D exchange process is presented, indicating that carbonaceous material is not part of the active site. Two types of carbonaceous residues are detected. One forms at lower temperatures and does not interfere with the reaction; the other forms at higher temperatures and acts to poison the catalyst

  18. Intramolecular C-H Bond Activation through a Flexible Ester Linkage

    Czech Academy of Sciences Publication Activity Database

    Shaffer, Christopher; Schröder, Detlef; Gutz, Ch.; Lutzen, A.


    Roč. 51, č. 32 (2012), s. 8097-8100 ISSN 1433-7851 Grant - others:European Research Council(XE) AdG HORIZOMS Institutional support: RVO:61388963 Keywords : C-H activation * copper * gas phase * ion mobility * oxidation Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 13.734, year: 2012

  19. Cobalt-catalysed C-H carbonylative cyclisation of aliphatic amides. (United States)

    Williamson, Patrick; Galván, Alicia; Gaunt, Matthew J


    A cobalt-catalysed C-H carbonylation of aliphatic carboxamide derivatives is described, employing commercially available Co(ii)-salts in the presence of a silver oxidant. This operationally simple process utilises an atmospheric pressure of CO and generates a range of substituted succinimide products bearing diverse functional groups that can be successfully accessed via this methodology.

  20. Cobalt-catalyzed C-H olefination of aromatics with unactivated alkenes. (United States)

    Manoharan, Ramasamy; Sivakumar, Ganesan; Jeganmohan, Masilamani


    A cobalt-catalyzed C-H olefination of aromatic and heteroaromatic amides with unactivated alkenes, allyl acetates and allyl alcohols is described. This method offers an efficient route for the synthesis of vinyl and allyl benzamides in a highly stereoselective manner. It is observed that the ortho substituent on the benzamide moiety is crucial for the observation of allylated products in unactivated alkenes.

  1. Palladium-catalysed transannular C-H functionalization of alicyclic amines (United States)

    Topczewski, Joseph J.; Cabrera, Pablo J.; Saper, Noam I.; Sanford, Melanie S.


    Discovering pharmaceutical candidates is a resource-intensive enterprise that frequently requires the parallel synthesis of hundreds or even thousands of molecules. C-H bonds are present in almost all pharmaceutical agents. Consequently, the development of selective, rapid and efficient methods for converting these bonds into new chemical entities has the potential to streamline pharmaceutical development. Saturated nitrogen-containing heterocycles (alicyclic amines) feature prominently in pharmaceuticals, such as treatments for depression (paroxetine, amitifadine), diabetes (gliclazide), leukaemia (alvocidib), schizophrenia (risperidone, belaperidone), malaria (mefloquine) and nicotine addiction (cytisine, varenicline). However, existing methods for the C-H functionalization of saturated nitrogen heterocycles, particularly at sites remote to nitrogen, remain extremely limited. Here we report a transannular approach to selectively manipulate the C-H bonds of alicyclic amines at sites remote to nitrogen. Our reaction uses the boat conformation of the substrates to achieve palladium-catalysed amine-directed conversion of C-H bonds to C-C bonds on various alicyclic amine scaffolds. We demonstrate this approach by synthesizing new derivatives of several bioactive molecules, including varenicline.

  2. Solar radiation absorbing material (United States)

    Googin, John M.; Schmitt, Charles R.; Schreyer, James M.; Whitehead, Harlan D.


    Solar energy absorbing means in solar collectors are provided by a solar selective carbon surface. A solar selective carbon surface is a microporous carbon surface having pores within the range of 0.2 to 2 micrometers. Such a surface is provided in a microporous carbon article by controlling the pore size. A thermally conductive substrate is provided with a solar selective surface by adhering an array of carbon particles in a suitable binder to the substrate, a majority of said particles having diameters within the range of about 0.2-10 microns.

  3. Renewable Formate from C-H Bond Formation with CO2: Using Iron Carbonyl Clusters as Electrocatalysts. (United States)

    Loewen, Natalia D; Neelakantan, Taruna V; Berben, Louise A


    promote C-H bond formation. Thermochemical insights into the disparate reactivities of these clusters were achieved through hydricity measurements using SEC. We found that only [H-Fe 4 N(CO) 12 ] - and its derivative [H-Fe 4 N(CO) 11 (PPh 3 )] - have hydricities modest enough to avoid H 2 production but strong enough to make formate. [H-Fe 4 C(CO) 12 ] 2- is a stronger hydride donor, theoretically capable of making formate, but due to an overwhelming thermodynamic driving force and the increased electrostatic attraction between the more negative cluster and H + , only H 2 is observed experimentally. This illustrates the fundamental importance of controlling thermochemistry when designing new catalysts selective for C-H bond formation and establishes a hydricity range of 15.5-24.1 or 44-49 kcal mol -1 where C-H bond formation may be favored in water or MeCN, respectively.

  4. Wide Spectral Sensitivity of Monolithic a-SiC:H pi’n/pin Photodiode Outside the Visible Spectrum

    Directory of Open Access Journals (Sweden)

    Manuela Vieira


    Full Text Available In this paper, we experimentally demonstrate the use of near-ultraviolet steady state illumination to increase the spectral sensitivity of a double a-SiC/Si pi’n/pin photodiode beyond the visible spectrum (400 nm-880 nm. The concept is extended to implement a 1 by 4 wavelength division multiplexer with channel separation in the visible/near infrared ranges. The device consists of a p-i'(a-SiC:H-n/p-i(a-Si:H-n heterostructure, sandwiched between two transparent contacts. Optoelectronic characterization of the device is presented and shows the feasibility of tailoring the wavelength and bandwidth of a polychromatic mixture of different wavelengths. Results show that the spectral current under steady state ultraviolet irradiation depends strongly on the wavelength of the impinging light, and on the background intensity and irradiation side allowing controlled high-pass filtering properties. If several monochromatic pulsed lights, in the visible/near infrared (VIS/NIR range, separately or in a polychromatic mixture illuminate the device, data shows that, front background enhances the light-to-dark sensitivity of the medium, long and infrared wavelength channels, and quench strongly the low wavelengths channels. Back background has the opposite behavior; it enhances only channel magnitude in short wavelength range and strongly reduces it in the long ones. This nonlinearity provides the possibility for selective tuning of a specific wavelength. A capacitive optoelectronic model supports the experimental results. A numerical simulation is presented.

  5. Mechanistic Basis for Efficient, Site-Selective, Aerobic Catalytic Turnover in Pd-Catalyzed C-H Imidoylation of Heterocycle-Containing Molecules. (United States)

    Tereniak, Stephen J; Stahl, Shannon S


    A recently reported Pd-catalyzed method for oxidative imidoylation of C-H bonds exhibits unique features that have important implications for Pd-catalyzed aerobic oxidation catalysis: (1) The reaction tolerates heterocycles that commonly poison Pd catalysts. (2) The site selectivity of C-H activation is controlled by an N-methoxyamide group rather than a suitably positioned heterocycle. (3) A Pd 0 source, Pd 2 (dba) 3 (dba = dibenzylideneacetone), is superior to Pd(OAc) 2 as a precatalyst, and other Pd II sources are ineffective. (4) The reaction performs better with air, rather than pure O 2 . The present study elucidates the origin of these features. Kinetic, mechanistic, and in situ spectroscopic studies establish that Pd II -mediated C-H activation is the turnover-limiting step. The t BuNC substrate is shown to coordinate more strongly to Pd II than pyridine, thereby contributing to the lack of heterocycle catalyst poisoning. A well-defined Pd II -peroxo complex is a competent intermediate that promotes substrate coordination via proton-coupled ligand exchange. The effectiveness of this substrate coordination step correlates with the basicity of the anionic ligands coordinated to Pd II , and Pd 0 catalyst precursors are most effective because they selectively afford the Pd II -peroxo in situ. Finally, elevated O 2 pressures are shown to contribute to background oxidation of the isonitrile, thereby explaining the improved performance of reactions conducted with air rather than 1 atm O 2 . These collective results explain the unique features of the aerobic C-H imidoylation of N-methoxybenzamides and have important implications for other Pd-catalyzed aerobic C-H oxidation reactions.

  6. Deposition of a-C:H films on a nanotrench pattern by bipolar PBII and D

    International Nuclear Information System (INIS)

    Hirata, Yuki; Nakahara, Yuya; Nagato, Keisuke; Choi, Junho


    In this study, hydrogenated amorphous carbon (a-C:H) films were deposited on a nanotrench pattern (300 nm pitch, aspect ratio: 2.0) by bipolar-type plasma based ion implantation and deposition technique (bipolar PBII and D), and the effects of bipolar pulse on the film properties were investigated. Moreover, the behaviour of ions and radicals surrounding the nanotrench was analyzed to clarify the coating mechanism and properties of the a-C:H films on the nanotrench. Further, thermal nanoimprint lithography was carried out using the nanotrench pattern coated with a-C:H films as the mold, and the mold release properties were evaluated. All nanotrench surfaces were successfully coated with the a-C:H films, but the film thickness on the top, sidewall, and bottom surfaces of the trench were not uniform. The surface roughness of the a-C:H films was found to decrease at a higher positive voltage; this happens due to the higher electron temperature around the nanotrench because of the surface migration of plasma particles arrived on the trench. The effects of the negative voltage on the behaviour of ions and radicals near the sidewall of the nanotrench are quite similar to those near the microtrench reported previously (Park et al 2014 J. Phys. D: Appl. Phys . 47 335306). However, the positive pulse voltage was also found to affect the behaviour of ions and radicals near the sidewall surface. The incident angles of ions on the sidewall surface increased with the positive pulse voltage because the energy of incoming ions on the trench decreases with increasing positive voltage. Moreover, the incident ion flux on the sidewall is affected by the positive voltage history. Further, the radical flux decreases with increasing positive voltage. It can be concluded that a higher positive voltage at a lower negative voltage condition is good to obtain better film properties and higher film thickness on the sidewall surface. Pattern transfer properties for the nanoimprint formed by

  7. The Flexible Bass Absorber

    DEFF Research Database (Denmark)

    Adelman-Larsen, Niels Werner; Thompson, Eric Robert; Gade, Anders Christian


    Multi-purpose concert halls face a dilemma. They host different performance types that require significantly different acoustic conditions in order to provide the best sound quality to both the performers, sound engineers and the audience. Pop and rock music often contain high levels of bass sound...... energy but still require high definition for good sound quality. The mid- and high-frequency absorption is easily regulated, but adjusting the low-frequency absorption has typically been too expensive or requires too much space to be practical for multi-purpose halls. A practical solution to this dilemma...... has been developed. Measurements were made on a variable and mobile low-frequency absorber. The paper presents the results of prototype sound absorption measurements as well as elements of the design....

  8. The Flexible Bass Absorber

    DEFF Research Database (Denmark)

    Adelman-Larsen, Niels Werner; Thompson, Eric Robert; Gade, Anders Christian


    Multi-purpose concert halls face a dilemma. They host different performance types that require significantly different acoustic conditions in order to provide the best sound quality to both the performers, sound engineers and the audience. Pop and rock music often contains high levels of bass sound...... energy but still require high definition for good sound quality. The mid- and high-frequency absorption is easily regulated, but adjusting the low-frequency absorption has typically been too expensive or requires too much space to be practical for multi-purpose halls. A practical solution to this dilemma...... has been developed. Measurements were made on a variable and mobile low-frequency absorber. The paper presents the results of prototype sound absorption measurements as well as elements of the design....

  9. Metamaterial electromagnetic wave absorbers. (United States)

    Watts, Claire M; Liu, Xianliang; Padilla, Willie J


    The advent of negative index materials has spawned extensive research into metamaterials over the past decade. Metamaterials are attractive not only for their exotic electromagnetic properties, but also their promise for applications. A particular branch-the metamaterial perfect absorber (MPA)-has garnered interest due to the fact that it can achieve unity absorptivity of electromagnetic waves. Since its first experimental demonstration in 2008, the MPA has progressed significantly with designs shown across the electromagnetic spectrum, from microwave to optical. In this Progress Report we give an overview of the field and discuss a selection of examples and related applications. The ability of the MPA to exhibit extreme performance flexibility will be discussed and the theory underlying their operation and limitations will be established. Insight is given into what we can expect from this rapidly expanding field and future challenges will be addressed. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Heterogeneous neutron absorbers development

    International Nuclear Information System (INIS)

    Boccaccini, Aldo; Agueda, Horacio; Russo, Diego; Perez, Edmundo


    The use of solid burnable absorber materials in power light water reactors has increased in the last years, specially due to improvements attained in costs of generated electricity. The present work summarizes the basic studies made on an alumina-gadolinia system, where alumina is the inert matrix and gadolinia acts as burnable poison, and describes the fabrication method of pellets with that material. High density compacts were obtained in the range of concentrations used by cold pressing and sintering at 1600 deg C in inert (Ar) atmosphere. Finally, the results of the irradiation experiences made at RA-6 reactor, located at the Bariloche Atomic Center, are given where variations on negative reactivity caused by introduction of burnable poison rods were measured. The results obtained from these experiences are in good agreement with those coming from calculation codes. (Author)

  11. Cp*Rh(III)/Bicyclic Olefin Cocatalyzed C-H Bond Amidation by Intramolecular Amide Transfer. (United States)

    Wang, Xiaoming; Gensch, Tobias; Lerchen, Andreas; Daniliuc, Constantin G; Glorius, Frank


    A bicyclic olefin was discovered as a cocatalyst in a Cp*Rh(III)-catalyzed C-H bond amidation proceeding by an intramolecular amide transfer in N-phenoxyacetamide derivatives. Combining experimental and theoretical studies, we propose that the olefin promotes a Rh(III) intermediate to undergo oxidative addition into the O-N bond to form a Rh(V) nitrenoid species and subsequently direct the nitrenoid to add to the ortho position. The amide directing group plays a dual role as a cleavable coordinating moiety as well as an essential coupling partner for the C-H amidation. This methodology was successfully applied to the late-stage diversification of natural products and a marketed drug under mild conditions.

  12. Recent advances in C-S bond formation via C-H bond functionalization and decarboxylation. (United States)

    Shen, Chao; Zhang, Pengfei; Sun, Qiang; Bai, Shiqiang; Hor, T S Andy; Liu, Xiaogang


    The development of mild and general methods for C-S bond formation has received significant attention because the C-S bond is indispensable in many important biological and pharmaceutical compounds. Early examples for the synthesis of C-S bonds are generally limited to the condensation reaction between a metal thiolate and an organic halide. Recent chemical approaches for C-S bond formation, based upon direct C-H bond functionalization and decarboxylative reactions, not only provide new insights into the mechanistic understanding of C-S coupling reactions but also allow the synthesis of sulfur-containing compounds from more effective synthetic routes with high atom economy. This review intends to explore recent advances in C-S bond formation via C-H functionalization and decarboxylation, and the growing opportunities they present to the construction of complex chemical scaffolds for applications encompassing natural product synthesis, synthetic methodology development, and functional materials as well as nanotechnology.

  13. Spectroscopy of C-H stretching overtones in dimethylacetylene, dimethylcadmium, and dimethylmercury

    Energy Technology Data Exchange (ETDEWEB)

    Manzanares I., C.; Yamasaki, N.L.S.; Weitz, E. (Northwestern Univ., Evanston, IL (USA))


    The overtone spectra of a number of C-H stretching vibrations of dimethylacetylene, dimethylcadmium, and dimethylmercury were obtained by using intracavity dye laser photoacoustic spectroscopy. Transitions corresponding to the {Delta}{nu} = 5, 6, and 7 overtones of the C-H stretch are assigned by using the local-mode model. In addition, a number of local-mode-normal-mode combination bands have been identified. Local-mode harmonic frequencies ({omega}{sub e}) and anharmonicities ({omega}{sub e}x{sub e}) are obtained from Birge-Sponer plots. The line widths of the pure local-mode transitions are analyzed in terms of possible resonances with local-mode-normal-mode combination bands. Line widths in this series of compounds are compared to line widths in the M(CH{sub 3}){sub 4} and M(CH{sub 3}){sub 3} series.

  14. Selective C-H Halogenation with a Highly Fluorinated Manganese Porphyrin. (United States)

    Li, Gang; Dilger, Andrew K; Cheng, Peter T; Ewing, William R; Groves, John T


    The selective C-H functionalization of aliphatic molecules remains a challenge in organic synthesis. While radical chain halogenation reactions provide efficient access to many halogenated molecules, the use of typical protocols for the selective halogenation of electron-deficient and strained aliphatic molecules is rare. Herein, we report selective C-H chlorination and fluorination reactions promoted by an electron-deficient manganese pentafluorophenyl porphyrin catalyst, Mn(TPFPP)Cl. This catalyst displays superior properties for the aliphatic halogenation of recalcitrant, electron-deficient, and strained substrates with unique regio- and stereoselectivity. UV/Vis analysis during the course of the reaction indicated that an oxo-Mn V species is responsible for hydrogen-atom abstraction. The observed stereoselectivity results from steric interactions between the bulky porphyrin ligand and the intermediate substrate radical in the halogen rebound step. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Ligand-enabled ortho-C-H olefination of phenylacetic amides with unactivated alkenes. (United States)

    Lu, Ming-Zhu; Chen, Xing-Rong; Xu, Hui; Dai, Hui-Xiong; Yu, Jin-Quan


    Although chelation-assisted C-H olefination has been intensely investigated, Pd(ii)-catalyzed C-H olefination reactions are largely restricted to acrylates and styrenes. Here we report a quinoline-derived ligand that enables the Pd(ii)-catalyzed olefination of the C(sp 2 )-H bond with simple aliphatic alkenes using a weakly coordinating monodentate amide auxiliary. Oxygen is used as the terminal oxidant with catalytic copper as the co-oxidant. A variety of functional groups in the aliphatic alkenes are tolerated. Upon hydrogenation, the ortho -alkylated product can be accessed. The utility of this reaction is also demonstrated by the late-stage diversification of drug molecules.

  16. Limits on top FCNC decay t$\\rightarrow$cH and t$\\rightarrow$c$\\gamma$ from CLIC at 380 GeV

    CERN Document Server

    Zarnecki, Aleksander


    FCNC top decays are very strongly suppressed in the Standard Model and the observation of any such decay would be a direct signature of physics beyond SM. Many "new physics" scenarios predict contributions to FCNC processes and the largest enhancement in many models is for t$\\rightarrow$cH decay. Enhancements for the decay channel t$\\rightarrow$c$\\gamma$ are more modest, but the decay still has a clearly identifiable kinematic signature. Prospects for measuring these decays at CLIC running at 380 GeV were studied with full detector simulation, taking the luminosity distribution, beam polarization and beam induced background into account. Top pair production events with t$\\rightarrow$cH decays can be identified based on the kinematic constraints and flavour tagging information. The analysis was divided into three steps: classification of top pair candidate events, event quality determination and kinematic reconstruction based on signal or background hypotheses, and final separation of signal from background. T...

  17. Cobalt dinitrosoalkane complexes in the C-H functionalization of olefins. (United States)

    Schomaker, Jennifer M; Boyd, W Christopher; Stewart, Ian C; Toste, F Dean; Bergman, Robert G


    The use of cobalt dinitrosoalkane complexes in the C-H functionalization of alkenes has been demonstrated. Reaction of a series of alkenes with Me4CpCo(CO)2 in the presence of NO generates intermediate cobalt dinitrosoalkane complexes that can be deprotonated alpha to the nitrosyl group and added to various Michael acceptors. The resultant products can then undergo retrocycloaddition reactions in the presence of the original alkene to regenerate the starting cobalt dinitrosoalkane complex and release the functionalized alkene.

  18. Ruthenium-catalyzed C7 amidation of indoline C-H bonds with sulfonyl azides. (United States)

    Pan, Changduo; Abdukader, Ablimit; Han, Jie; Cheng, Yixiang; Zhu, Chengjian


    A ruthenium-catalyzed direct C7 amidation of indoline C-H bonds with sulfonyl azides was developed. This procedure allows the synthesis of a variety of 7-amino-substituted indolines, which are useful in pharmaceutical. The good functional tolerances, as well as the mild conditions, are prominent feature of this method. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Aromatic C-H bond activation revealed by infrared multiphoton dissociation spectroscopy

    Czech Academy of Sciences Publication Activity Database

    Jašíková, L.; Hanikýřová, E.; Schröder, Detlef; Roithová, J.


    Roč. 47, č. 4 (2012), s. 460-465 ISSN 1076-5174 Grant - others:GA ČR(CZ) GAP207/11/0338; Seventh Framework Program(XE) 226716 Institutional research plan: CEZ:AV0Z40550506 Keywords : C-H activation * density functional theory calculations * ion spectroscopy * metal oxides * rearrangements Subject RIV: CC - Organic Chemistry Impact factor: 3.214, year: 2012

  20. Enantioselective synthesis of a PKC inhibitor via catalytic C-H bond activation. (United States)

    Wilson, Rebecca M; Thalji, Reema K; Bergman, Robert G; Ellman, Jonathan A


    [reaction: see text] The syntheses of two biologically active molecules possessing dihydropyrroloindole cores (1 and 2) were completed using rhodium-catalyzed imine-directed C-H bond functionalization, with the second of these molecules containing a stereocenter that can be set with 90% ee during cyclization using chiral nonracemic phosphoramidite ligands. Catalytic decarbonylation and direct indole/maleimide coupling provide efficient access to 2.

  1. Regioselective Annulation of Aryl Sulfonamides with Allenes through Cobalt-Promoted C-H Functionalization. (United States)

    Lan, Tianlong; Wang, Liguo; Rao, Yu


    The development of an efficient method for the construction of biologically relevant sultams is described, which represents the first case of cobalt-promoted C-H/N-H functionalization of sulfonamides with allenes. This newly developed annulation reaction demonstrated good functional group tolerance and excellent regioselectivity. Both terminal monosubstituted allenes and internal disubstituted allenes can be employed to give the desired sultams in good yields. This strategy can be successfully used to build a unique sultam library with novel structural diversity.

  2. Some growth peculiarities of a-C:H films in ECR microwavw plasma

    Czech Academy of Sciences Publication Activity Database

    Kulikovsky, V.; Shaginyan, L. R.; Jastrabík, Lubomír; Soukup, Ladislav; Boháč, Petr; Musil, Jindřich


    Roč. 60, - (2001), s. 315-323 ISSN 0042-207X R&D Projects: GA AV ČR IAA1010827 Institutional research plan: CEZ:A02/98:Z1-010-914 Keywords : a-C:H polymer-like films * ECR microwave plasma * CVD Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 0.541, year: 2001

  3. Pd-Catalyzed regioselective C-H halogenation of quinazolinones and benzoxazinones. (United States)

    Dabiri, Minoo; Farajinia Lehi, Noushin; Kazemi Movahed, Siyavash; Khavasi, Hamid Reza


    A Pd-catalyzed ortho-selective halogenation of benzoxazinone and quinazolinone scaffolds has been described employing N-halosuccinimide as both a halogen source and an oxidant reagent via C-H bond activation. This transformation shows high chemo- and regioselectivities and demonstrates a broad range of benzoxazinone and quinazolinone substrates with different functional groups and has been scaled up to the gram level.

  4. Synthesis of all eight L-glycopyranosyl donors using C-H activation

    DEFF Research Database (Denmark)

    Frihed, Tobias; Pedersen, Christian Marcus; Bols, Mikael


    by an intramolecular C-H activation of the methyl group in g-position; both steps were catalyzed by iridium. The following Fleming-Tamao oxidation and acetylation gave the suitably protected L-hexoses. This is the first general method for the preparation of all eight L-hexoses as their thioglycosyl donors ready...... for glycosylation and the first example of an iridium-catalyzed C(sp3)-H activation on sulfide-containing compounds....

  5. Excess C/O and C/H in Outer Protoplanetary Disk Gas (United States)

    Öberg, Karin I.; Bergin, Edwin A.


    The compositions of nascent planets depend on the compositions of their birth disks. In particular, the elemental compositions of gas giant gaseous envelopes depend on the elemental compositions of the disk gas from which the envelopes are accreted. Previous models have demonstrated that sequential freeze-out of O- and C-bearing volatiles in disks will result in supersolar C/O ratios and subsolar C/H ratios in the gas between water and CO snowlines. However, this result does not take into account the expected grain growth and radial drift of pebbles in disks, and the accompanying redistribution of volatiles from the outer to the inner disk. Using a toy model we demonstrate that when drift is considered, CO is enhanced between the water and CO snowline, resulting in both supersolar C/O and C/H ratios in the disk gas in the gas giant formation zone. This result appears to be robust for the disk model as long as there is substantial pebble drift across the CO snowline, and the efficiency of CO vapor diffusion is limited. Gas giants that accrete their gaseous envelopes exterior to the water snowline and do not experience substantial core-envelope mixing may thus feature both superstellar C/O and C/H ratios in their atmospheres. Pebble drift will also affect the nitrogen and noble gas abundances in the planet-forming zones, which may explain some of Jupiter’s peculiar abundance patterns.

  6. Atomic and electronic structures of a-SiC:H from tight-binding molecular dynamics

    CERN Document Server

    Ivashchenko, V I; Shevchenko, V I; Ivashchenko, L A; Rusakov, G V


    The atomic and electronic properties of amorphous unhydrogenated (a-SiC) and hydrogenated (a-SiC:H) silicon carbides are studied using an sp sup 3 s sup * tight-binding force model with molecular dynamics simulations. The parameters of a repulsive pairwise potential are determined from ab initio pseudopotential calculations. Both carbides are generated from dilute vapours condensed from high temperature, with post-annealing at low temperature for a-SiC:H. A plausible model for the inter-atomic correlations and electronic states in a-SiC:H is suggested. According to this model, the formation of the amorphous network is weakly sensitive to the presence of hydrogen. Hydrogen passivates effectively only the weak bonds of threefold-coordinated atoms. Chemical ordering is very much affected by the cooling rate and the structure of the high-temperature vapour. The as-computed characteristics are in rather good agreement with the results for a-SiC and a-Si:H from ab initio calculations.

  7. Aperiodic-metamaterial-based absorber

    Directory of Open Access Journals (Sweden)

    Quanlong Yang


    Full Text Available The periodic-metamaterial-based perfect absorber has been studied broadly. Conversely, if the unit cell in the metamaterial-based absorber is arranged aperiodically (aperiodic-metamaterial-based absorber, how does it perform? Inspired by this, here we present a systematic study of the aperiodic-metamaterial-based absorber. By investigating the response of metamaterial absorbers based on periodic, Fibonacci, Thue-Morse, and quasicrystal lattices, we found that aperiodic-metamaterial-based absorbers could display similar absorption behaviors as the periodic one in one hand. However, their absorption behaviors show different tendency depending on the thicknesses of the spacer. Further studies on the angle and polarization dependence of the absorption behavior are also presented.

  8. Cyanthiwigin Natural Product Core as a Complex Molecular Scaffold for Comparative Late-Stage C-H Functionalization Studies. (United States)

    Kim, Kelly E; Adams, Ashley M; Chiappini, Nicholas D; Du Bois, J; Stoltz, Brian M


    The desire for maximally efficient transformations in complex molecule synthesis has contributed to a surge of interest in C-H functionalization methods development in recent years. In contrast to the steady stream of methodological reports, however, there are noticeably fewer studies comparing the efficacies of different C-H functionalization protocols on a single structurally intricate substrate. Recognizing the importance of heteroatom incorporation in complex molecule synthesis, this report discloses a comparative examination of diverse strategies for C-O, C-N, and C-X bond formation through late-stage C-H oxidation of the tricyclic cyanthiwigin natural product core. Methods for allylic C-H acetoxylation, tertiary C-H hydroxylation, tertiary C-H amination, tertiary C-H azidation, and secondary C-H halogenation are explored. These efforts highlight the robustness and selectivities of many well-established protocols for C-H oxidation when applied to a complex molecular framework, and the findings are relevant to chemists aiming to employ such strategies in the context of chemical synthesis.

  9. Burnable absorber coated nuclear fuel

    International Nuclear Information System (INIS)

    Chubb, W.; Radford, K.C.; Parks, B.H.


    A nuclear fuel body which is at least partially covered by a burnable neutron absorber layer is provided with a hydrophobic overcoat generally covering the burnable absorber layer and bonded directly to it. In a method for providing a UO 2 fuel pellet with a zirconium diboride burnable poison layer, the fuel body is provided with an intermediate niobium layer. (author)

  10. Metal-shearing energy absorber (United States)

    Fay, R. J.; Wittrock, E. P.


    Device, consisting of tongue of thin aluminum alloy strip, pull tab, slotted steel plate which serves as cutter, and steel buckle, absorbs mechanical energy when its ends are subjected to tensile loading. Device is applicable as auxiliary shock absorbing anchor for automobile and airplane safety belts.

  11. Leaf absorbance and photosynthesis (United States)

    Schurer, Kees


    The absorption spectrum of a leaf is often thought to contain some clues to the photosynthetic action spectrum of chlorophyll. Of course, absorption of photons is needed for photosynthesis, but the reverse, photosynthesis when there is absorption, is not necessarily true. As a check on the existence of absorption limits we measured spectra for a few different leaves. Two techniques for measuring absorption have been used, viz. the separate determination of the diffuse reflectance and the diffuse transmittance with the leaf at a port of an integrating sphere and the direct determination of the non-absorbed fraction with the leaf in the sphere. In a cross-check both methods yielded the same results for the absorption spectrum. The spectrum of a Fuchsia leaf, covering the short-wave region from 350 to 2500 nm, shows a high absorption in UV, blue and red, the well known dip in the green and a steep fall-off at 700 nm. Absorption drops to virtually zero in the near infrared, with subsequent absorptions, corresponding to the water absorption bands. In more detailed spectra, taken at 5 nm intervals with a 5 nm bandwidth, differences in chlorophyll content show in the different depths of the dip around 550 nm and in a small shift of the absorption edge at 700 nm. Spectra for Geranium (Pelargonium zonale) and Hibiscus (with a higher chlorophyll content) show that the upper limit for photosynthesis can not be much above 700 nm. No evidence, however, is to be seen of a lower limit for photosynthesis and, in fact, some experiments down to 300 nm still did not show a decrease of the absorption although it is well recognized that no photosynthesis results with 300 nm wavelengths.

  12. Molecular heterogeneous catalysts derived from bipyridine-based organosilica nanotubes for C-H bond activation. (United States)

    Zhang, Shengbo; Wang, Hua; Li, Mei; Han, Jinyu; Liu, Xiao; Gong, Jinlong


    Heterogeneous metal complex catalysts for direct C-H activation with high activity and durability have always been desired for transforming raw materials into feedstock chemicals. This study described the design and synthesis of one-dimensional organosilica nanotubes containing 2,2'-bipyridine (bpy) ligands in the framework (BPy-NT) and their post-synthetic metalation to provide highly active and robust molecular heterogeneous catalysts. By adjusting the ratios of organosilane precursors, very short BPy-NT with ∼50 nm length could be controllably obtained. The post-synthetic metalation of bipyridine-functionalized nanotubes with [IrCp*Cl(μ-Cl)] 2 (Cp* = η 5 -pentamethylcyclopentadienyl) and [Ir(cod)(OMe)] 2 (cod = 1,5-cyclooctadiene) afforded solid catalysts, IrCp*-BPy-NT and Ir(cod)-BPy-NT, which were utilized for C-H oxidation of heterocycles and cycloalkanes as well as C-H borylation of arenes. The cut-short nanotube catalysts displayed enhanced activities and durability as compared to the analogous homogeneous catalysts and other conventional heterogeneous catalysts, benefiting from the isolated active sites as well as the fast transport of substrates and products. After the reactions, a detailed characterization of Ir-immobilized BPy-NT via TEM, SEM, nitrogen adsorption, UV/vis, XPS, and 13 C CP MAS NMR indicated the molecular nature of the active species as well as stable structures of nanotube scaffolds. This study demonstrates the potential of BPy-NT with a short length as an integration platform for the construction of efficient heterogeneous catalytic systems for organic transformations.

  13. Properties of a-C:H:O plasma polymer films deposited from acetone vapors

    Energy Technology Data Exchange (ETDEWEB)

    Drabik, M., E-mail: [Empa, Swiss Federal Laboratories for Materials Science and Technology, Lerchenfeldstrasse 5, 9014 St. Gallen (Switzerland); Celma, C. [Empa, Swiss Federal Laboratories for Materials Science and Technology, Lerchenfeldstrasse 5, 9014 St. Gallen (Switzerland); Kousal, J.; Biederman, H. [Charles University in Prague, Faculty of Mathematics and Physics, Department of Macromolecular Physics, V Holešovičkách 2, 180 00 Prague 8 (Czech Republic); Hegemann, D. [Empa, Swiss Federal Laboratories for Materials Science and Technology, Lerchenfeldstrasse 5, 9014 St. Gallen (Switzerland)


    To gain insight into the deposition and stability of oxygen-containing plasma polymer films, the properties of amorphous oxygenated hydrocarbon (a-C:H:O) plasma polymer coatings deposited from acetone vapors under various experimental conditions are investigated. Apart from the discharge power, the influence of the reactive carbon dioxide (CO{sub 2}) gas on the structure of the resulting films is studied. It is found by characterization using X-ray Photoelectron Spectroscopy and Fourier-Transform Infrared Spectroscopy that the experimental conditions particularly influence the amount of oxygen in the deposited a-C:H:O plasma polymer films. The O/C elemental ratio increases with increasing amount of CO{sub 2} in the working gas mixture (up to 0.2 for 24 sccm of CO{sub 2} at 30 W) and decreases with increasing RF discharge power (down to 0.17 for 50 W). Furthermore, the nature of bonds between the oxygen and carbon atoms has been examined. Only low amounts of double and triple bonded carbon are observed. This has a particular influence on the aging of the plasma polymer films which is studied both in ambient air and in distilled water for up to 4 months. Overall, stable a-C:H:O plasma polymer films are deposited comprising low amounts (up to about 5%) of ester/carboxyl groups. - Highlights: • Hydrocarbon plasma polymer films with variable oxygen content can be prepared. • Stable oxygenated hydrocarbon plasma polymers contain max 5% of ester/carboxyl groups. • Acetone-derived plasma polymer films can be used as permanent hydrophilic surfaces.

  14. Tribological properties of TiC/a-C:H nanocomposite coatings prepared via HiPIMS (United States)

    Sánchez-López, J. C.; Dominguez-Meister, S.; Rojas, T. C.; Colasuonno, M.; Bazzan, M.; Patelli, A.


    High power impulse magnetron sputtering (HiPIMS) technology has been employed to prepare TiC/a-C:H nanocomposite coatings from a titanium target in acetylene (C2H2) reactive atmospheres. Gas fluxes were varied from 1.3 to 4.4 sccm to obtain C/Ti ratios from 2 to 15 as measured by electron probe microanalysis (EPMA). X-ray diffraction and transmission electron microscopy demonstrate the presence of TiC nanocrystals embedded in an amorphous carbon-based matrix. The hardness properties decrease from 17 to 10 GPa as the carbon content increases. The tribological properties were measured using a pin-on-disk tribometer in ambient air (RH = 30-40%) at 10 cm/s with 5 N of applied load against 6-mm 100Cr6 balls. The friction coefficient and the film wear rates are gradually improved from 0.3 and 7 × 10-6 mm3/N m to 0.15 and 2 × 10-7 mm3/N m, respectively, by increasing the C2H2 flux. To understand the tribological processes appearing at the interface and to elucidate the wear mechanism, microstructural and chemical investigations of the coatings were performed before and after the friction test. EPMA, X-ray photoelectron and electron energy-loss spectroscopies were employed to obtain an estimation of the fraction of the a-C:H phase, which can be correlated with the tribological behavior. Examination of the friction counterfaces (ball and track) by Raman microanalysis reveals an increased ordering of the amorphous carbon phase concomitant with friction reduction. The tribological results were compared with similar TiC/a-C(:H) composites prepared by the conventional direct current process.

  15. Selective C-H Bond Oxidation Catalyzed by the Fe-bTAML Complex: Mechanistic Implications. (United States)

    Ghosh, Munmun; Pattanayak, Santanu; Dhar, Basab B; Singh, Kundan K; Panda, Chakadola; Sen Gupta, Sayam


    Nonheme iron complexes bearing tetradentate N-atom-donor ligands with cis labile sites show great promise for chemoselective aliphatic C-H hydroxylation. However, several challenges still limit their widespread application. We report a mechanism-guided development of a peroxidase mimicking iron complex based on the bTAML macrocyclic ligand framework (Fe-bTAML: biuret-modified tetraamido macrocyclic ligand) as a catalyst to perform selective oxidation of unactivated 3° bonds with unprecedented regioselectivity (3°:2° of 110:1 for adamantane oxidation), high stereoretention (99%), and turnover numbers (TONs) up to 300 using mCPBA as the oxidant. Ligand decomposition pathways involving acid-induced demetalation were identified, and this led to the development of more robust and efficient Fe-bTAML complexes that catalyzed chemoselective C-H oxidation. Mechanistic studies, which include correlation of the product formed with the Fe V (O) reactive intermediates generated during the reaction, indicate that the major pathway involves the cleavage of C-H bonds by Fe V (O). When these oxidations were performed in the presence of air, the yield of the oxidized product doubled, but the stereoretention remained unchanged. On the basis of 18 O labeling and other mechanistic studies, we propose a mechanism that involves the dual activation of mCPBA and O 2 by Fe-bTAML, leading to formation of the Fe V (O) intermediate. This high-valent iron oxo remains the active intermediate for most of the reaction, resulting in high regio- and stereoselectivity during product formation.

  16. Origins of Protons in C-H Bond Insertion Products of Phenols: Proton-Self-Sufficient Function via Water Molecules. (United States)

    Luo, Zhoujie; Gao, Ya; Zhu, Tong; Zhang, John Zenghui; Xia, Fei


    Water molecules can serve as proton shuttles for proton transfer in the C-H bond insertion reactions catalyzed by transition metal complexes. Recently, the control experiments performed for C-H bond insertion of phenol and anisol by gold carbenes show that large discrepancy exists in the yields of hydrogenated and deuterated products. Thus, we conducted a detailed theoretical analysis on the function of water molecules in the C-H bond insertion reactions. The comparison of calculated results and control experiments indicates that the solution water molecules play a crucial role of proton shuttle in C-H bond insertion. In particular, it was found that the hydroxyl groups in phenols were capable of donating protons via water shuttles for the production of C-H products, which had a substantial influence on the yields of inserted products. The hydroxyl groups instead of C-H bonds in phenols function like "proton reservoirs" in the C-H bond insertion, which we call the "proton self-sufficient" (PSS) function of phenol. The PSS function of phenol indicates that the substrates with and without proton reservoirs will lead to different C-H bond insertion products.

  17. Photocatalytic C??H Activation of Hydrocarbons over VO@g??C3N4 (United States)

    A highly selective and sustainable method has been developed for the oxidation of methyl arenes and their analogues. The VO@g-C3N4 catalyst is very efficient in the C??H activation and oxygen insertion reaction resulting in formation of the corresponding carbonyl compounds and phenols.This dataset is associated with the following publication:Verma, S., R.B. Nasir Baig, M. Nadagouda , and R. Varma. Photocatalytic C−H Activation of Hydrocarbons over VO@g‑C3N4. ACS Sustainable Chemistry & Engineering. American Chemical Society, Washington, DC, USA, 4(4): 2333-2336, (2016).

  18. Canangalias C-H, juvenile hormone III analogues from the roots of Cananga latifolia. (United States)

    Phatchana, Ratchanee; Thongsri, Yordhathai; Yenjai, Chavi


    Chemical investigation of the roots of Cananga latifolia led to the isolation and purification of thirteen juvenile hormone III analogues. Six new analogues, canangalias C-H (1-6) and a new natural product, (2E,6E,10R)-10-acetoxy-11-hydroxy-3,7,11-trimethyldodeca-2,6-dienoic acid methyl ester (7), were isolated. In addition, six known juvenile hormone III analogues were isolated. Their structures were established by spectroscopic methods including 1D and 2D NMR, IR and mass spectrometry. Copyright © 2016 Elsevier B.V. All rights reserved.

  19. Studies of beauty baryon decays to $D^0 ph^-$ and $\\Lambda_c^+ h^-$ final states


    Aaij, Roel; Adeva, Bernardo; Adinolfi, Marco; Adrover, Cosme; Affolder, Anthony; Ajaltouni, Ziad; Albrecht, Johannes; Alessio, Federico; Alexander, Michael; Ali, Suvayu; Alkhazov, Georgy; Alvarez Cartelle, Paula; Alves Jr, Antonio; Amato, Sandra; Amerio, Silvia


    Decays of beauty baryons to the D[superscript 0]ph[superscript −] and Λ[+ over c]h[superscript −] final states (where h indicates a pion or a kaon) are studied using a data sample of pp collisions, corresponding to an integrated luminosity of 1.0  fb[superscript −1], collected by the LHCb detector. The Cabibbo-suppressed decays Λ[0 over b] → D[superscript 0]pK[superscript −] and Λ[0 over b] → Λ[+ over c]K[superscript −] are observed, and their branching fractions are measured with respect to ...

  20. Annulation of aromatic imines via directed C-H bond activation. (United States)

    Thalji, Reema K; Ahrendt, Kateri A; Bergman, Robert G; Ellman, Jonathan A


    A directed C-H bond activation approach to the synthesis of indans, tetralins, dihydrofurans, dihydroindoles, and other polycyclic aromatic compounds is presented. Cyclization of aromatic ketimines and aldimines containing alkenyl groups tethered at the meta position relative to the imine directing group has been achieved using (PPh3)3RhCl (Wilkinson's catalyst). The cyclization of a range of aromatic ketimines and aldimines provides bi- and tricyclic ring systems with good regioselectivity. Different ring sizes and substitution patterns can be accessed through the coupling of monosubstituted, 1,1- or 1,2-disubstituted, and trisubstituted alkenes bearing both electron-rich and electron-deficient functionality.

  1. Highly efficient and enantioselective cyclization of aromatic imines via directed C-H bond activation. (United States)

    Thalji, Reema K; Ellman, Jonathan A; Bergman, Robert G


    The first highly enantioselective catalytic reaction involving aromatic C-H bond activation is communicated. Enantioselective cyclization of aromatic ketimines containing alkenyl groups tethered at the meta position of an imine directing group has been achieved using 5 mol % [RhCl(coe)2]2 and 15 mol % of an (S)-binol-derived phosphoramidite ligand. Selectivities of up to 96% ee and up to quantitative yields were obtained. Moreover, the identified catalyst system enables the intramolecular alkylation reaction to be performed at temperatures 75 degrees C lower than our previously reported achiral system. The reaction can even be performed at room temperature for one of the optimal substrates.

  2. C-H to C-N Cross-Coupling of Sulfonamides with Olefins. (United States)

    Ma, Rulin; White, M Christina


    Cross-coupling of nitrogen with hydrocarbons under fragment coupling conditions stands to significantly impact chemical synthesis. Herein, we disclose a C(sp 3 )-N fragment coupling reaction between terminal olefins and N-triflyl protected aliphatic and aromatic amines via Pd(II)/SOX (sulfoxide-oxazoline) catalyzed intermolecular allylic C-H amination. A range of (56) allylic amines are furnished in good yields (avg. 75%) and excellent regio- and stereoselectivity (avg. >20:1 linear:branched, >20:1 E: Z). Mechanistic studies reveal that the SOX ligand framework is effective at promoting functionalization by supporting cationic π-allyl Pd.

  3. Selective molecular recognition, C-H bond activation, and catalysis in nanoscale reaction vessels

    Energy Technology Data Exchange (ETDEWEB)

    Fiedler, Dorothea; Leung, Dennis H.; Raymond, Kenneth N.; Bergman, Robert G.


    Supramolecular chemistry represents a way to mimic enzyme reactivity by using specially designed container molecules. We have shown that a chiral self-assembled M{sub 4}L{sub 6} supramolecular tetrahedron can encapsulate a variety of cationic guests, with varying degrees of stereoselectivity. Reactive iridium guests can be encapsulated and the C-H bond activation of aldehydes occurs, with the host cavity controlling the ability of substrates to interact with the metal center based upon size and shape. In addition, the host container can act as a catalyst by itself. By restricting reaction space and preorganizing the substrates into reactive conformations, it accelerates the sigmatropic rearrangement of enammonium cations.

  4. New Approach to 1,4-Benzoxazin-3-ones by Electrochemical C-H Amination. (United States)

    Wesenberg, Lars Julian; Herold, Sebastian; Shimizu, Akihiro; Yoshida, Jun-Ichi; Waldvogel, Siegfried R


    1,4-Benzoxazin-3-ones are important structural motifs in natural products and bioactive compounds. Usually, the synthesis of benzoxazinones requires transition-metal catalysts and pre-functionalized substrates such as aryl halides. However, the anodic C-H amination of phenoxy acetates offers a very efficient and sustainable access to these heterocycles. The presented electrochemical protocol can be applied to a broad scope of alkylated substrates. Even tert-butyl moieties or halogen substituents are compatible with this versatile method. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Magnetic graphitic carbon nitride: its applicationin the C-& H-activation of amines. (United States)

    Magnetic graphitic carbon nitride, Fe@g-C3N4, has been synthesized by adorning graphitic carbon nitride (g-C3N4) support with iron oxide via non-covalent interaction. The magnetically recyclable catalyst showed excellent reactivity for expeditious C-H activation and cyanation of amines.This dataset is associated with the following publication:Verma, S., R.B. Nasir Baig, H. Changseok, M. Nadagouda , and R. Varma. Magnetic graphitic carbon nitride: its applicationin the C–H activation of amines. CHEMICAL COMMUNICATIONS. Royal Society of Chemistry, Cambridge, UK, 51(85): 15554 - 15557, (2015).

  6. Kinetics of Hydrocarbon formation in a- C:H Film deposition plasmas

    Energy Technology Data Exchange (ETDEWEB)

    Cal, E. de la; Tabares, F. L.


    The formation of C2 and Cp hydrocarbons during the PACVD of a-C:H films from admixtures of methane with H2 and He has been investigated by mass spectrometry under several deposition condition. The time evolution of the observed species indicates that the formation mechanisms of ethylene and acetylene are sensitive to the conditions of the wall during the growing of the film. Acetylene are sensitive to the conditions of the wall during the growing of the film. Acetylene formation was found to be directly related to the formation of the film on top of the carburized metal. (Author) 12 refs.

  7. Visible light broadband perfect absorbers

    Energy Technology Data Exchange (ETDEWEB)

    Jia, X. L.; Meng, Q. X.; Yuan, C. X.; Zhou, Z. X.; Wang, X. O., E-mail: [School of Science, Harbin Institute of Technology, Harbin 150001 (China)


    The visible light broadband perfect absorbers based on the silver (Ag) nano elliptical disks and holes array are studied using finite difference time domain simulations. The semiconducting indium silicon dioxide thin film is introduced as the space layer in this sandwiched structure. Utilizing the asymmetrical geometry of the structures, polarization sensitivity for transverse electric wave (TE)/transverse magnetic wave (TM) and left circular polarization wave (LCP)/right circular polarization wave (RCP) of the broadband absorption are gained. The absorbers with Ag nano disks and holes array show several peaks absorbance of 100% by numerical simulation. These simple and flexible perfect absorbers are particularly desirable for various potential applications including the solar energy absorber.

  8. Neutron diffraction study of phase relationship of Ti-C-H system

    International Nuclear Information System (INIS)

    Khidirov, I.; Mukhtarova, N.N.; Mirzaev, B.B.; Serikbaev, B.T.; Zaginaichenko, S.Yu.; Schur, D.V.; Pishuk, V.K.; Kuzmenko, L.V.; Garbuz, V.V.; Nuzhda, S.V.; Pishuk, O.V.


    temperature the sintering process is very active. Later on, the step increasing of temperature was carried out till 1000 deg. C with a step of 100 deg. C. The briquettes were exposed during 24 h at each temperature. With increasing temperature up to 800-1000 deg. C the pressured powder became well sintered and hydrogen emission from the sample was prevented. The final product was prepared after the annealing at 1000 deg. C followed by quenching in water. Compound of the samples was controlled by chemical analysis and compound of the single-phase samples also was controlled by minimizing the divergence factors of structure determination using neutron diffraction patterns. It is established that at hardening from 1000 deg. C in the samples with low concentration of C and H the solid solution of C and H in BCC β-Ti (with impurity of FCC- TiC x H y -phase) is formed. This metastable phase is stable enough at the room temperature. It is shown that at carbon concentration of 0.30 ≤ x ≤ 0.50 and y ≥ x in Ti-C-H system the ordered hexagonal close-packed (HCP) structure is stabilized, and at y x H y compounds have the ordered HCP structure corresponding to formula Ti 2 C 1-z H 2-z . The crystal structure of the phase is described within the framework of space group, where metal atoms are strongly displaced along c axis (Z Me =0.234±0.001) with respect to their ideal positions (z id =1/4). Step annealing of the single-phase solid solutions at temperatures of 700-600-500 deg. C during 24 h leads to decay of the samples, having concentration C/Ti≤0.43, the hydride phases being separated. Hence, the ordered solid solution Ti 2 C 1-x H 2-y is stable at concentrations 1.00≥C/Ti>0.43 (near carbon stoichiometry Ti 2 C), but it is metastable at concentrations 0.30≤C/T≤0.43. Compound TiC x H y at concentrations 0.45≤x≤0.55 and y< x can have both disordered (sp. gr. Fm3m) and ordered FCC-structure (sp. gr. Fd3m) depending on temperature. At temperatures lower than 600 deg. C

  9. The mechanism of stereospecific C-H oxidation by Fe(Pytacn) complexes: bioinspired non-heme iron catalysts containing cis-labile exchangeable sites. (United States)

    Prat, Irene; Company, Anna; Postils, Verònica; Ribas, Xavi; Que, Lawrence; Luis, Josep M; Costas, Miquel


    A detailed mechanistic study of the hydroxylation of alkane C-H bonds using H2O2 by a family of mononuclear non heme iron catalysts with the formula [Fe(II)(CF3SO3)2(L)] is described, in which L is a tetradentate ligand containing a triazacyclononane tripod and a pyridine ring bearing different substituents at the α and γ positions, which tune the electronic or steric properties of the corresponding iron complexes. Two inequivalent cis-labile exchangeable sites, occupied by triflate ions, complete the octahedral iron coordination sphere. The C-H hydroxylation mediated by this family of complexes takes place with retention of configuration. Oxygen atoms from water are incorporated into hydroxylated products and the extent of this incorporation depends in a systematic manner on the nature of the catalyst, and the substrate. Mechanistic probes and isotopic analyses, in combination with detailed density functional theory (DFT) calculations, provide strong evidence that C-H hydroxylation is performed by highly electrophilic [Fe(V)(O)(OH)L] species through a concerted asynchronous mechanism, involving homolytic breakage of the C-H bond, followed by rebound of the hydroxyl ligand. The [Fe(V)(O)(OH)L] species can exist in two tautomeric forms, differing in the position of oxo and hydroxide ligands. Isotopic-labeling analysis shows that the relative reactivities of the two tautomeric forms are sensitively affected by the α substituent of the pyridine, and this reactivity behavior is rationalized by computational methods. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Erosion of a-B/C : H films under deuterium plasma irradiation (United States)

    Sharapov, V. M.; Kanaev, A. I.; Rybakov, S. Yu.; Gavrilov, L. E.


    The erosion of amorphous boronized carbon a-B/C : H films under low energy deuterium plasma irradiation was investigated. The films were deposited on a silicon substrate by the PCVD-method using the carborane vapour C 2B 10H 12 as a precursor. The deuterium plasma parameters in the erosion experiments were the following: ion flux density 3 × 10 16 cm -2 s -1, ion energy 50 eV, thermal atom flux density 1 × 10 16 cm -2 s -1. The erosion yields were calculated on the basis of mass thickness losses which were measured by electron probe micro-analysis. The erosion yields of a-B/C : H films do not depend on the temperature in the range 100-550°C and are more than one order of magnitude lower compared to those of boronized graphite USB-15. It was shown that the film erodes through the developing porosity which initially exists in the film and that the erosion has a chemical nature.

  11. C-H Hot Bands in the Near-IR Emission Spectra of Leonids (United States)

    Freund, F. T.; Scoville, J.; Holm, R.; Seelemann, R.; Freund, M. M.


    The reported infrared (IR) emission spectra from 1999 Leonid fireballs show a 3.4 micron C-H emission band and unidentified bands at longer wavelengths. Upon atmospheric entry, the Leonid meteorites were flash-heated to temperatures around 2400K, which would destroy any organics on the surface of the meteorite grains. We propose that the nu(sub )CH emission band in the Leonid emission spectra arises from matrix-embedded C(sub n)-H-O entities that are protected from instant pyrolysis. Our model is based on IR absorption nu(sub )CH bands, which we observed in laboratory-grown MgO and natural olivine single crystals, where they arise from C(sub n)-H-O units imbedded in the mineral matrix, indicative of aliphatic -CH2- and -CH3 organics. Instead of being pyrolyzed, the C(sub n)-H-O entities in the Leonid trails become vibrationally excited to higher levels n = 1, 2, 3 etc. During de-excitation they emit at 3.4 microns, due to the (0 => 1) transition, and at longer wavelengths, due to hot bands. As a first step toward verifying this hypothesis we measured the C-H vibrational manifold of hexane (C6H14). The calculated positions of the (2 => l ) , (3 => 2), and possibly (4 => 3) hot bands agree with the Leonid emission bands at 3.5, 3.8 and 4.l microns.

  12. Ion beam analysis of a-C:H films on alloy steel substrate

    International Nuclear Information System (INIS)

    Silva, T.F.; Moro, M.V.; Trindade, G.F.; Added, N.; Tabacniks, M.H.; Santos, R.J.; Santana, P.L.; Bortoleto, J.R.R.


    An a-C:H thin film deposited by plasma immersion ion implantation and deposition on alloy steel (16MnCr5) was analyzed using a self-consistent ion beam analysis technique. In the self-consistent analysis, the results of each individual technique are combined in a unique model, increasing confidence and reducing simulation errors. Self-consistent analysis, then, is able to improve the regular ion beam analysis since several analyses commonly used to process ion beam data still rely on handling each spectrum independently. The sample was analyzed by particle-induced x-ray emission (for trace elements), elastic backscattering spectrometry (for carbon), forward recoil spectrometry (for hydrogen) and Rutherford backscattering spectrometry (for film morphology). The self-consistent analysis provided reliable chemical information about the film, despite its “heavy” substrate. As a result, we could determine precisely the H/C ratio, contaminant concentration and some morphological characteristics of the film, such as roughness and discontinuities. - Highlights: • Self-consistent approach of ion beam analysis was used to characterize an a-C:H film. • The self-consistent analysis provided a unequivocal and reliable model of the sample. • Morphological aspects of the film were assessed with the ion beam analysis

  13. Spontaneous reduction and C-H borylation of arenes mediated by uranium(III) disproportionation (United States)

    Arnold, Polly L.; Mansell, Stephen M.; Maron, Laurent; McKay, David


    Transition-metal-arene complexes such as bis(benzene)chromium Cr(η6-C6H6)2 are historically important to d-orbital bonding theory and have modern importance in organic synthesis, catalysis and organic spintronics. In investigations of f-block chemistry, however, arenes are invariably used as solvents rather than ligands. Here, we show that simple uranium complexes UX3 (X = aryloxide, amide) spontaneously disproportionate, transferring an electron and X-ligand, allowing the resulting UX2 to bind and reduce arenes, forming inverse sandwich molecules [X2U(µ-η6:η6-arene)UX2] and a UX4 by-product. Calculations and kinetic studies suggest a ‘cooperative small-molecule activation’ mechanism involving spontaneous arene reduction as an X-ligand is transferred. These mild reaction conditions allow functionalized arenes such as arylsilanes to be incorporated. The bulky UX3 are also inert to reagents such as boranes that would react with the traditional harsh reaction conditions, allowing the development of a new in situ arene C-H bond functionalization methodology converting C-H to C-B bonds.

  14. Grieks aan die P.U. vir C.H.O.*

    Directory of Open Access Journals (Sweden)

    J.H. Grobler


    Full Text Available Met hierdie rede word betoog dat die patroon van die studie van Grieks wat deur die Atheners vier tot vyf eeue v.C. daargestel is en deur die Alexandryne en Pergamon van drie eeue v.C. tot drie eeu n.C. verder gevorm is, deur die eeue nagevolg is, telkens met die oogmerke wat gepas het by die bepaalde tye, tot in die twintigste eeu. Volgens hierdie patroon is Attiese Grieks bestudeer. Die Attiese Grieks is die literêre taal, die skryftaal, van Athene in die vyfde en vierde eeue v.C. Hierdie tradisie is ook aan die P.U. vir C.H.O. nagevolg. Aan hierdie Universiteit is die studente van Grieks hoofsaaklik, indien nie uitsluitlik nie, voornemende teologiese studente.

  15. Modification of Purine and Pyrimidine Nucleosides by Direct C-H Bond Activation

    Directory of Open Access Journals (Sweden)

    Yong Liang


    Full Text Available Transition metal-catalyzed modifications of the activated heterocyclic bases of nucleosides as well as DNA or RNA fragments employing traditional cross-coupling methods have been well-established in nucleic acid chemistry. This review covers advances in the area of cross-coupling reactions in which nucleosides are functionalized via direct activation of the C8-H bond in purine and the C5-H or C6-H bond in uracil bases. The review focuses on Pd/Cu-catalyzed couplings between unactivated nucleoside bases with aryl halides. It also discusses cross-dehydrogenative arylations and alkenylations as well as other reactions used for modification of nucleoside bases that avoid the use of organometallic precursors and involve direct C-H bond activation in at least one substrate. The scope and efficiency of these coupling reactions along with some mechanistic considerations are discussed.

  16. Designing Homogeneous Bromine Redox Catalysis for Selective Aliphatic C-H Bond Functionalization. (United States)

    Muniz, Kilian; Becker, Peter; Duhamel, Thomas; Martinez, Claudio


    The potential of homogeneous oxidation catalysis employing bromine has remained largely unexplored. The combination of tetraalkylammonium bromide and 3-chloroperbenzoic acid offers a unique catalyst system for the convenient and selective oxidation of saturated Csp3-H bonds upon photochemical initiation with visible light. It enables remote intramolecular, position-selective C-H amination as demonstrated for 20 different examples. For the first time, a N-halogenated intermediate could be isolated as the active catalyst state in a catalytic Hofmann-Löffler reaction. In addition, a novel expeditious one-pot synthesis of N-sulfonyloxaziridines from N-sulfonamides was developed and exemplified for 15 transformations. These pioneering examples provide a change in paradigm for molecular catalysis with bromine. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. R.E.A.C.H. to Teach: Making Patient and Family Education "Stick". (United States)

    Cutilli, Carolyn Crane


    Healthcare professionals teach patients and families about their health every day. Regulatory and accreditation organizations mandate patient and family education to promote better health outcomes. And recently, financial rewards for healthcare organizations are being tied to patient satisfaction (Hospital Consumer Assessment of Healthcare Providers and Systems-HCAHPS). A University of Pennsylvania Health System group of staff and patients, devoted to excellence in patient and family education, developed the graphic "R.E.A.C.H. to Teach." The purpose of the graphic is to make evidence-based practice (EBP) for patient and family education "stick" with staff. The group used concepts from the marketing book, Made to Stick, to demonstrate how to develop effective staff and patient and family education. Ideas (education) that survive ("stick") have the following attributes: simple, unexpected, concrete, credible, emotional, and narrative (story). This article demonstrates how to apply these principles and EBP to patient and family education.

  18. Studies of beauty baryon decays to $D^0 ph^-$ and $\\Lambda_c^+ h^-$ final states

    CERN Document Server

    Aaij, Roel; Adinolfi, Marco; Adrover, Cosme; Affolder, Anthony; Ajaltouni, Ziad; Albrecht, Johannes; Alessio, Federico; Alexander, Michael; Ali, Suvayu; Alkhazov, Georgy; Alvarez Cartelle, Paula; Alves Jr, Antonio; Amato, Sandra; Amerio, Silvia; Amhis, Yasmine; Anderlini, Lucio; Anderson, Jonathan; Andreassen, Rolf; Andreotti, Mirco; Andrews, Jason; Appleby, Robert; Aquines Gutierrez, Osvaldo; Archilli, Flavio; Artamonov, Alexander; Artuso, Marina; Aslanides, Elie; Auriemma, Giulio; Baalouch, Marouen; Bachmann, Sebastian; Back, John; Badalov, Alexey; Balagura, Vladislav; Baldini, Wander; Barlow, Roger; Barschel, Colin; Barsuk, Sergey; Barter, William; Batozskaya, Varvara; Bauer, Thomas; Bay, Aurelio; Beddow, John; Bedeschi, Franco; Bediaga, Ignacio; Belogurov, Sergey; Belous, Konstantin; Belyaev, Ivan; Ben-Haim, Eli; Bencivenni, Giovanni; Benson, Sean; Benton, Jack; Berezhnoy, Alexander; Bernet, Roland; Bettler, Marc-Olivier; van Beuzekom, Martinus; Bien, Alexander; Bifani, Simone; Bird, Thomas; Bizzeti, Andrea; Bjørnstad, Pål Marius; Blake, Thomas; Blanc, Frédéric; Blouw, Johan; Blusk, Steven; Bocci, Valerio; Bondar, Alexander; Bondar, Nikolay; Bonivento, Walter; Borghi, Silvia; Borgia, Alessandra; Bowcock, Themistocles; Bowen, Espen Eie; Bozzi, Concezio; Brambach, Tobias; van den Brand, Johannes; Bressieux, Joël; Brett, David; Britsch, Markward; Britton, Thomas; Brook, Nicholas; Brown, Henry; Bursche, Albert; Busetto, Giovanni; Buytaert, Jan; Cadeddu, Sandro; Calabrese, Roberto; Callot, Olivier; Calvi, Marta; Calvo Gomez, Miriam; Camboni, Alessandro; Campana, Pierluigi; Campora Perez, Daniel; Carbone, Angelo; Carboni, Giovanni; Cardinale, Roberta; Cardini, Alessandro; Carranza-Mejia, Hector; Carson, Laurence; Carvalho Akiba, Kazuyoshi; Casse, Gianluigi; Castillo Garcia, Lucia; Cattaneo, Marco; Cauet, Christophe; Cenci, Riccardo; Charles, Matthew; Charpentier, Philippe; Cheung, Shu-Faye; Chiapolini, Nicola; Chrzaszcz, Marcin; Ciba, Krzystof; Cid Vidal, Xabier; Ciezarek, Gregory; Clarke, Peter; Clemencic, Marco; Cliff, Harry; Closier, Joel; Coca, Cornelia; Coco, Victor; Cogan, Julien; Cogneras, Eric; Collins, Paula; Comerma-Montells, Albert; Contu, Andrea; Cook, Andrew; Coombes, Matthew; Coquereau, Samuel; Corti, Gloria; Couturier, Benjamin; Cowan, Greig; Craik, Daniel Charles; Cruz Torres, Melissa Maria; Cunliffe, Samuel; Currie, Robert; D'Ambrosio, Carmelo; Dalseno, Jeremy; David, Pascal; David, Pieter; Davis, Adam; De Bonis, Isabelle; De Bruyn, Kristof; De Capua, Stefano; De Cian, Michel; De Miranda, Jussara; De Paula, Leandro; De Silva, Weeraddana; De Simone, Patrizia; Decamp, Daniel; Deckenhoff, Mirko; Del Buono, Luigi; Déléage, Nicolas; Derkach, Denis; Deschamps, Olivier; Dettori, Francesco; Di Canto, Angelo; Dijkstra, Hans; Dogaru, Marius; Donleavy, Stephanie; Dordei, Francesca; Dorosz, Piotr; Dosil Suárez, Alvaro; Dossett, David; Dovbnya, Anatoliy; Dupertuis, Frederic; Durante, Paolo; Dzhelyadin, Rustem; Dziurda, Agnieszka; Dzyuba, Alexey; Easo, Sajan; Egede, Ulrik; Egorychev, Victor; Eidelman, Semen; van Eijk, Daan; Eisenhardt, Stephan; Eitschberger, Ulrich; Ekelhof, Robert; Eklund, Lars; El Rifai, Ibrahim; Elsasser, Christian; Falabella, Antonio; Färber, Christian; Farinelli, Chiara; Farry, Stephen; Ferguson, Dianne; Fernandez Albor, Victor; Ferreira Rodrigues, Fernando; Ferro-Luzzi, Massimiliano; Filippov, Sergey; Fiore, Marco; Fiorini, Massimiliano; Fitzpatrick, Conor; Fontana, Marianna; Fontanelli, Flavio; Forty, Roger; Francisco, Oscar; Frank, Markus; Frei, Christoph; Frosini, Maddalena; Furfaro, Emiliano; Gallas Torreira, Abraham; Galli, Domenico; Gandelman, Miriam; Gandini, Paolo; Gao, Yuanning; Garofoli, Justin; Garosi, Paola; Garra Tico, Jordi; Garrido, Lluis; Gaspar, Clara; Gauld, Rhorry; Gersabeck, Evelina; Gersabeck, Marco; Gershon, Timothy; Ghez, Philippe; Gibson, Valerie; Giubega, Lavinia-Helena; Gligorov, V.V.; Göbel, Carla; Golubkov, Dmitry; Golutvin, Andrey; Gomes, Alvaro; Gordon, Hamish; Grabalosa Gándara, Marc; Graciani Diaz, Ricardo; Granado Cardoso, Luis Alberto; Graugés, Eugeni; Graziani, Giacomo; Grecu, Alexandru; Greening, Edward; Gregson, Sam; Griffith, Peter; Grillo, Lucia; Grünberg, Oliver; Gui, Bin; Gushchin, Evgeny; Guz, Yury; Gys, Thierry; Hadjivasiliou, Christos; Haefeli, Guido; Haen, Christophe; Hafkenscheid, Tom; Haines, Susan; Hall, Samuel; Hamilton, Brian; Hampson, Thomas; Hansmann-Menzemer, Stephanie; Harnew, Neville; Harnew, Samuel; Harrison, Jonathan; Hartmann, Thomas; He, Jibo; Head, Timothy; Heijne, Veerle; Hennessy, Karol; Henrard, Pierre; Hernando Morata, Jose Angel; van Herwijnen, Eric; Heß, Miriam; Hicheur, Adlène; Hicks, Emma; Hill, Donal; Hoballah, Mostafa; Hombach, Christoph; Hulsbergen, Wouter; Hunt, Philip; Huse, Torkjell; Hussain, Nazim; Hutchcroft, David; Hynds, Daniel; Iakovenko, Viktor; Idzik, Marek; Ilten, Philip; Jacobsson, Richard; Jaeger, Andreas; Jans, Eddy; Jaton, Pierre; Jawahery, Abolhassan; Jing, Fanfan; John, Malcolm; Johnson, Daniel; Jones, Christopher; Joram, Christian; Jost, Beat; Jurik, Nathan; Kaballo, Michael; Kandybei, Sergii; Kanso, Wallaa; Karacson, Matthias; Karbach, Moritz; Kenyon, Ian; Ketel, Tjeerd; Khanji, Basem; Klaver, Suzanne; Kochebina, Olga; Komarov, Ilya; Koopman, Rose; Koppenburg, Patrick; Korolev, Mikhail; Kozlinskiy, Alexandr; Kravchuk, Leonid; Kreplin, Katharina; Kreps, Michal; Krocker, Georg; Krokovny, Pavel; Kruse, Florian; Kucharczyk, Marcin; Kudryavtsev, Vasily; Kurek, Krzysztof; Kvaratskheliya, Tengiz; La Thi, Viet Nga; Lacarrere, Daniel; Lafferty, George; Lai, Adriano; Lambert, Dean; Lambert, Robert W; Lanciotti, Elisa; Lanfranchi, Gaia; Langenbruch, Christoph; Latham, Thomas; Lazzeroni, Cristina; Le Gac, Renaud; van Leerdam, Jeroen; Lees, Jean-Pierre; Lefèvre, Regis; Leflat, Alexander; Lefrançois, Jacques; Leo, Sabato; Leroy, Olivier; Lesiak, Tadeusz; Leverington, Blake; Li, Yiming; Li Gioi, Luigi; Liles, Myfanwy; Lindner, Rolf; Linn, Christian; Lionetto, Federica; Liu, Bo; Liu, Guoming; Lohn, Stefan; Longstaff, Ian; Lopes, Jose; Lopez-March, Neus; Lu, Haiting; Lucchesi, Donatella; Luisier, Johan; Luo, Haofei; Luppi, Eleonora; Lupton, Oliver; Machefert, Frederic; Machikhiliyan, Irina V; Maciuc, Florin; Maev, Oleg; Malde, Sneha; Manca, Giulia; Mancinelli, Giampiero; Maratas, Jan; Marconi, Umberto; Marino, Pietro; Märki, Raphael; Marks, Jörg; Martellotti, Giuseppe; Martens, Aurelien; Martín Sánchez, Alexandra; Martinelli, Maurizio; Martinez Santos, Diego; Martins Tostes, Danielle; Martynov, Aleksandr; Massafferri, André; Matev, Rosen; Mathe, Zoltan; Matteuzzi, Clara; Maurice, Emilie; Mazurov, Alexander; McCann, Michael; McCarthy, James; McNab, Andrew; McNulty, Ronan; McSkelly, Ben; Meadows, Brian; Meier, Frank; Meissner, Marco; Merk, Marcel; Milanes, Diego Alejandro; Minard, Marie-Noelle; Molina Rodriguez, Josue; Monteil, Stephane; Moran, Dermot; Morawski, Piotr; Mordà, Alessandro; Morello, Michael Joseph; Mountain, Raymond; Mous, Ivan; Muheim, Franz; Müller, Katharina; Muresan, Raluca; Muryn, Bogdan; Muster, Bastien; Naik, Paras; Nakada, Tatsuya; Nandakumar, Raja; Nasteva, Irina; Needham, Matthew; Neubert, Sebastian; Neufeld, Niko; Nguyen, Anh Duc; Nguyen, Thi-Dung; Nguyen-Mau, Chung; Nicol, Michelle; Niess, Valentin; Niet, Ramon; Nikitin, Nikolay; Nikodem, Thomas; Nomerotski, Andrey; Novoselov, Alexey; Oblakowska-Mucha, Agnieszka; Obraztsov, Vladimir; Oggero, Serena; Ogilvy, Stephen; Okhrimenko, Oleksandr; Oldeman, Rudolf; Onderwater, Gerco; Orlandea, Marius; Otalora Goicochea, Juan Martin; Owen, Patrick; Oyanguren, Maria Arantza; Pal, Bilas Kanti; Palano, Antimo; Palutan, Matteo; Panman, Jacob; Papanestis, Antonios; Pappagallo, Marco; Pappalardo, Luciano; Parkes, Christopher; Parkinson, Christopher John; Passaleva, Giovanni; Patel, Girish; Patel, Mitesh; Patrignani, Claudia; Pavel-Nicorescu, Carmen; Pazos Alvarez, Antonio; Pearce, Alex; Pellegrino, Antonio; Penso, Gianni; Pepe Altarelli, Monica; Perazzini, Stefano; Perez Trigo, Eliseo; Pérez-Calero Yzquierdo, Antonio; Perret, Pascal; Perrin-Terrin, Mathieu; Pescatore, Luca; Pesen, Erhan; Pessina, Gianluigi; Petridis, Konstantin; Petrolini, Alessandro; Picatoste Olloqui, Eduardo; Pietrzyk, Boleslaw; Pilař, Tomas; Pinci, Davide; Playfer, Stephen; Plo Casasus, Maximo; Polci, Francesco; Polok, Grzegorz; Poluektov, Anton; Polycarpo, Erica; Popov, Alexander; Popov, Dmitry; Popovici, Bogdan; Potterat, Cédric; Powell, Andrew; Prisciandaro, Jessica; Pritchard, Adrian; Prouve, Claire; Pugatch, Valery; Puig Navarro, Albert; Punzi, Giovanni; Qian, Wenbin; Rachwal, Bartolomiej; Rademacker, Jonas; Rakotomiaramanana, Barinjaka; Rangel, Murilo; Raniuk, Iurii; Rauschmayr, Nathalie; Raven, Gerhard; Redford, Sophie; Reichert, Stefanie; Reid, Matthew; dos Reis, Alberto; Ricciardi, Stefania; Richards, Alexander; Rinnert, Kurt; Rives Molina, Vincente; Roa Romero, Diego; Robbe, Patrick; Roberts, Douglas; Rodrigues, Ana Barbara; Rodrigues, Eduardo; Rodriguez Perez, Pablo; Roiser, Stefan; Romanovsky, Vladimir; Romero Vidal, Antonio; Rotondo, Marcello; Rouvinet, Julien; Ruf, Thomas; Ruffini, Fabrizio; Ruiz, Hugo; Ruiz Valls, Pablo; Sabatino, Giovanni; Saborido Silva, Juan Jose; Sagidova, Naylya; Sail, Paul; Saitta, Biagio; Salustino Guimaraes, Valdir; Sanmartin Sedes, Brais; Santacesaria, Roberta; Santamarina Rios, Cibran; Santovetti, Emanuele; Sapunov, Matvey; Sarti, Alessio; Satriano, Celestina; Satta, Alessia; Savrie, Mauro; Savrina, Darya; Schiller, Manuel; Schindler, Heinrich; Schlupp, Maximilian; Schmelling, Michael; Schmidt, Burkhard; Schneider, Olivier; Schopper, Andreas; Schune, Marie Helene; Schwemmer, Rainer; Sciascia, Barbara; Sciubba, Adalberto; Seco, Marcos; Semennikov, Alexander; Senderowska, Katarzyna; Sepp, Indrek; Serra, Nicola; Serrano, Justine; Seyfert, Paul; Shapkin, Mikhail; Shapoval, Illya; Shcheglov, Yury; Shears, Tara; Shekhtman, Lev; Shevchenko, Oksana; Shevchenko, Vladimir; Shires, Alexander; Silva Coutinho, Rafael; Sirendi, Marek; Skidmore, Nicola; Skwarnicki, Tomasz; Smith, Anthony; Smith, Edmund; Smith, Eluned; Smith, Jackson; Smith, Mark; Sokoloff, Michael; Soler, Paul; Soomro, Fatima; Souza, Daniel; Souza De Paula, Bruno; Spaan, Bernhard; Sparkes, Ailsa; Spradlin, Patrick; Stagni, Federico; Stahl, Sascha; Steinkamp, Olaf; Stevenson, Scott; Stoica, Sabin; Stone, Sheldon; Storaci, Barbara; Stracka, Simone; Straticiuc, Mihai; Straumann, Ulrich; Subbiah, Vijay Kartik; Sun, Liang; Sutcliffe, William; Swientek, Stefan; Syropoulos, Vasileios; Szczekowski, Marek; Szczypka, Paul; Szilard, Daniela; Szumlak, Tomasz; T'Jampens, Stephane; Teklishyn, Maksym; Tellarini, Giulia; Teodorescu, Eliza; Teubert, Frederic; Thomas, Christopher; Thomas, Eric; van Tilburg, Jeroen; Tisserand, Vincent; Tobin, Mark; Tolk, Siim; Tomassetti, Luca; Tonelli, Diego; Topp-Joergensen, Stig; Torr, Nicholas; Tournefier, Edwige; Tourneur, Stephane; Tran, Minh Tâm; Tresch, Marco; Tsaregorodtsev, Andrei; Tsopelas, Panagiotis; Tuning, Niels; Ubeda Garcia, Mario; Ukleja, Artur; Ustyuzhanin, Andrey; Uwer, Ulrich; Vagnoni, Vincenzo; Valenti, Giovanni; Vallier, Alexis; Vazquez Gomez, Ricardo; Vazquez Regueiro, Pablo; Vázquez Sierra, Carlos; Vecchi, Stefania; Velthuis, Jaap; Veltri, Michele; Veneziano, Giovanni; Vesterinen, Mika; Viaud, Benoit; Vieira, Daniel; Vilasis-Cardona, Xavier; Vollhardt, Achim; Volyanskyy, Dmytro; Voong, David; Vorobyev, Alexey; Vorobyev, Vitaly; Voß, Christian; Voss, Helge; de Vries, Jacco; Waldi, Roland; Wallace, Charlotte; Wallace, Ronan; Wandernoth, Sebastian; Wang, Jianchun; Ward, David; Watson, Nigel; Webber, Adam Dane; Websdale, David; Whitehead, Mark; Wicht, Jean; Wiechczynski, Jaroslaw; Wiedner, Dirk; Wiggers, Leo; Wilkinson, Guy; Williams, Matthew; Williams, Mike; Wilson, Fergus; Wimberley, Jack; Wishahi, Julian; Wislicki, Wojciech; Witek, Mariusz; Wormser, Guy; Wotton, Stephen; Wright, Simon; Wu, Suzhi; Wyllie, Kenneth; Xie, Yuehong; Xing, Zhou; Yang, Zhenwei; Yuan, Xuhao; Yushchenko, Oleg; Zangoli, Maria; Zavertyaev, Mikhail; Zhang, Feng; Zhang, Liming; Zhang, Wen Chao; Zhang, Yanxi; Zhelezov, Alexey; Zhokhov, Anatoly; Zhong, Liang; Zvyagin, Alexander


    Decays of beauty baryons to the $D^0 p h^-$ and $\\Lambda_c^+ h^-$ final states (where $h$ indicates a pion or a kaon) are studied using a data sample of $pp$ collisions, corresponding to an integrated luminosity of 1.0 fb$^{-1}$, collected by the LHCb detector. The Cabibbo-suppressed decays $\\Lambda_b^0\\to D^0 p K^-$ and $\\Lambda_b^0\\to \\Lambda_c^+ K^-$ are observed and their branching fractions are measured with respect to the decays $\\Lambda_b^0\\to D^0 p \\pi^-$ and $\\Lambda_b^0\\to \\Lambda_c^+ \\pi^-$. In addition, the first observation is reported of the decay of the neutral beauty-strange baryon $\\Xi_b^0$ to the $D^0 p K^-$ final state, and a measurement of the $\\Xi_b^0$ mass is performed. Evidence of the $\\Xi_b^0\\to \\Lambda_c^+ K^-$ decay is also reported.

  19. Dual Ligand-Enabled Nondirected C-H Olefination of Arenes. (United States)

    Chen, Hao; Wedi, Philipp; Meyer, Tim; Tavakoli, Ghazal; van Gemmeren, Manuel


    The application of the Pd-catalyzed oxidative C-H olefination of arenes, also known as the Fujiwara-Moritani reaction, has traditionally been limited by the requirement for directing groups on the substrate or the need to use the arene in large excess, typically as a (co)solvent. Herein the development of a catalytic system is described that, through the combined action of two complementary ligands, makes it possible to use directing-group-free arenes as limiting reagents for the first time. The reactions proceed under a combination of both steric and electronic control and enable the application of this powerful reaction to valuable arenes, which cannot be utilized in excess. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Annulation of Aromatic Imines via Directed C-H BondActivation

    Energy Technology Data Exchange (ETDEWEB)

    Thalji, Reema K.; Ahrendt, Kateri A.; Bergman, Robert G.; Ellman,Jonathan A.


    A directed C-H bond activation approach to the synthesis of indans, tetralins, dihydrofurans, dihydroindoles, and other polycyclic aromatic compounds is presented. Cyclization of aromatic ketimines and aldimines containing alkenyl groups tethered at the meta position relative to the imine directing group has been achieved using (PPh{sub 3}){sub 3}RhCl (Wilkinson's catalyst). The cyclization of a range of aromatic ketimines and aldimines provides bi- and tricyclic ring systems with good regioselectivity. Different ring sizes and substitution patterns can be accessed through the coupling of monosubstituted, 1,1- or 1,2-disubstituted, and trisubstituted alkenes bearing both electron-rich and electron-deficient functionality.

  1. Direct α-C-H bond functionalization of unprotected cyclic amines (United States)

    Chen, Weijie; Ma, Longle; Paul, Anirudra; Seidel, Daniel


    Cyclic amines are ubiquitous core structures of bioactive natural products and pharmaceutical drugs. Although the site-selective abstraction of C-H bonds is an attractive strategy for preparing valuable functionalized amines from their readily available parent heterocycles, this approach has largely been limited to substrates that require protection of the amine nitrogen atom. In addition, most methods rely on transition metals and are incompatible with the presence of amine N-H bonds. Here we introduce a protecting-group-free approach for the α-functionalization of cyclic secondary amines. An operationally simple one-pot procedure generates products via a process that involves intermolecular hydride transfer to generate an imine intermediate that is subsequently captured by a nucleophile, such as an alkyl or aryl lithium compound. Reactions are regioselective and stereospecific and enable the rapid preparation of bioactive amines, as exemplified by the facile synthesis of anabasine and (-)-solenopsin A.

  2. 2008 C. H. McCloy lecture. Social psychology and physical activity: back to the future. (United States)

    Gill, Diane L


    In the early 1970s, both my academic career and the psychology subdiscipline within kinesiology began as "social psychology and physical activity. "Since then, sport and exercise psychology research has shifted away from the social to a narrower biopsycho-(no social) approach, and professional practice has focused on the elite rather than the larger public. Psychology can contribute to an integrative and relevant professional discipline by going back to the future as social psychology and physical activity and by incorporating three of C. H. McCloy's themes (a) evidence-based practice, (b) beyond dualisms, and (c) commitment to public service. Our scholarship must move beyond dualisms to recognize complexities and connections and be truly scholarship for practice. Social psychology and physical activity can serve the public by advocating for inclusive, empowering physical activity programs that promote health and well being for all.

  3. C.H. Dodd se verstaansraamwerk vir die Johannes-evangelie: ’n Evaluasie

    Directory of Open Access Journals (Sweden)

    Jan G. van der Watt


    Full Text Available C.H. Dodd’s framework for understanding the Gospel according to John: An evaluation. During the previous century Dodd was one of the most significant and influential interpreters of the Gospel of John. His views on the symbolic nature of the Gospel formed the basis of his hermeneutical program for understanding the Gospel. He understood the Johannine symbols in the light of what he regarded as the relevant background material. Theologically he interprets the symbols within a Platonic-like structure, arguing that the symbols in John function as hermeneutical bridges between the background material and the theological formation of the Gospel of John. In subsequent literary studies this approach was and still is questioned.

  4. Oxidant-free Rh(III)-catalyzed direct C-H olefination of arenes with allyl acetates. (United States)

    Feng, Chao; Feng, Daming; Loh, Teck-Peng


    Rh(III)-catalyzed direct olefination of arenes with allyl acetate via C-H bond activation is described using N,N-disubstituted aminocarbonyl as the directing group. The catalyst undergoes a redox neutral process, and high to excellent yields of trans-products are obtained. This protocol exhibits a wide spectrum of functionality compatibility because of the simple reaction conditions employed and provides a highly effective synthetic method in the realm of C-H olefination.

  5. Absorber materials in CANDU PHWR's

    International Nuclear Information System (INIS)

    Price, E.G.; Boss, C.R.; Novak, W.Z.; Fong, R.W.L.


    In a CANDU reactor the fuel channels are arranged on a square lattice in a calandria filled with heavy water moderator. This arrangement allows five types of tubular neutron absorber devices to be located in a relatively benign environment of low pressure, low temperature heavy water between neighbouring rows of columns of fuel channels. This paper will describe the roles of the devices and outline the design requirements of the absorber component from a reactor physics viewpoint. Nuclear heating and activation problems associated with the different absorbers will be briefly discussed. The design and manufacture of the devices will be also discussed. The control rod absorbers and shut off materials are cadmium and stainless steel. In the tubular arrangement, the cadmium is sandwiched between stainless steel tubes. This type of device has functioned well, but there is now concern over the availability and expense of cadmium which is used in two types of CANDU control devices. There are also concerns about the toxicity of cadmium during the fabrication of the absorbers. These concerns are prompting AECL to study alternatives. To minimize design changes, pure boron-10 alloyed in stainless steel is a favoured option. Work is underway to confirm the suitability of the boron-loaded steel and identify other encapsulated absorber materials for practical application. Because the reactivity devices or their guide tubes span the calandria vessel, the long slender components must be sufficiently rigid to resist operational vibration and also be seismically stable. Some of these components are made of Zircaloy to minimize neutron absorption. Slow irradiation growth and creep can reduce the spring tension, and periodic adjustments to the springs are required. Experience with the control absorber devices has generally been good. In one instance liquid zone controllers had a problem of vibration induced fretting but a designed back-fit resolved the problem. (author). 3 refs., 1

  6. Carbon Absorber Retrofit Equipment (CARE)

    Energy Technology Data Exchange (ETDEWEB)

    Klein, Eric [Neumann Systems Group, Incorporated, Colorado Springs, CO (United States)


    During Project DE-FE0007528, CARE (Carbon Absorber Retrofit Equipment), Neumann Systems Group (NSG) designed, installed and tested a 0.5MW NeuStream® carbon dioxide (CO2) capture system using the patented NeuStream® absorber equipment and concentrated (6 molal) piperazine (PZ) as the solvent at Colorado Springs Utilities’ (CSU’s) Martin Drake pulverized coal (PC) power plant. The 36 month project included design, build and test phases. The 0.5MW NeuStream® CO2 capture system was successfully tested on flue gas from both coal and natural gas combustion sources and was shown to meet project objectives. Ninety percent CO2 removal was achieved with greater than 95% CO2product purity. The absorbers tested support a 90% reduction in absorber volume compared to packed towers and with an absorber parasitic power of less than 1% when configured for operation with a 550MW coal plant. The preliminary techno-economic analysis (TEA) performed by the Energy and Environmental Research Center (EERC) predicted an over-the-fence cost of $25.73/tonne of CO2 captured from a sub-critical PC plant.

  7. Additive manufacturing of RF absorbers (United States)

    Mills, Matthew S.

    The ability of additive manufacturing techniques to fabricate integrated electromagnetic absorbers tuned for specific radio frequency bands within structural composites allows for unique combinations of mechanical and electromagnetic properties. These composites and films can be used for RF shielding of sensitive electromagnetic components through in-plane and out-of-plane RF absorption. Structural composites are a common building block of many commercial platforms. These platforms may be placed in situations in which there is a need for embedded RF absorbing properties along with structural properties. Instead of adding radar absorbing treatments to the external surface of existing structures, which adds increased size, weight and cost; it could prove to be advantageous to integrate the microwave absorbing properties directly into the composite during the fabrication process. In this thesis, a method based on additive manufacturing techniques of composites structures with prescribed electromagnetic loss, within the frequency range 1 to 26GHz, is presented. This method utilizes screen printing and nScrypt micro dispensing to pattern a carbon based ink onto low loss substrates. The materials chosen for this study will be presented, and the fabrication technique that these materials went through to create RF absorbing structures will be described. The calibration methods used, the modeling of the RF structures, and the applications in which this technology can be utilized will also be presented.

  8. Direct Functionalization of Nitrogen Heterocycles via Rh-Catalyzed C-H Bond Activation

    Energy Technology Data Exchange (ETDEWEB)

    Lewis, Jared; Bergman, Robert; Ellman, Jonathan


    Nitrogen heterocycles are present in many compounds of enormous practical importance, ranging from pharmaceutical agents and biological probes to electroactive materials. Direct funtionalization of nitrogen heterocycles through C-H bond activation constitutes a powerful means of regioselectively introducing a variety of substituents with diverse functional groups onto the heterocycle scaffold. Working together, our two groups have developed a family of Rh-catalyzed heterocycle alkylation and arylation reactions that are notable for their high level of functional-group compatibility. This Account describes their work in this area, emphasizing the relevant mechanistic insights that enabled synthetic advances and distinguished the resulting transformations from other methods. They initially discovered an intramolecular Rh-catalyzed C-2-alkylation of azoles by alkenyl groups. That reaction provided access to a number of di-, tri-, and tetracyclic azole derivatives. They then developed conditions that exploited microwave heating to expedite these reactions. While investigating the mechanism of this transformation, they discovered that a novel substrate-derived Rh-N-heterocyclic carbene (NHC) complex was involved as an intermediate. They then synthesized analogous Rh-NHC complexes directly by treating precursors to the intermediate [RhCl(PCy{sub 3}){sub 2}] with N-methylbenzimidazole, 3-methyl-3,4-dihydroquinazolein, and 1-methyl-1,4-benzodiazepine-2-one. Extensive kinetic analysis and DFT calculations supported a mechanism for carbene formation in which the catalytically active RhCl(PCy{sub 3}){sub 2} fragment coordinates to the heterocycle before intramolecular activation of the C-H bond occurs. The resulting Rh-H intermediate ultimately tautomerizes to the observed carbene complex. With this mechanistic information and the discovery that acid co-catalysts accelerate the alkylation, they developed conditions that efficiently and intermolecularly alkylate a variety of

  9. Dimethylphosphinate bridged binuclear Rh(i) catalysts for the alkoxycarbonylation of aromatic C-H bonds. (United States)

    Iturmendi, Amaia; Sanz Miguel, Pablo J; Popoola, Saheed A; Al-Saadi, Abdulaziz A; Iglesias, Manuel; Oro, Luis A


    A variety of binuclear rhodium(i) complexes featuring two bridging dimethylphosphinate ligands ((CH 3 ) 2 PO 2 - ) have been prepared and tested in the alkoxycarbonylation of aromatic C-H bonds. The complex [Rh(μ-κO,O'-(CH 3 ) 2 PO 2 )(cod)] 2 has been prepared by a reaction of [Rh(μ-MeO)(cod)] 2 with 2 equivalents of dimethylphosphinic acid. Binuclear complexes [Rh(μ-κO,O'-(CH 3 ) 2 PO 2 )(CO)L] 2 (L = PPh 3 , P(OMe)Ph 2 and P(OPh) 3 ) were obtained by carbonylation of the related mononuclear complexes [Rh(κO-(CH 3 ) 2 PO 2 )(cod)(L)], which were prepared in situ by the reaction of [Rh(μ-κO,O'-(CH 3 ) 2 PO 2 )(cod)] 2 with 2 equivalents of L. Conversely, if L = IPr, the reaction of [Rh(μ-κO,O'-(CH 3 ) 2 PO 2 )(CO)L] 2 with carbon monoxide affords the mononuclear complex [Rh(κO-(CH 3 ) 2 PO 2 )(CO) 2 IPr]. The subsequent reaction with trimethylamine N-oxide gives the corresponding binuclear complex [Rh(μ-κO,O'-(CH 3 ) 2 PO 2 )(CO)(IPr)] 2 by abstraction of one of the carbonyl ligands. Complexes [Rh(μ-κO,O'-(CH 3 ) 2 PO 2 )(cod)] 2 and [Rh(κO-(CH 3 ) 2 PO 2 )(cod)(L)] (L = IPr, PPh 3 , P(OMe)Ph 2 , P(OPh) 3 ) are active precatalysts in the alkoxycarbonylation of C-H bonds, with the ligand system playing a key role in the catalytic activity. The complexes that feature more labile Rh-L bonds give rise to better catalysts, probably due to the more straightforward substitution of L by a second carbonyl ligand, since a more electrophilic carbonyl carbon atom is more susceptible toward aryl migration. In fact, complexes [Rh(μ-κO,O'-(CH 3 ) 2 PO 2 )(CO) 2 ] 2 and [Rh(μ-Cl)(CO) 2 ] 2 , generated in situ from [Rh(μ-κO,O'-(CH 3 ) 2 PO 2 )(cod)] 2 and [Rh(μ-Cl)(cod) 2 ] 2 , respectively, are the most active catalysts tested in this work.

  10. Development of deuterium labeling method based on the heterogeneous platinum group metal-catalyzed C-H activation. (United States)

    Sajiki, Hironao


    Deuterium (D) labeled compounds are utilized in various scientific fields such as mechanistic elucidation of reactions, preparation of new functional materials, tracers for microanalysis, deuterium labeled heavy drugs and so on. Although the H-D exchange reaction is a straightforward method to produce deuterated organic compounds, many precedent methods require expensive deuterium gas and/or harsh reaction conditions. A part of our leading research agendas is intended to the development of novel and functional heterogeneous platinum-group catalysts and the reclamation of unknown functionalities of existing heterogeneous platinum-group catalysts. During the course of the study, benzylic positions of substrates were site-selectively deuterated under mild and palladium-on-carbon (Pd/C)-catalyzed hydrogenation conditions in heavy water (D2O). Heat conditions promoted the H-D exchange reactivity and facilitated the H-D exchange reaction at not only the benzylic sites but also inactive C-H bonds and heterocyclic nuclei. It is noteworthy that platinum-on-carbon (Pt/C) indicated a quite high affinity toward aromatic nuclei, and the H-D exchange reaction was strongly enhanced by the use of Pt/C as a catalyst under milder conditions. The mixed use of Pd/C and Pt/C was found to be more efficient in the H-D exchange reaction compared to the independent use of Pd/C or Pt/C. Furthermore, simple alkanes could also be efficiently deuterated under rhodium-on-carbon (Rh/C)-catalyzed conditions. The use of ruthenium-on-carbon (Ru/C) enabled the regiospecific and efficient deuterium incorporation at α-positions of alcohols and results were applied as a regio- and stereoselective multi-deuteration method of sugar derivatives.

  11. Water fugacity in absorbing polymers. (United States)

    Burg, K J; Shalaby, S W


    Absorbable biomaterials, as dynamic systems, require special handling, processing, and characterization techniques beyond those of the traditional nonabsorbable materials. As the material degrades or absorbs, in vitro or in vivo, it undergoes structural, physical, and chemical changes. These changes in the base material may significantly impact the performance of a particular biomedical device; hence, it is important that the investigator consider the full range of properties that constitute the lifetime of a given absorbable material. The long term degradation study presented here sought to identify one such property, the change in water retention of a degrading oriented polylactide film. The investigation found through differential scanning calorimetry that later stages of degradation are often characterized by a stronger retention of water, potentially due to a higher number of polar carboxyl groups within the relatively hydrophobic polymer matrix.

  12. Adaptive inertial shock-absorber

    International Nuclear Information System (INIS)

    Faraj, Rami; Holnicki-Szulc, Jan; Knap, Lech; Seńko, Jarosław


    This paper introduces and discusses a new concept of impact absorption by means of impact energy management and storage in dedicated rotating inertial discs. The effectiveness of the concept is demonstrated in a selected case-study involving spinning management, a recently developed novel impact-absorber. A specific control technique performed on this device is demonstrated to be the main source of significant improvement in the overall efficiency of impact damping process. The influence of various parameters on the performance of the shock-absorber is investigated. Design and manufacturing challenges and directions of further research are formulated. (paper)

  13. Spectroscopic Study of Plasma Polymerized a-C:H Films Deposited by a Dielectric Barrier Discharge

    Directory of Open Access Journals (Sweden)

    Thejaswini Halethimmanahally Chandrashekaraiah


    Full Text Available Plasma polymerized a-C:H thin films have been deposited on Si (100 and aluminum coated glass substrates by a dielectric barrier discharge (DBD operated at medium pressure using C2Hm/Ar (m = 2, 4, 6 gas mixtures. The deposited films were characterized by Fourier transform infrared reflection absorption spectroscopy (FT-IRRAS, Raman spectroscopy, and ellipsometry. FT-IRRAS revealed the presence of sp3 and sp2 C–H stretching and C–H bending vibrations of bonds in the films. The presence of D and G bands was confirmed by Raman spectroscopy. Thin films obtained from C2H4/Ar and C2H6/Ar gas mixtures have ID/IG ratios of 0.45 and 0.3, respectively. The refractive indices were 2.8 and 3.1 for C2H4/Ar and C2H6/Ar films, respectively, at a photon energy of 2 eV.

  14. Stereodivergent synthesis of arylcyclopropylamines by sequential C-H borylation and Suzuki-Miyaura coupling. (United States)

    Miyamura, Shin; Araki, Misaho; Suzuki, Takayoshi; Yamaguchi, Junichiro; Itami, Kenichiro


    A step-economical and stereodivergent synthesis of privileged 2-arylcyclopropylamines (ACPAs) through a C(sp(3))-H borylation and Suzuki-Miyaura coupling sequence has been developed. The iridium-catalyzed C-H borylation of N-cyclopropylpivalamide proceeds with cis selectivity. The subsequent B-cyclopropyl Suzuki-Miyaura coupling catalyzed by [PdCl2(dppf)]/Ag2O proceeds with retention of configuration at the carbon center bearing the Bpin group, while epimerization at the nitrogen-bound carbon atoms of both the starting materials and products is observed under the reaction conditions. This epimerization is, however, suppressed in the presence of O2. The present new ACPA synthesis results in not only a significant reduction in the steps required for making ACPA derivatives, but also the ability to access either isomer (cis or trans) by simply changing the atmosphere (N2 or O2) in the coupling stage. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Influence of modulation periods on the tribological behavior of Si/a-C: H multilayer film (United States)

    Zhu, Linan; Wu, Yanxia; Zhang, Shujiao; Yu, Shengwang; Tang, Bin; Liu, Ying; Zhou, Bing; Shen, Yanyan


    A series of Si/a-C: H multilayer films with different modulation periods were fabricated on stainless steel and silicon substrates by radio-frequency magnetron sputtering. The influence of the modulation period on the structure, morphology, mechanical properties and tribological behaviors in different environments (air, simulated acid rain, and NaCl solution) was investigated. The results show that the content of the sp2 hybrid carbon, surface roughness and hardness of the multilayer film increased firstly and then decreased with the decreased modulation period. Furthermore, the combination of the sublayer agrees well with the formation of the SiC crystal at the interface. Interestingly, the films show quite substantially different tribological properties in various test environments. The lowest friction coefficient is 0.2 for the S1 film in air. However, the lowest friction coefficient can reach 0.13 in solution. Importantly, the tribological behavior of the multilayer film is mainly determined by its hardness, as well as surface roughness in air while it is closely related with modulation period and interface structure in solution.

  16. Brown carbon: a significant atmospheric absorber of solar radiation?

    Directory of Open Access Journals (Sweden)

    Y. Feng


    Full Text Available Several recent observational studies have shown organic carbon aerosols to be a significant source of absorption of solar radiation. The absorbing part of organic aerosols is referred to as "brown" carbon (BrC. Using a global chemical transport model and a radiative transfer model, we estimate for the first time the enhanced absorption of solar radiation due to BrC in a global model. The simulated wavelength dependence of aerosol absorption, as measured by the absorption Ångström exponent (AAE, increases from 0.9 for non-absorbing organic carbon to 1.2 (1.0 for strongly (moderately absorbing BrC. The calculated AAE for the strongly absorbing BrC agrees with AERONET spectral observations at 440–870 nm over most regions but overpredicts for the biomass burning-dominated South America and southern Africa, in which the inclusion of moderately absorbing BrC has better agreement. The resulting aerosol absorption optical depth increases by 18% (3% at 550 nm and 56% (38% at 380 nm for strongly (moderately absorbing BrC. The global simulations suggest that the strongly absorbing BrC contributes up to +0.25 W m−2 or 19% of the absorption by anthropogenic aerosols, while 72% is attributed to black carbon, and 9% is due to sulfate and non-absorbing organic aerosols coated on black carbon. Like black carbon, the absorption of BrC (moderately to strongly inserts a warming effect at the top of the atmosphere (TOA (0.04 to 0.11 W m−2, while the effect at the surface is a reduction (−0.06 to −0.14 W m−2. Inclusion of the strongly absorption of BrC in our model causes the direct radiative forcing (global mean of organic carbon aerosols at the TOA to change from cooling (−0.08 W m−2 to warming (+0.025 W m−2. Over source regions and above clouds, the absorption of BrC is higher and thus can play an important role in photochemistry and the hydrologic cycle.

  17. General synthesis of 2,1-benzisoxazoles (anthranils) from nitroarenes and benzylic C-H acids in aprotic media promoted by combination of strong bases and silylating agents. (United States)

    Wiȩcław, Michał; Bobin, Mariusz; Kwast, Andrzej; Bujok, Robert; Wróbel, Zbigniew; Wojciechowski, Krzysztof


    Carbanions of phenylacetonitriles, benzyl sulfones, and dialkyl benzylphosphonates add nitroarenes at the ortho-position to the nitro group to form [Formula: see text]-adducts that, upon treatment with trialkylchlorosilane and additional base (t-BuOK or DBU), transform into 3-aryl-2,1-benzisoxazoles in moderate-to-good yields.

  18. N-heterocyclic carbene gold(I) and copper(I) complexes in C-H bond activation. (United States)

    Gaillard, Sylvain; Cazin, Catherine S J; Nolan, Steven P


    Environmental concerns have and will continue to have a significant role in determining how chemistry is carried out. Chemists will be challenged to develop new, efficient synthetic processes that have the fewest possible steps leading to a target molecule, the goal being to decrease the amount of waste generated and reduce energy use. Along this path, chemists will need to develop highly selective reactions with atom-economical pathways producing nontoxic byproduct. In this context, C-H bond activation and functionalization is an extremely attractive method. Indeed, for most organic transformations, the presence of a reactive functionality is required. In Total Synthesis, the "protection and deprotection" approach with such reactive groups limits the overall yield of the synthesis, involves the generation of significant chemical waste, costs energy, and in the end is not as green as one would hope. In turn, if a C-H bond functionalization were possible, instead of the use of a prefunctionalized version of the said C-H bond, the number of steps in a synthesis would obviously be reduced. In this case, the C-H bond can be viewed as a dormant functional group that can be activated when necessary during the synthetic strategy. One issue increasing the challenge of such a desired reaction is selectivity. The cleavage of a C-H bond (bond dissociation requires between 85 and 105 kcal/mol) necessitates a high-energy species, which could quickly become a drawback for the control of chemo-, regio-, and stereoselectivity. Transition metal catalysts are useful reagents for surmounting this problem; they can decrease the kinetic barrier of the reaction yet retain control over selectivity. Transition metal complexes also offer important versatility in having distinct pathways that can lead to activation of the C-H bond. An oxidative addition of the metal in the C-H bond, and a base-assisted metal-carbon bond formation in which the base can be coordinated (or not) to the metal

  19. Absorbing-and-diffusing coating


    Tkalich, N. V.; Mokeev, Yu. G.; Onipko, A. F.; Vashchenko, V. F.; Topchev, M. D.; Glebov, V. V.; Ivanchenko, Dmitrij D.; Kolchigin, Nikolay N.; Yevdokimov, V. V.


    The paper presents the results of complex experimental research of the absorbing-and-diffusing material "Contrast". It is shown to be an efficient wideband-camouflage material in the radiolocation and the video bands. Ways for improving the material characteristics are outlined.

  20. Tunable differentiation of tertiary C-H bonds in intramolecular transition metal-catalyzed nitrene transfer reactions. (United States)

    Corbin, Joshua R; Schomaker, Jennifer M


    Metal-catalyzed nitrene transfer reactions are an appealing and efficient strategy for accessing tetrasubstituted amines through the direct amination of tertiary C-H bonds. Traditional catalysts for these reactions rely on substrate control to achieve site-selectivity in the C-H amination event; thus, tunability is challenging when competing C-H bonds have similar steric or electronic features. One consequence of this fact is that the impact of catalyst identity on the selectivity in the competitive amination of tertiary C-H bonds has not been well-explored, despite the potential for progress towards predictable and catalyst-controlled C-N bond formation. In this communication, we report investigations into tunable and site-selective nitrene transfers between tertiary C(sp 3 )-H bonds using a combination of transition metal catalysts, including complexes based on Ag, Mn, Rh and Ru. Particularly striking was the ability to reverse the selectivity of nitrene transfer by a simple change in the identity of the N-donor ligand supporting the Ag(i) complex. The combination of our Ag(i) catalysts with known Rh 2 (ii) complexes expands the scope of successful catalyst-controlled intramolecular nitrene transfer and represents a promising springboard for the future development of intermolecular C-H N-group transfer methods.

  1. A meta-selective C-H borylation directed by a secondary interaction between ligand and substrate (United States)

    Kuninobu, Yoichiro; Ida, Haruka; Nishi, Mitsumi; Kanai, Motomu


    Regioselective C-H bond transformations are potentially the most efficient method for the synthesis of organic molecules. However, the presence of many C-H bonds in organic molecules and the high activation barrier for these reactions make these transformations difficult. Directing groups in the reaction substrate are often used to control regioselectivity, which has been especially successful for the ortho-selective functionalization of aromatic substrates. Here, we describe an iridium-catalysed meta-selective C-H borylation of aromatic compounds using a newly designed catalytic system. The bipyridine-derived ligand that binds iridium contains a pendant urea moiety. A secondary interaction between this urea and a hydrogen-bond acceptor in the substrate places the iridium in close proximity to the meta-C-H bond and thus controls the regioselectivity. 1H NMR studies and control experiments support the participation of hydrogen bonds in inducing regioselectivity. Reversible direction of the catalyst through hydrogen bonds is a versatile concept for regioselective C-H transformations.

  2. Pt/Cu single-atom alloys as coke-resistant catalysts for efficient C-H activation (United States)

    Marcinkowski, Matthew D.; Darby, Matthew T.; Liu, Jilei; Wimble, Joshua M.; Lucci, Felicia R.; Lee, Sungsik; Michaelides, Angelos; Flytzani-Stephanopoulos, Maria; Stamatakis, Michail; Sykes, E. Charles H.


    The recent availability of shale gas has led to a renewed interest in C-H bond activation as the first step towards the synthesis of fuels and fine chemicals. Heterogeneous catalysts based on Ni and Pt can perform this chemistry, but deactivate easily due to coke formation. Cu-based catalysts are not practical due to high C-H activation barriers, but their weaker binding to adsorbates offers resilience to coking. Using Pt/Cu single-atom alloys (SAAs), we examine C-H activation in a number of systems including methyl groups, methane and butane using a combination of simulations, surface science and catalysis studies. We find that Pt/Cu SAAs activate C-H bonds more efficiently than Cu, are stable for days under realistic operating conditions, and avoid the problem of coking typically encountered with Pt. Pt/Cu SAAs therefore offer a new approach to coke-resistant C-H activation chemistry, with the added economic benefit that the precious metal is diluted at the atomic limit.

  3. Selective solar absorber emittance measurement at elevated temperature (United States)

    Giraud, Philémon; Braillon, Julien; Raccurt, Olivier


    Durability of solar components for CSP (Concentrated Solar Power Plant) technologies is a key point to lower cost and ensure their large deployment. These technologies concentrated the solar radiation by means of mirrors on a receiver tube where it is collected as thermal energy. The absorbers are submitted to strong environmental constraints and the degradation of their optical properties (emittance and solar absorbance) have a direct impact on performance. The characterization of a material in such condition is complicated and requires advanced apparatuses, and different measurement methods exist for the determination of the two quantities of relevance regarding an absorber, which are its emittance and its solar absorbance. The objective is to develop new optical equipment for measure the emittance of this solar absorber at elevated temperature. In this paper, we present an optical bench developed for emittance measurement on absorbers is conditions of use. Results will be shown, with a discussion of some factors of influence over this measurement and how to control them.

  4. Interplay of Electronic Cooperativity and Exchange Coupling in Regulating the Reactivity of Diiron(IV)-oxo Complexes towards C-H and O-H Bond Activation. (United States)

    Ansari, Azaj; Ansari, Mursaleem; Singha, Asmita; Rajaraman, Gopalan


    Activation of inert C-H bonds such as those of methane are extremely challenging for chemists but in nature, the soluble methane monooxygenase (sMMO) enzyme readily oxidizes methane to methanol by using a diiron(IV) species. This has prompted chemists to look for similar model systems. Recently, a (μ-oxo)bis(μ-carboxamido)diiron(IV) ([Fe IV 2 O(L) 2 ] 2+ L=N,N-bis-(3',5'-dimethyl-4'-methoxypyridyl-2'-methyl)-N'-acetyl-1,2-diaminoethane) complex has been generated by bulk electrolysis and this species activates inert C-H bonds almost 1000 times faster than mononuclear Fe IV =O species and at the same time selectively activates O-H bonds of alcohols. The very high reactivity and selectivity of this species is puzzling and herein we use extensive DFT calculations to shed light on this aspect. We have studied the electronic and spectral features of diiron {Fe III -μ(O)-Fe III } +2 (complex I), {Fe III -μ(O)-Fe IV } +3 (II), and {Fe IV -μ(O)-Fe IV } +4 (III) complexes. Strong antiferromagnetic coupling between the Fe centers leads to spin-coupled S=0, S=3/2, and S=0 ground state for species I-III respectively. The mechanistic study of the C-H and O-H bond activation reveals a multistate reactivity scenario where C-H bond activation is found to occur through the S=4 spin-coupled state corresponding to the high-spin state of individual Fe IV centers. The O-H bond activation on the other hand, occurs through the S=2 spin-coupled state corresponding to an intermediate state of individual Fe IV centers. Molecular orbital analysis reveals σ-π/π-π channels for the reactivity. The nature of the magnetic exchange interaction is found to be switched during the course of the reaction and this offers lower energy pathways. Significant electronic cooperativity between two metal centers during the course of the reaction has been witnessed and this uncovers the reason behind the efficiency and selectivity observed. The catalyst is found to prudently choose the desired spin

  5. Ruthenium(II)-catalysed remote C-H alkylations as a versatile platform to meta-decorated arenes (United States)

    Li, Jie; Korvorapun, Korkit; de Sarkar, Suman; Rogge, Torben; Burns, David J.; Warratz, Svenja; Ackermann, Lutz


    The full control of positional selectivity is of prime importance in C-H activation technology. Chelation assistance served as the stimulus for the development of a plethora of ortho-selective arene functionalizations. In sharp contrast, meta-selective C-H functionalizations continue to be scarce, with all ruthenium-catalysed transformations currently requiring difficult to remove or modify nitrogen-containing heterocycles. Herein, we describe a unifying concept to access a wealth of meta-decorated arenes by a unique arene ligand effect in proximity-induced ruthenium(II) C-H activation catalysis. The transformative nature of our strategy is mirrored by providing a step-economical entry to a range of meta-substituted arenes, including ketones, acids, amines and phenols--key structural motifs in crop protection, material sciences, medicinal chemistry and pharmaceutical industries.

  6. Characterization of the visible photoluminescence from porous a-Si:H and porous a-Si:C:H thin films

    Energy Technology Data Exchange (ETDEWEB)

    Estes, M.J. [Wright Lab., Wright-Patterson AFB, OH (United States). Avionics Directorate; Hirsch, L.R.; Wichart, S.; Moddel, G. [Univ. of Colorado, Boulder, CO (United States)


    The authors report on the influence of doping, temperature, porosity, and bandgap on the visible photoluminescence properties of anodically-etched porous a-Si:H and a-Si:C:H thin films. Only boron-doped, p-type a-Si:H or a-Si:C:H samples exhibited any visible photoluminescence. The authors see evidence of discrete defect or impurity levels in temperature-dependent luminescence measurements. Unlike in porous crystalline silicon, they see no correlation of luminescence energy with porosity. The authors do, though, observe a correlation of luminescence energy with bandgap of the starting a-Si:C:H films. They discuss the implication of these observations on the nature of the luminescence mechanism.

  7. Secure data storage by three-dimensional absorbers in highly scattering volume medium

    International Nuclear Information System (INIS)

    Matoba, Osamu; Matsuki, Shinichiro; Nitta, Kouichi


    A novel data storage in a volume medium with highly scattering coefficient is proposed for data security application. Three-dimensional absorbers are used as data. These absorbers can not be measured by interferometer when the scattering in a volume medium is strong enough. We present a method to reconstruct three-dimensional absorbers and present numerical results to show the effectiveness of the proposed data storage.

  8. Nickel-Catalyzed C-H Silylation of Arenes with Vinylsilanes: Rapid and Reversible β-Si Elimination. (United States)

    Elsby, Matthew R; Johnson, Samuel A


    The reaction of C 6 F 5 H and H 2 C═CHSiMe 3 with catalytic [ i Pr 2 Im]Ni(η 2 -H 2 C═CHSiMe 3 ) 2 (1b) exclusively forms the C-H silylation product C 6 F 5 SiMe 3 with ethylene as a byproduct ([ i Pr 2 Im] = 1,3-di(isopropyl)imidazole-2-ylidene). Catalytic C-H bond silylation is facile with partially fluorinated aromatic substrates containing two ortho fluorine substituents adjacent to the C-H bond and 1,2,3,4-tetrafluorobenzene. Less fluorinated substrates react slower. Under the same reaction conditions, catalytic [IPr]Ni(η 2 -H 2 C═CHSiMe 3 ) 2 (1a) ([IPr] = 1,3-bis[2,6-diisopropylphenyl]-1,3-dihydro-2H-imidazol-2-ylidene) provided only the alkene hydroarylation product C 6 F 5 CH 2 CH 2 SiMe 3 . Mechanistic studies reveal that the C-H activation and β-Si elimination steps are reversible under catalytic conditions with both catalysts 1a and 1b. With catalytic 1a, reversible ethylene loss after β-Si elimination was also observed despite its inability to catalyze C-H silylation; the reductive elimination step to form the silylation product is much slower than reductive elimination to form the alkene hydroarylation product. Reversible ethylene loss was not observed with 1b, which suggests that the rate-limiting step in the reaction is neither C-H activation nor β-Si elimination but either ethylene loss or reductive elimination of cis-disposed aryl and SiMe 3 moieties.

  9. Radiation sterilization of absorbent cotton and of absorbent gauze

    International Nuclear Information System (INIS)

    Hosobuchi, Kazunari; Oka, Mitsuru; Kaneko, Akira; Ishiwata, Hiroshi.


    The bioburden of absorbent cotton and of absorbent gauze and their physical and chemical characteristics after irradiation are investigated. The survey conducted on contaminants of 1890 cotton samples from 53 lots and 805 gauze samples from 56 lots showed maximum numbers of microbes per g of the cotton and gauze were 859 (an average of 21.4) and 777 (an average of 42.2), respectively. Isolation and microbiological and biochemical tests of representative microbes indicated that all of them, except one, were bacilli. The sterilization dose at 10 -6 of sterlity assurance level was found to be 2.0 Mrad when irradiated the spores loaded on paper strips and examined populations having graded D values from 0.10 to 0.28 Mrad. The sterilization dose would be about 1.5 Mrad if subjected the average numbers of contaminants observed in this study to irradiation. No significant differences were found between the irradiated samples and control up to 2 Mrad in tensile strength, change of color, absorbency, sedimentation rate, soluble substances, and pH of solutions used for immersion and other tests conventionally used. These results indicate that these products can be sterilized by irradiation. (author)

  10. Synthesis of Fluorine-Containing 6-Arylpurine Derivatives via Cp*Co(III)-Catalyzed C-H Bond Activation. (United States)

    Murakami, Nanami; Yoshida, Misaki; Yoshino, Tatsuhiko; Matsunaga, Shigeki


    Cp*Co(III)-catalyzed (Cp*=pentamethylcyclopentadienyl) C-H bond functionalization of 6-arylpurines using gem-difluoroalkenes and allyl fluorides is described. The reaction with gem-difluoroalkenes afforded monofluoroalkenes with high (Z)-selectivity, while the reaction with allyl fluorides led to C-H allylation in moderate (Z)-selectivity. Both reactions proceeded using a user-friendly single-component catalyst [Cp*Co(CH 3 CN) 3 ](SbF 6 ) 2 in fluorinated alcohol solvents without any additives. Robustness was also demonstrated by a preparative-scale reaction under air.

  11. Palladium(II)-catalyzed ortho-C-H arylation/alkylation of N-benzoyl α-amino ester derivatives. (United States)

    Misal Castro, Luis C; Chatani, Naoto


    The palladium-catalyzed arylation/alkylation of ortho-C-H bonds in N-benzoyl α-amino ester derivatives is described. In such a system both the NH-amido and the CO2R groups in the α-amino ester moieties play a role in successful C-H activation/C-C bond formation using iodoaryl coupling partners. A wide variety of functional groups and electron-rich/deficient iodoarenes are tolerated. The yields obtained range from 20 to 95%. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Rhodium-catalyzed enantioselective intramolecular C-H silylation for the syntheses of planar-chiral metallocene siloles. (United States)

    Zhang, Qing-Wei; An, Kun; Liu, Li-Chuan; Yue, Yuan; He, Wei


    Reported herein is the rhodium-catalyzed enantioselective C-H bond silylation of the cyclopentadiene rings in Fe and Ru metallocenes. Thus, in the presence of (S)-TMS-Segphos, the reactions took place under very mild conditions to afford metallocene-fused siloles in good to excellent yields and with ee values of up to 97%. During this study it was observed that the steric hindrance of chiral ligands had a profound influence on the reactivity and enantioselectivity of the reaction, and might hold the key to accomplishing conventionally challenging asymmetric C-H silylations. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. P(O)R2-Directed Enantioselective C-H Olefination toward Chiral Atropoisomeric Phosphine-Olefin Compounds. (United States)

    Li, Shi-Xia; Ma, Yan-Na; Yang, Shang-Dong


    An effective synthesis of chiral atropoisomeric biaryl phosphine-olefin compounds via palladium-catalyzed enantioselective C-H olefination has been developed for the first time. The reactions are operationally simple, tolerate wide functional groups, and have a good ee value. Notably, P(O)R 2 not only acts as the directing group to direct C-H activation in order to make a useful ligand but also serves to facilitate composition of the product in a useful manner in this transformation.

  14. Rhodium-Catalyzed C-C Bond Formation via Heteroatom-Directed C-H Bond Activation

    Energy Technology Data Exchange (ETDEWEB)

    Colby, Denise; Bergman, Robert; Ellman, Jonathan


    Once considered the 'holy grail' of organometallic chemistry, synthetically useful reactions employing C-H bond activation have increasingly been developed and applied to natural product and drug synthesis over the past decade. The ubiquity and relative low cost of hydrocarbons makes C-H bond functionalization an attractive alternative to classical C-C bond forming reactions such as cross-coupling, which require organohalides and organometallic reagents. In addition to providing an atom economical alternative to standard cross - coupling strategies, C-H bond functionalization also reduces the production of toxic by-products, thereby contributing to the growing field of reactions with decreased environmental impact. In the area of C-C bond forming reactions that proceed via a C-H activation mechanism, rhodium catalysts stand out for their functional group tolerance and wide range of synthetic utility. Over the course of the last decade, many Rh-catalyzed methods for heteroatom-directed C-H bond functionalization have been reported and will be the focus of this review. Material appearing in the literature prior to 2001 has been reviewed previously and will only be introduced as background when necessary. The synthesis of complex molecules from relatively simple precursors has long been a goal for many organic chemists. The ability to selectively functionalize a molecule with minimal pre-activation can streamline syntheses and expand the opportunities to explore the utility of complex molecules in areas ranging from the pharmaceutical industry to materials science. Indeed, the issue of selectivity is paramount in the development of all C-H bond functionalization methods. Several groups have developed elegant approaches towards achieving selectivity in molecules that possess many sterically and electronically similar C-H bonds. Many of these approaches are discussed in detail in the accompanying articles in this special issue of Chemical Reviews. One approach

  15. Ultrathin microwave metamaterial absorber utilizing embedded resistors (United States)

    Kim, Young Ju; Hwang, Ji Sub; Yoo, Young Joon; Khuyen, Bui Xuan; Rhee, Joo Yull; Chen, Xianfeng; Lee, YoungPak


    We numerically and experimentally studied an ultrathin and broadband perfect absorber by enhancing the bandwidth with embedded resistors into the metamaterial structure, which is easy to fabricate in order to lower the Q-factor and by using multiple resonances with the patches of different sizes. We analyze the absorption mechanism in terms of the impedance matching with the free space and through the distribution of surface current at each resonance frequency. The magnetic field, induced by the antiparallel surface currents, is formed strongly in the direction opposite to the incident electromagnetic wave, to cancel the incident wave, leading to the perfect absorption. The corresponding experimental absorption was found to be higher than 97% in 0.88-3.15 GHz. The agreement between measurement and simulation was good. The aspects of our proposed structure can be applied to future electronic devices, for example, advanced noise-suppression sheets in the microwave regime.

  16. Ru(II)-catalyzed selective C-H amination of xanthones and chromones with sulfonyl azides: synthesis and anticancer evaluation. (United States)

    Shin, Youngmi; Han, Sangil; De, Umasankar; Park, Jihye; Sharma, Satyasheel; Mishra, Neeraj Kumar; Lee, Eui-Kyung; Lee, Youngil; Kim, Hyung Sik; Kim, In Su


    A ketone-assisted ruthenium-catalyzed selective amination of xanthones and chromones C-H bonds with sulfonyl azides is described. The reactions proceed efficiently with a broad range of substrates with excellent functional group compatibility. This protocol provides direct access to 1-aminoxanthones, 5-aminochromones, and 5-aminoflavonoid derivatives known to exhibit potent anticancer activity.

  17. Investigation of the structure and properties of a-C:H coatings with metal and silicon containing interlayers (United States)

    Nöthe, M.; Breuer, U.; Koch, F.; Penkalla, H. J.; Rehbach, W. P.; Bolt, H.


    The structure of the interface of a-C:H coatings deposited with metal and Si-containing interlayers has been studied. Carbide forming metals (Al, Ti, Cr) can improve the chemical bonding compared with a substrate material which does not form carbides extensively by itself. In addition, a graded transition zone enlarges the interface between the carbon layer and the interlayer metal. In the present work the metal atoms were evaporated and ionized into a dense Ar plasma and deposited onto Si (100) substrates. A graded interface between the metal interlayer and the a-C:H coating was produced by introducing C 2H 2 with increasing amount into the Ar/He plasma during the PAPVD metal deposition process. The PACVD a-C:H deposition process was continued after the termination of metal evaporation to produce the pure a-C:H top layer. Further to Al-, Cr-, Ti- and Cu-interlayers, Si-containing interlayers were investigated. The Si-containing interlayers were deposited by a PACVD process using tetraethoxysilane Si(OC 2H 5) 4 (TEOS) and tetramethylsilane Si(CH 3) 4 (TMS). The characterization of the deposited layer systems was performed by SIMS, SNMS and XPS analyses as well as SEM and analytical TEM methods.

  18. Sulfonamides as new hydrogen atom transfer (HAT) catalysts for photoredox allylic and benzylic C-H arylations. (United States)

    Tanaka, Hirotaka; Sakai, Kentaro; Kawamura, Atsushi; Oisaki, Kounosuke; Kanai, Motomu


    A catalytic amount of a sterically and electronically tuned diarylsulfonamide promoted allylic and benzylic C-H arylations in cooperation with a visible light photoredox catalyst. This is the first example of the catalytic use of a sulfonamidyl radical to promote the hydrogen atom transfer process.

  19. Direct sp(3)C-H acroleination of N-aryl-tetrahydroisoquinolines by merging photoredox catalysis with nucleophilic catalysis. (United States)

    Feng, Zhu-Jia; Xuan, Jun; Xia, Xu-Dong; Ding, Wei; Guo, Wei; Chen, Jia-Rong; Zou, You-Quan; Lu, Liang-Qiu; Xiao, Wen-Jing


    Sequence catalysis merging photoredox catalysis (PC) and nucleophilic catalysis (NC) has been realized for the direct sp(3) C-H acroleination of N-aryl-tetrahydroisoquinoline (THIQ). The reaction was performed under very mild conditions and afforded products in 50-91% yields. A catalytic asymmetric variant was proved to be successful with moderate enantioselectivities (up to 83 : 17 er).

  20. Asymmetric Synthesis of (-)-Incarvillateine Employing an Intramolecular Alkylation via Rh-Catalyzed Olefinic C-H Bond Activation

    Energy Technology Data Exchange (ETDEWEB)

    Tsai, Andy; Bergman, Robert; Ellman, Jonathan


    An asymmetric total synthesis of (-)-incarvillateine, a natural product having potent analgesic properties, has been achieved in 11 steps and 15.4% overall yield. The key step is a rhodium-catalyzed intramolecular alkylation of an olefinic C-H bond to set two stereocenters. Additionally, this transformation produces an exocyclic, tetrasubstituted alkene through which the bicyclic piperidine moiety can readily be accessed.

  1. Palladium-Catalyzed Enantioselective C-H Activation of Aliphatic Amines Using Chiral Anionic BINOL-Phosphoric Acid Ligands. (United States)

    Smalley, Adam P; Cuthbertson, James D; Gaunt, Matthew J


    The design of an enantioselective Pd(II)-catalyzed C-H amination reaction is described. The use of a chiral BINOL phosphoric acid ligand enables the conversion of readily available amines into synthetically valuable aziridines in high enantiomeric ratios. The aziridines can be derivatized to afford a range of chiral amine building blocks incorporating motifs readily encountered in pharmaceutically relevant molecules.

  2. A selective C-H insertion/olefination protocol for the synthesis of α-methylene-γ-butyrolactone natural products. (United States)

    Lloyd, Matthew G; D'Acunto, Mariantonietta; Taylor, Richard J K; Unsworth, William P


    A regio- and stereoselective one-pot C-H insertion/olefination protocol has been developed for the late stage installation of α-methylene-γ-butyrolactones into conformationally restricted cyclohexanol-derivatives. The method has been successfully applied in the total synthesis of eudesmanolide natural product frameworks, including α-cyclocostunolide.

  3. Rh(iii)-catalyzed C-H olefination of N-pentafluoroaryl benzamides using air as the sole oxidant. (United States)

    Lu, Yi; Wang, Huai-Wei; Spangler, Jillian E; Chen, Kai; Cui, Pei-Pei; Zhao, Yue; Sun, Wei-Yin; Yu, Jin-Quan


    The oxidative olefination of a broad array of arenes and heteroarenes with a variety of activated and unactivated olefins has be achieved via a rhodium(iii)-catalyzed C-H activation reaction. The use of an N -pentafluorophenyl benzamide directing group is crucial for achieving catalytic turnovers in the presence of air as the sole oxidant without using a co-oxidant.

  4. Palladium-Catalyzed C-H Functionalization Using Guanidine as a Directing Group: Ortho Arylation and Olefination of Arylguanidines (United States)

    Shao, Jiaan; Chen, Wenteng; Giulianotti, Marc A.; Houghten, Richard A.; Yu, Yongping


    Palladium-catalyzed C-H functionalization using guanidine as the directing group was achieved under mild reaction conditions. Various guanidine derivatives were produced in moderate to good yields by using simple unactivated arenes or ethyl acrylate as the source of arylation or olefination respectively. PMID:23095022

  5. Palladium-catalyzed C-H olefination of uracils and caffeines using molecular oxygen as the sole oxidant. (United States)

    Zhang, Xinyu; Su, Lv; Qiu, Lin; Fan, Zhenwei; Zhang, Xiaofeng; Lin, Shen; Huang, Qiufeng


    The palladium-catalyzed oxidative C-H olefination of uracils or caffeines with alkenes using an atmospheric pressure of molecular oxygen as the sole oxidant has been disclosed. This novel strategy offers an efficient and environmentally friendly method to biologically important C5-alkene uracil derivatives or C8-alkene caffeine derivatives.

  6. C5-Regioselective C-H fluorination of 8-aminoquinoline amides and sulfonamides with Selectfluor under metal-free conditions. (United States)

    Zhang, Yingchao; Wen, Chunxia; Li, Jizhen


    A novel and efficient regioselective C-H fluorination of 8-aminoquinoline amides and sulfonamides at the C5 position was achieved. Using Selectfluor as a "F" reagent and HOAc as an additive, the reaction proceeds smoothly via a radical pathway. This method features metal-free conditions, a broad substrate scope and operational simplicity.

  7. Origin of the Ability of α-Fe2 O3 Mesopores to Activate C-H Bonds in Methane. (United States)

    Dong, Bing; Han, Zhen; Zhang, Yongbo; Yu, Youyi; Kong, Aiguo; Shan, Yongkui


    Methane is a most abundant and inexpensive hydrocarbon feedstock for the production of chemicals and fuels. However, it is extremely difficult to directly convert methane to higher hydrocarbons because the C-H bonds in methane are the most stable C-H bonds of all hydrocarbons. The activation of the C-H bonds in methane by using an efficient and mild route remains a daunting challenge. Here, we show that the inner surface structures of the pore walls in mesoporous α-Fe 2 O 3 possess excellent catalytic performance for methane activation and convert C-H bonds into the C-O bonds in an O 2 atmosphere at 140 °C. We found that such unusual structures are mainly comprised of turbostratic ribbons and K crystal faces and have higher catalytic activity than the (110) plane. These results are without precedent in the history of catalysis chemistry and will provide a new pathway for designing and preparing highly efficient catalytic materials. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Rhodium-Catalyzed Direct Ortho C-H Arylation Using Ketone as Directing Group with Boron Reagent. (United States)

    Zhang, Bing; Wang, Huai-Wei; Kang, Yan-Shang; Zhang, Ping; Xu, Hua-Jin; Lu, Yi; Sun, Wei-Yin


    A general method for selective ortho C-H arylation of ketone, with boron reagent enabled by rhodium complexes with excellent yields, is developed. The transformation is characterized by the use of air-stable Rh catalyst, high monoarylation selectivity, and excellent yields of most of the substrates.

  9. The HCClF_2-HCCH Complex: Microwave Spectrum, Structure and C-H\\cdotsπ Interactions (United States)

    Peebles, Rebecca A.; Sexton, John M.; Elliott, Ashley A.; Steber, Amanda L.; Peebles, Sean A.; Neill, Justin L.; Muckle, Matt T.; Pate, Brooks H.


    The HCF_3-HCCH complex was recently found to have a weak C-H\\cdotsπ interaction between the fluoroform and acetylene, as well as having a secondary interaction between the fluorine atoms and one of the acetylene hydrogen atoms; however, extensive splittings due to large amplitude motions within the complex have complicated our efforts at making a full assignment of the HCF_3-HCCH spectrum. In an attempt to remove some of the ambiguity in the HCF_3-HCCH study, we have substituted a chlorine atom for one fluorine atom and undertaken an investigation of the HCClF_2-HCCH complex. This eliminates the possibility of internal rotation of the methane subunit, while still maintaining a C-H\\cdotsπ interaction. Using the chirped-pulse Fourier-transform microwave (CP-FTMW) spectrometer at the University of Virginia and the Balle-Flygare FTMW spectrometer at Eastern Illinois University, the spectra of four isotopologues of HCClF_2-HCCH have been assigned, with no indication of internal motions within the complex. The structure has been determined from the experimental moments of inertia, confirming that this dimer has the expected weak C-H\\cdotsπ interaction. In addition, the off-diagonal χab quadrupole coupling constant has been used to determine the angle between the C-Cl bond and the a-axis of the complex. This, and Kraitchman coordinates for the chlorine atom, help confirm the structural details from the inertial fit. The structural results will be compared with other complexes showing C-H\\cdotsπ and C-H\\cdotsO interactions. S. A. Peebles, M. M. Serafin, R. A. Peebles, 61st International Symposium on Molecular Spectroscopy, Talk MH13, June 19, 2006.

  10. Combined UV-C/H2O2-VUV processes for the treatment of an actual slaughterhouse wastewater. (United States)

    Naderi, Kambiz Vaezzadeh; Bustillo-Lecompte, Ciro Fernando; Mehrvar, Mehrab; Abdekhodaie, Mohammad Jafar


    In this study, a three-factor, three-level Box-Behnken design with response surface methodology were used to maximize the TOC removal and minimize the H 2 O 2 residual in the effluent of the combined UV-C/H 2 O 2 -VUV system for the treatment of an actual slaughterhouse wastewater (SWW) collected from one of the meat processing plants in Ontario, Canada. The irradiation time and the initial concentrations of total organic carbon (TOC o ) and hydrogen peroxide (H 2 O 2o ) were the three predictors, as independent variables, studied in the design of experiments. The multiple response approach was used to obtain desirability response surfaces at the optimum factor settings. Subsequently, the optimum conditions to achieve the maximum percentage TOC removal of 46.19% and minimum H 2 O 2 residual of 1.05% were TOC o of 213 mg L -1 , H 2 O 2o of 450 mg L -1 , and irradiation time of 9 min. The attained optimal operating conditions were validated with a complementary test. Consequently, the TOC removal of 45.68% and H 2 O 2 residual of 1.03% were achieved experimentally, confirming the statistical model reliability. Three individual processes, VUV alone, VUV/H 2 O 2 , and UV-C/H 2 O 2 , were also evaluated to compare their performance for the treatment of the actual SWW using the optimum parameters obtained in combined UV-C/H 2 O 2 -VUV processes. Results confirmed that an adequate combination of the UV-C/H 2 O 2 -VUV processes is essential for an optimized TOC removal and H 2 O 2 residual. Finally, respirometry analyses were also performed to evaluate the biodegradability of the SWW and the BOD removal efficiency of the combined UV-C/H 2 O 2 -VUV processes.

  11. Plasmonic titanium nitride nanostructures for perfect absorbers

    DEFF Research Database (Denmark)

    Guler, Urcan; Li, Wen-Wei; Kinsey, Nathaniel


    We propose a metamaterial based perfect absorber in the visible region, and investigate the performance of titanium nitride as an alternative plasmonic material. Numerical and experimental results reveal that titanium nitride performs better than gold as a plasmonic absorbing material...

  12. Piezooptic effect of absorbing environment

    Directory of Open Access Journals (Sweden)

    Ю. А. Рудяк


    Full Text Available Application of piezooptic effect of absorbing environment for the definition of the parameter of stress deformation state was examined. The analysis of dielectric permeability tensor of imaginary parts was done. It is shown that changes in the real part dielectric permeability tensor mainly the indicator of fracture was fixed by means of mechanics interference methods and the changes in the imaginary part (α – real rate of absorption can be measured by means of analysis of light absorption and thus stress deformation state can be determined

  13. Aging of oxygen and hydrogen plasma discharge treated a-C:H and ta-C coatings

    Energy Technology Data Exchange (ETDEWEB)

    Bachmann, Svenja [Physics of Surfaces, Institute of Materials Science, Technische Universität Darmstadt, Alarich-Weiss-Str. 16, 64287 Darmstadt (Germany); BMW Group, Hufelandstraße 4, 80788 Munich (Germany); Schulze, Marcus [Physics of Surfaces, Institute of Materials Science, Technische Universität Darmstadt, Alarich-Weiss-Str. 16, 64287 Darmstadt (Germany); Center of Smart Interfaces, Technische Universität Darmstadt, Alarich-Weiss-Str. 10, 64287 Darmstadt (Germany); Morasch, Jan [Institute of Materials Science, Technische Universität Darmstadt, Surface Science Division, Jovanka-Bonschits-Straße 2, 64287 Darmstadt (Germany); Hesse, Sabine [Physics of Surfaces, Institute of Materials Science, Technische Universität Darmstadt, Alarich-Weiss-Str. 16, 64287 Darmstadt (Germany); Center of Smart Interfaces, Technische Universität Darmstadt, Alarich-Weiss-Str. 10, 64287 Darmstadt (Germany); Hussein, Laith [Eduard-Zintl-Institut, Department of Chemistry, Technische Universität Darmstadt, Alarich-Weiss-Str. 12, 64287, Darmstadt (Germany); Krell, Lisa; Schnagl, Johann [BMW Group, Hufelandstraße 4, 80788 Munich (Germany); Stark, Robert W. [Physics of Surfaces, Institute of Materials Science, Technische Universität Darmstadt, Alarich-Weiss-Str. 16, 64287 Darmstadt (Germany); Center of Smart Interfaces, Technische Universität Darmstadt, Alarich-Weiss-Str. 10, 64287 Darmstadt (Germany); and others


    Highlights: • The water CA of O{sub 2} and H{sub 2} plasma treated a-C:H and ta-C changes from hydrophillic to hydrophobic on aging. • XPS study indicates that the decrease in surface energy of plasma treated a-C:H and ta-C could be due to adsorption of organic component from air. • The COFLFM of O{sub 2} and H{sub 2} plasma treated a-C:H and ta-C decreased upon aging. • The COF of glycerol lubricated ta-C showed no sign of change upon aging. - Abstract: Surface modification with gas plasma is an efficient and easy way to improve the surface energy and the tribological behavior of diamond-like carbon (DLC) coatings, e.g., in biomedical implants or as protective coatings. However, the long-term performance of the plasma treated DLC coatings is not fully clear. We thus studied the long-term stability of two kinds of DLC coatings, namely (a) hydrogenated amorphous carbon (a-C:H) and (b) tetrahedral amorphous carbon (ta-C) treated at different radio frequency (RF) power and time of oxygen (O{sub 2}) and hydrogen (H{sub 2}) plasma. Their surface properties, e.g. surface wettability, structure and tribological behavior, were studied at regular intervals for a period of two months using contact angle goniometer, Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), lateral force microscopy (LFM) and ball on disc apparatus. The surface energy of both the coatings decreased upon aging. The higher the RF power and time of treatment, the higher was the hydrophobicity upon aging. XPS analysis showed that the increase in hydrophobicity could be due to adsorption of unavoidable volatile organic components in the atmosphere. The H{sub 2} plasma treated ta-C was capable of rearranging its structural bonds upon aging. The nano-friction measurements by LFM showed that the coefficient of friction of plasma treated a-C:H and ta-C decreased upon aging. The results indicate that the surface properties of plasma treated a‐C:H and ta‐C are not stable on long-term and are

  14. Ab Initio Reaction Kinetics of CH 3 O$\\dot{C}$(=O) and $\\dot{C}$H 2 OC(=O)H Radicals

    Energy Technology Data Exchange (ETDEWEB)

    Tan, Ting; Yang, Xueliang; Ju, Yiguang; Carter, Emily A.


    The dissociation and isomerization kinetics of the methyl ester combustion intermediates methoxycarbonyl radical (CH3O$\\dot{C}$(=O)) and (formyloxy)methyl radical ($\\dot{C}$H2OC(=O)H) are investigated theoretically using high-level ab initio methods and Rice–Ramsperger–Kassel–Marcus (RRKM)/master equation (ME) theory. Geometries obtained at the hybrid density functional theory (DFT) and coupled cluster singles and doubles with perturbative triples correction (CCSD(T)) levels of theory are found to be similar. We employ high-level ab initio wave function methods to refine the potential energy surface: CCSD(T), multireference singles and doubles configuration interaction (MRSDCI) with the Davidson–Silver (DS) correction, and multireference averaged coupled-pair functional (MRACPF2) theory. MRSDCI+DS and MRACPF2 capture the multiconfigurational character of transition states (TSs) and predict lower barrier heights than CCSD(T). The temperature- and pressure-dependent rate coefficients are computed using RRKM/ME theory in the temperature range 300–2500 K and a pressure range of 0.01 atm to the high-pressure limit, which are then fitted to modified Arrhenius expressions. Dissociation of CH3O$\\dot{C}$(=O) to $\\dot{C}$H3 and CO2 is predicted to be much faster than dissociating to CH3$\\dot{O}$ and CO, consistent with its greater exothermicity. Isomerization between CH3O$\\dot{C}$(=O) and $\\dot{C}$H2OC(=O)H is predicted to be the slowest among the studied reactions and rarely happens even at high temperature and high pressure, suggesting the decomposition pathways of the two radicals are not strongly coupled. The predicted rate coefficients and branching fractions at finite pressures differ significantly from the corresponding high-pressure-limit results, especially at relatively high temperatures. Finally, because it is one of the most important CH3$\\dot{O}$ removal mechanisms under atmospheric conditions, the reaction kinetics of CH3$\\dot{O}$ + CO was

  15. Multi-channel coherent perfect absorbers

    KAUST Repository

    Bai, Ping


    The absorption efficiency of a coherent perfect absorber usually depends on the phase coherence of the incident waves on the surfaces. Here, we present a scheme to create a multi-channel coherent perfect absorber in which the constraint of phase coherence is loosened. The scheme has a multi-layer structure such that incident waves in different channels with different angular momenta can be simultaneously and perfectly absorbed. This absorber is robust in achieving high absorption efficiency even if the incident waves become "incoherent" and possess "random" wave fronts. Our work demonstrates a unique approach to designing highly efficient metamaterial absorbers. © CopyrightEPLA, 2016.

  16. Graphene based salisbury screen for terahertz absorber (United States)

    Min Woo, Jeong; Kim, Min-Sik; Woong Kim, Hyun; Jang, Jae-Hyung


    A graphene-based, multiband absorber operating in terahertz (THz) frequency range was demonstrated. Graphene film was transferred onto the top of a flexible polymer substrate backed with a gold reflector. The graphene acts as a resistive film that partially attenuates and reflects THz waves. The destructive interference between THz waves reflected from graphene and backside reflector gives rise to perfect absorbance at multiple frequencies. To enhance the absorbance on/off ratio (AR), the conductivity of graphene was varied using a chemical doping method. The resulting p-doped, graphene-based THz absorber exhibited absorbance at maxima and AR higher than 0.95 and 25 dB, respectively.

  17. (NHC)Cu-Catalyzed Mild C-H Amidation of (Hetero)arenes with Deprotectable Carbamates: Scope and Mechanistic Studies. (United States)

    Xie, Weilong; Yoon, Jung Hee; Chang, Sukbok


    Primary arylamines are an important unit broadly found in synthetic, biological, and materials science. Herein we describe the development of a (NHC)Cu system that mediates a direct C-H amidation of (hetero)arenes by using N-chlorocarbamates or their sodio derivatives as the practical amino sources. A facile stoichiometric reaction of reactive copper-aryl intermediates with the amidating reagent led us to isolate key copper arylcarbamate species with the formation of a C-N bond. The use of (t)BuONa base made this transformation catalytic under mild conditions. The present (NHC)Cu-catalyzed C-H amidation works efficiently and selectively on a large scale over a range of arenes including polyfluorobenzenes, azoles, and quinoline N-oxides. Deprotection of the newly installed carbamate groups such as Boc and Cbz was readily performed to afford the corresponding primary arylamines.

  18. Salt-Free Strategy for the Insertion of CO2 into C-H Bonds: Catalytic Hydroxymethylation of Alkynes. (United States)

    Wendling, Timo; Risto, Eugen; Krause, Thilo; Gooßen, Lukas J


    A copper(I) catalyst enables the insertion of carbon dioxide into alkyne C-H bonds by using a suitable organic base with which hydrogenation of the resulting carboxylate salt with regeneration of the base becomes thermodynamically feasible. In the presence of catalytic copper(I) chloride/4,7-diphenyl-1,10-phenanthroline, polymer-bound triphenylphosphine, and 2,2,6,6-tetramethylpiperidine as the base, terminal alkynes undergo carboxylation at 15 bar CO 2 and room temperature. After filtration, the ammonium alkynecarboxylate can be hydrogenated to the primary alcohol and water at a rhodium/molybdenum catalyst, regenerating the amine base. This demonstrates the feasibility of a salt-free overall process, in which carbon dioxide serves as a C1 building block in a C-H functionalization. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Mechanistic Investigations of C-H Activations on Silica-Supported Co(ii) Sites in Catalytic Propane Dehydrogenation. (United States)

    Estes, Deven P


    Catalytic reactions involving C-H bond activations are central to the chemical industry. One such example, alkane dehydrogenation, has recently become very important due to shortfalls in propene production and a large supply of cheap propane. However, current technologies are inefficient and have only moderate selectivity. In order to understand how to improve currently used catalysts, we must know more about the mechanism by which propane is dehydrogenated. We show here that Co(ii) sites on silica are good catalysts for the dehydrogenation of propane, having high activity and selectivity that is reasonably stable over the course of 10 h. Mechanistic investigations of this catalyst show that the main activation mechanism is most likely C-H activation by 1,2 addition.

  20. Rhodium-catalyzed direct C-H amination of benzamides with aryl azides: a synthetic route to diarylamines. (United States)

    Ryu, Jaeyune; Shin, Kwangmin; Park, Sae Hume; Kim, Ji Young; Chang, Sukbok


    No muss, no fuss: A rhodium-catalyzed direct intermolecular C-H amination of benzamides and ketoximes using aryl azides as the amine source has been developed. The reaction exhibits a broad substrate scope with excellent functional-group tolerance, requires no external oxidants, releases N(2) as the only by-product, and produces diarylamines in high yields. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Up-scaling the production of modified a-C:H coatings in the framework of plasma polymerization processes (United States)

    Corbella, C.; Bialuch, I.; Kleinschmidt, M.; Bewilogua, K.


    Hydrogenated amorphous carbon (a-C:H) films with silicon and oxygen additions, which exhibit mechanical, tribological and wetting properties adequate for protective coating performance, have been synthesized at room temperature in a small- (0.1 m 3) and a large-scale (1 m 3) coaters by low-pressure Plasma-Activated Chemical Vapour Deposition (PACVD). Hence, a-C:H:Si and a-C:H:Si:O coatings were produced in atmospheres of tetramethylsilane (TMS) and hexamethyldisiloxane (HMDSO), respectively, excited either by radiofrequency (RF - small scale) or by pulsed-DC power (large scale). Argon was employed as a carrier gas to stabilize the glow discharge. Several series of 2-5 μm thick coatings have been prepared at different mass deposition rates, Rm, by varying total gas flow, F, and input power, W. Arrhenius-type plots of Rm/ F vs. ( W/ F) -1 show linear behaviours for both plasma reactors, as expected for plasma polymerization processes at moderated energies. The calculation of apparent activation energy, Ea, in each series permitted us to define the regimes of energy-deficient and monomer-deficient PACVD processes as a function of the key parameter W/ F. Moreover, surface properties of the modified a-C:H coatings, such as contact angle, abrasive wear rate and hardness, appear also correlated to this parameter. This work shows an efficient methodology to scale up PACVD processes from small, lab-scale plasma machines to industrial plants by the unique evaluation of macroscopic parameters of deposition.

  2. Activation of Propane C-H and C-C Bonds by Gas-Phase Pt Atom: A Theoretical Study

    Directory of Open Access Journals (Sweden)

    Chang-Wei Hu


    Full Text Available The reaction mechanism of the gas-phase Pt atom with C3H8 has been systematically investigated on the singlet and triplet potential energy surfaces at CCSD(T//BPW91/6-311++G(d, p, Lanl2dz level. Pt atom prefers the attack of primary over secondary C-H bonds in propane. For the Pt + C3H8 reaction, the major and minor reaction channels lead to PtC3H6 + H2 and PtCH2 + C2H6, respectively, whereas the possibility to form products PtC2H4 + CH4 is so small that it can be neglected. The minimal energy reaction pathway for the formation of PtC3H6 + H2, involving one spin inversion, prefers to start at the triplet state and afterward proceed along the singlet state. The optimal C-C bond cleavages are assigned to C-H bond activation as the first step, followed by cleavage of a C-C bond. The C-H insertion intermediates are kinetically favored over the C-C insertion intermediates. From C-C to C-H oxidative insertion, the lowering of activation barrier is mainly caused by the more stabilizing transition state interaction ΔEint, which is the actual interaction energy between the deformed reactants in the transition state.

  3. C-H...pi interactions in the low-temperature crystal structures of alpha,omega-unsaturated linear hydrocarbons. (United States)

    Bond, Andrew D


    The low-temperature crystal structures of 1,7-octadiene (C8H14), 1,9-decadiene (C10H18), 1,7-octadiyne (C8H10) and 1,9-decadiyne (C10H14), determined following in situ crystal growth from the liquid, reveal the role of C-H...pi interactions in alpha,omega-unsaturated linear hydrocarbons in the solid state.

  4. Vapour-induced solid-state C-H bond activation for the clean synthesis of an organopalladium biothiol sensor. (United States)

    Monas, Andrea; Užarević, Krunoslav; Halasz, Ivan; Kulcsár, Marina Juribašić; Ćurić, Manda


    Room-temperature accelerated aging in the solid state has been applied for atom- and energy-efficient activation of either one or two C-H bonds of azobenzene and methyl orange by palladium(ii) acetate. Organopalladium complexes are prepared in quantitative reactions without potentially harmful side products. Dicyclopalladated methyl orange is water-soluble and is a selective chromogenic biothiol sensor at physiologically-relevant micromolar concentrations in buffered aqueous media.

  5. Palladium-Catalyzed ortho-Olefination of Phenyl Acetic and Phenyl Propylacetic Esters via C-H Bond Activation. (United States)

    Hu, Jundie; Guan, Mingyu; Han, Jian; Huang, Zhi-Bin; Shi, Da-Qing; Zhao, Yingsheng


    A highly regioselective palladium-catalyzed ester-directed ortho-olefination of phenyl acetic and propionic esters with olefins via C-H bond activation has been developed. A wide variety of phenyl acetic and propionic esters were tolerated in this transformation, affording the corresponding olefinated aromatic compounds. The ortho-olefination of heterocyclic acetic and propionic esters also took place smoothly giving the products in good yields, thus proving the potential utility of this protocol in synthetic chemistry.

  6. Rh(III) -Catalyzed C-H Olefination of Benzoic Acids under Mild Conditions using Oxygen as the Sole Oxidant. (United States)

    Jiang, Quandi; Zhu, Changlei; Zhao, Huaiqing; Su, Weiping


    Phthalide skeletons have been synthesized for the first time through a Rh(III) -catalyzed C-H olefination of benzoic acids under mild conditions using oxygen as the sole oxidant. Aromatic acids bearing a variety of functional groups could react with diverse alkenes to afford the desired cyclized lactones or uncyclized alkenylarenes in moderate-to-excellent yields. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Remote meta-C-H olefination of phenylacetic acids directed by a versatile U-shaped template. (United States)

    Deng, Youqian; Yu, Jin-Quan


    meta-C-H olefination of phenylacetic acid derivatives has been achieved using a commercially available nitrile-containing template. The identification of N-formyl-protected glycine as the ligand (Formyl-Gly-OH) was crucial for the development of this reaction. Versatility of the template approach in accommodating macrocyclopalladation processes with different ring sizes is demonstrated. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Pärt: Collage sur B-A-C-H für Kammerorschester / Hans-Christian Dadelsen

    Index Scriptorium Estoniae

    Dadelsen, Hans-Christian


    Uuest heliplaadist "Pärt: Collage sur B-A-C-H für Kammerorschester, Summa (1991) für Streichorchester, Fratres, Sinfonie Nr. 2, Festina lente, Wenn Bach Bienen gezüchtet hätte, Credo für Klavier, Chor und Orchester. Philharmonia Orchestra and Chorus, Neeme Järvi". Chandos/Koch CD 9134 (WD: 63'02")

  9. Structure and spectroscopic properties of neutral and cationic tetratomic [C,H,N,Zn] isomers: A theoretical study

    Energy Technology Data Exchange (ETDEWEB)

    Redondo, Pilar; Largo, Antonio; Vega-Vega, Álvaro; Barrientos, Carmen, E-mail: [Departamento de Química Física y Química Inorgánica, Facultad de Ciencias, Universidad de Valladolid, 47011 Valladolid (Spain)


    The structure and spectroscopic parameters of the most relevant [C,H,N,Zn] isomers have been studied employing high-level quantum chemical methods. For each isomer, we provide predictions for their molecular structure, thermodynamic stabilities as well as vibrational and rotational spectroscopic parameters which could eventually help in their experimental detection. In addition, we have carried out a detailed study of the bonding situations by means of a topological analysis of the electron density in the framework of the Bader’s quantum theory of atoms in molecules. The analysis of the relative stabilities and spectroscopic parameters suggests two linear isomers of the neutral [C,H,N,Zn] composition, namely, cyanidehydridezinc HZnCN ({sup 1}Σ) and hydrideisocyanidezinc HZnNC ({sup 1}Σ), as possible candidates for experimental detections. For the cationic [C,H,N,Zn]{sup +} composition, the most stable isomers are the ion-molecule complexes arising from the direct interaction of the zinc cation with either the nitrogen or carbon atom of either hydrogen cyanide or hydrogen isocyanide, namely, HCNZn{sup +} ({sup 2}Σ) and HCNZn{sup +} ({sup 2}Σ)

  10. Influence of nitrogen on the tribological properties of a-C:H layers on the polycarbonate substrates

    Directory of Open Access Journals (Sweden)

    Rafal M. Nowak


    Full Text Available Polycarbonate (PC possesses many commercial applications. However, PC is still limited to non-abrasive and chemical-free environments due to its low hardness, low scratching resistance and high susceptibility to chemical attacks. To overcome this limitation, PC can be coated by hydrogenated amorphous carbon layers. The a-C:H layers have very attractive properties such as high hardness, infrared transparency, chemical inertness, low friction coefficients, and biocompatibility. Addition of nitrogen in the structure allows lowering internal stress and improve tribological properties of a-C:H layers. In this work, a-C:N:H layers were deposited from mixture CH4/N2 gases by RF PECVD method. Effects of the nitrogen incorporation on structure and tribological properties of deposited layers were investigated. The structure of layers were characterized by Fourier Transform Infrared spectroscopy (FTIR and X-ray photoelectron spectroscopy (XPS. The friction coefficient, wear resistance of a-C:H:N layers were estimated by tribometer in ball-on-disc configuration. The IR spectra of the obtained layers have demonstrated a presence of nitrogen bonded both to carbon and to hydrogen. A formation of the following bonds has been confirmed: -C≡N, -NH2, -C−NH2, >C=NH. They are all typical for a-C:N:H layers. The tribological tests have shown that the layers reduce the friction coefficient of the polycarbonate (up to 50 % and considerably improve wear resistance.

  11. Rats Born to Mothers Treated with Dexamethasone 15 cH Present Changes in Modulation of Inflammatory Process

    Directory of Open Access Journals (Sweden)

    Leoni V. Bonamin


    Full Text Available As little information about the effect of ultra high dilutions of glucocorticoid in reproduction is available in the literature, pregnant female Wistar rats (N=12 were blindly subcutaneously treated during all gestational and lactation period with: dexamethasone 4 mg/kg diluted into dexamethasone 15 cH (mixed; or dexamethasone 4 mg/kg diluted in water; or dexamethasone 15 cH, or vehicle. Parental generation had body weight, food and water consumption monitored. The F1 generation was monitored regarding to newborn development. No birth occurred in both groups treated with dexamethasone 4 mg/kg. After 60 days from birth, 12 male F1 rats were randomly selected from each remaining group and inoculated subcutaneously with 1% carrageenan into the footpad, for evaluation of inflammatory performance. Edema and histopathology of the footpad were evaluated, using specific staining methods, immunohistochemistry and digital histomorphometry. Mothers treated with mixed dexamethasone presented reduced water consumption. F1 rats born to dexamethasone 15 cH treated females presented significant increase in mast cell degranulation, decrease in monocyte percentage, increase in CD18+ PMN cells, and early expression of ED2 protein, in relation to control. The results show that the exposure of parental generation to highly diluted dexamethasone interferes in inflammation modulation in the F1 generation.

  12. A general approach to intermolecular carbonylation of arene C-H bonds to ketones through catalytic aroyl triflate formation (United States)

    Garrison Kinney, R.; Tjutrins, Jevgenijs; Torres, Gerardo M.; Liu, Nina Jiabao; Kulkarni, Omkar; Arndtsen, Bruce A.


    The development of metal-catalysed methods to functionalize inert C-H bonds has become a dominant research theme in the past decade as an approach to efficient synthesis. However, the incorporation of carbon monoxide into such reactions to form valuable ketones has to date proved a challenge, despite its potential as a straightforward and green alternative to Friedel-Crafts reactions. Here we describe a new approach to palladium-catalysed C-H bond functionalization in which carbon monoxide is used to drive the generation of high-energy electrophiles. This offers a method to couple the useful features of metal-catalysed C-H functionalization (stable and available reagents) and electrophilic acylations (broad scope and selectivity), and synthesize ketones simply from aryl iodides, CO and arenes. Notably, the reaction proceeds in an intermolecular fashion, without directing groups and at very low palladium-catalyst loadings. Mechanistic studies show that the reaction proceeds through the catalytic build-up of potent aroyl triflate electrophiles.

  13. Cu-catalyzed cross-dehydrogenative coupling: A versatile strategy for C-C bond formations via the oxidative activation of sp3 C-H bonds (United States)

    Li, Zhiping; Bohle, D. Scott; Li, Chao-Jun


    Cu-catalyzed cross-dehydrogenative coupling (CDC) methodologies were developed based on the oxidative activation of sp3 C-H bonds adjacent to a nitrogen atom. Various sp, sp2, and sp3 C-H bonds of pronucleophiles were used in the Cu-catalyzed CDC reactions. Based on these results, the mechanisms of the CDC reactions also are discussed. C-H activation | catalysis | Baylis-Hillman reaction | Mannich reaction | Friedel-Crafts reaction

  14. Flexible metamaterial absorbers for stealth applications at terahertz frequencies

    DEFF Research Database (Denmark)

    Iwaszczuk, Krzysztof; Strikwerda, Andrew; Fan, K.


    We have wrapped metallic cylinders with strongly absorbing metamaterials. These resonant structures, which are patterned on flexible substrates, smoothly coat the cylinder and give it an electromagnetic response designed to minimize its radar cross section. We compare the normal-incidence, small...... frequency of 0.87 THz. In addition we discuss the effect of finite sample dimensions and the spatial dependence of the reflection spectrum of the metamaterial. (C)2011 Optical Society of America...

  15. Diagnostics in dusty C-H-O plasmas with diamond and graphitic nanoparticle generation

    International Nuclear Information System (INIS)

    Gries, T; Vandenbulcke, L; De Persis, S; Rouzaud, J N


    A decrease in electron density and a strong increase of electron energy, which induce the enhancement of excitation rates, have been observed in CH 4 -CO 2 plasmas when the inlet methane concentration is high enough and the input microwave power sufficiently low. Together with the decrease in the electron density with plasma duration, they are characteristic of dust formation in these plasmas. In these conditions, the formation of hydrocarbon radicals which are well known precursors of soot and the formation of first stable aromatics are reported, as observed by molecular beam mass spectrometry. Modelling of the chemistry in the plasma is carried out, which can also predict the formation of low concentrations of polyaromatic hydrocarbons. These species could be involved in the homogeneous nucleation process of carbon. As a function of the plasma duration, various carbon nanostructures are observed in the particles collected downstream of the plasma. For short durations, nanodiamond grains are formed with the size range 15-100 nm. They are composed of diamond nanocrystals of about 2-10 nm in size; these values are generally observed for all diamond nanocrystals formed in extraterrestrial and terrestrial conditions. For longer plasma durations, sp 2 -hybridized carbons are obtained. Their structure varies from soot to more ordered graphitic carbons nearly similar to 'onions' and structures similar to those observed in tokamaks. The control of the size and the microstructure of the nanodiamond grains are especially important as this could open possibilities for applications in a wide range of fields.

  16. Engineering Porous Polymer Hollow Fiber Microfluidic Reactors for Sustainable C-H Functionalization. (United States)

    He, Yingxin; Rezaei, Fateme; Kapila, Shubhender; Rownaghi, Ali A


    Highly hydrophilic and solvent-stable porous polyamide-imide (PAI) hollow fibers were created by cross-linking of bare PAI hollow fibers with 3-aminopropyl trimethoxysilane (APS). The APS-grafted PAI hollow fibers were then functionalized with salicylic aldehyde for binding catalytically active Pd(II) ions through a covalent postmodification method. The catalytic activity of the composite hollow fiber microfluidic reactors (Pd(II) immobilized APS-grafted PAI hollow fibers) was tested via heterogeneous Heck coupling reaction of aryl halides under both batch and continuous-flow reactions in polar aprotic solvents at high temperature (120 °C) and low operating pressure. X-ray photoelectron spectroscopy (XPS) and inductively coupled plasma (ICP) analyses of the starting and recycled composite hollow fibers indicated that the fibers contain very similar loadings of Pd(II), implying no degree of catalyst leaching from the hollow fibers during reaction. The composite hollow fiber microfluidic reactors showed long-term stability and strong control over the leaching of Pd species.

  17. Testing strong interaction theories

    International Nuclear Information System (INIS)

    Ellis, J.


    The author discusses possible tests of the current theories of the strong interaction, in particular, quantum chromodynamics. High energy e + e - interactions should provide an excellent means of studying the strong force. (W.D.L.)

  18. An omnidirectional electromagnetic absorber made of metamaterials

    International Nuclear Information System (INIS)

    Cheng Qiang; Cui Tiejun; Jiang Weixiang; Cai Bengeng


    In a recent theoretical work by Narimanov and Kildishev (2009 Appl. Phys. Lett. 95 041106) an optical omnidirectional light absorber based on metamaterials was proposed, in which theoretical analysis and numerical simulations showed that all optical waves hitting the absorber are trapped and absorbed. Here we report the first experimental demonstration of an omnidirectional electromagnetic absorber in the microwave frequency. The proposed device is composed of non-resonant and resonant metamaterial structures, which can trap and absorb electromagnetic waves coming from all directions spirally inwards without any reflections due to the local control of electromagnetic fields. It is shown that the absorption rate can reach 99 per cent in the microwave frequency. The all-directional full absorption property makes the device behave like an 'electromagnetic black body', and the wave trapping and absorbing properties simulate, to some extent, an 'electromagnetic black hole.' We expect that such a device could be used as a thermal emitting source and to harvest electromagnetic waves.

  19. Comments on liquid hydrogen absorbers for MICE

    International Nuclear Information System (INIS)

    Green, Michael A.


    This report describes the heat transfer problems associated with a liquid hydrogen absorber for the MICE experiment. This report describes a technique for modeling heat transfer from the outside world, to the absorber case and in its vacuum vessel, to the hydrogen and then into helium gas at 14 K. Also presented are the equation for free convection cooling of the liquid hydrogen in the absorber

  20. Multiband Negative Permittivity Metamaterials and Absorbers

    Directory of Open Access Journals (Sweden)

    Yiran Tian


    Full Text Available Design and characteristics of multiband negative permittivity metamaterial and its absorber configuration are presented in this paper. The proposed multiband metamaterial is composed of a novel multibranch resonator which can possess four electric resonance frequencies. It is shown that, by controlling the length of the main branches of such resonator, the resonant frequencies and corresponding absorbing bands of metamaterial absorber can be shifted in a large frequency band.

  1. Atoms in strong laser fields

    International Nuclear Information System (INIS)

    L'Huillier, A.


    When a high-power laser focuses into a gas of atoms, the electromagnetic field becomes of the same magnitude as the Coulomb field which binds a 1s electron in a hydrogen atom. 3 highly non-linear phenomena can happen: 1) ATI (above threshold ionization): electrons initially in the ground state absorb a large number of photons, many more than the minimum number required for ionization; 2) multiple ionization: many electrons can be emitted one at a time, in a sequential process, or simultaneously in a mechanism called direct or non-sequential; and 3) high order harmonic generation (HHG): efficient photon emission in the extreme ultraviolet range, in the form of high-order harmonics of the fundamental laser field can occur. The theoretical problem consists in solving the time dependent Schroedinger equation (TDSE) that describes the interaction of a many-electron atom with a laser field. A number of methods have been proposed to solve this problem in the case of a hydrogen atom or a single-active electron atom in a strong laser field. A large effort is presently being devoted to go beyond the single-active approximation. The understanding of the physics of the interaction between atoms and strong laser fields has been provided by a very simple model called ''simple man's theory''. A unified view of HHG, ATI, and non-sequential ionization, originating from the simple man's model and the strong field approximation, expressed in terms of electrons trajectories or quantum paths is slowly emerging. (A.C.)

  2. Aging of oxygen and hydrogen plasma discharge treated a-C:H and ta-C coatings (United States)

    Bachmann, Svenja; Schulze, Marcus; Morasch, Jan; Hesse, Sabine; Hussein, Laith; Krell, Lisa; Schnagl, Johann; Stark, Robert W.; Narayan, Suman


    Surface modification with gas plasma is an efficient and easy way to improve the surface energy and the tribological behavior of diamond-like carbon (DLC) coatings, e.g., in biomedical implants or as protective coatings. However, the long-term performance of the plasma treated DLC coatings is not fully clear. We thus studied the long-term stability of two kinds of DLC coatings, namely (a) hydrogenated amorphous carbon (a-C:H) and (b) tetrahedral amorphous carbon (ta-C) treated at different radio frequency (RF) power and time of oxygen (O2) and hydrogen (H2) plasma. Their surface properties, e.g. surface wettability, structure and tribological behavior, were studied at regular intervals for a period of two months using contact angle goniometer, Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), lateral force microscopy (LFM) and ball on disc apparatus. The surface energy of both the coatings decreased upon aging. The higher the RF power and time of treatment, the higher was the hydrophobicity upon aging. XPS analysis showed that the increase in hydrophobicity could be due to adsorption of unavoidable volatile organic components in the atmosphere. The H2 plasma treated ta-C was capable of rearranging its structural bonds upon aging. The nano-friction measurements by LFM showed that the coefficient of friction of plasma treated a-C:H and ta-C decreased upon aging. The results indicate that the surface properties of plasma treated a-C:H and ta-C are not stable on long-term and are influenced by the environmental conditions.

  3. Quality Improvements in the Early Care and Education Workforce: Outcomes and Impact of the T.E.A.C.H. Early Childhood[R] Project (United States)

    Miller, Joyce Ann; Bogatova, Tania


    To date there has not been a systematic, longitudinal research to assess the efficacy of public investments in the professional development of early childhood educators that are funded through the T.E.A.C.H. Early Childhood[R] Project. This study of the T.E.A.C.H. Early Childhood[R] Project Pennsylvania provides a longitudinal analysis of the data…

  4. Device for absorbing mechanical shock (United States)

    Newlon, C.E.


    This invention is a comparatively inexpensive but efficient shock-absorbing device having special application to the protection of shipping and storage cylinders. In a typical application, two of the devices are strapped to a cylinder to serve as saddle-type supports for the cylinder during storage and to protect the cylinder in the event it is dropped during lifting or lowering operations. In its preferred form, the invention includes a hardwood plank whose grain runs in the longitudinal direction. The basal portion of the plank is of solid cross-section, whereas the upper face of the plank is cut away to form a concave surface fittable against the sidewall of a storage cylinder. The concave surface is divided into a series of segments by transversely extending, throughgoing relief slots. A layer of elastomeric material is positioned on the concave face, the elastomer being extrudable into slots when pressed against the segments by a preselected pressure characteristic of a high-energy impact. The compressive, tensile, and shear properties of the hardwood and the elastomer are utilized in combination to provide a surprisingly high energy-absorption capability.

  5. Gaseous carbon dioxide absorbing column

    International Nuclear Information System (INIS)

    Harashina, Heihachi.


    The absorbing column of the present invention comprises a cyclone to which CO 2 gas and Ca(OH) 2 are blown to form CaCO 3 , a water supply means connected to an upper portion of the cyclone for forming a thin water membrane on the inner wall thereof, and a water processing means connected to a lower portion of the cyclone for draining water incorporating CaCO 3 . If a mixed fluid of CO 2 gas and Ca(OH) 2 is blown in a state where a flowing water membrane is formed on the inner wall of the cyclone, formation of CaCO 3 is promoted also in the inside of the cyclone in addition to the formation of CaCO 3 in the course of blowing. Then, formed CaCO 3 is discharged from the lower portion of the cyclone together with downwardly flowing water. With such procedures, solid contents such as CaCO 3 separated at the inner circumferential wall are sent into the thin water membrane, adsorbed and captured, and the solid contents are successively washed out, so that a phenomenon that the solid contents deposit and grow on the inner wall of the cyclone can be prevented effectively. (T.M.)

  6. Iridium-Catalyzed Direct C-H Sulfamidation of Aryl Nitrones with Sulfonyl Azides at Room Temperature. (United States)

    Pi, Chao; Cui, Xiuling; Wu, Yangjie


    Ir(III)-catalyzed direct C-H sulfamidation of aryl nitrones has been developed to synthesize various sulfamidated nitrones in moderate to excellent yields with excellent regioselectivity and broad functional group tolerance. This transformation could proceed smoothly at room temperature with low catalyst loading in the absence of external oxidants, acids, or bases. Molecular nitrogen was released as the sole byproduct, thus providing an environmentally benign sulfamidation process. And this protocol could efficiently apply to synthesize the substituted benzisoxazoline via one-step transformation from the product.

  7. Carboxylate-Assisted Iridium-Catalyzed C-H Amination of Arenes with Biologically Relevant Alkyl Azides. (United States)

    Zhang, Tao; Hu, Xuejiao; Wang, Zhen; Yang, Tiantian; Sun, Hao; Li, Guigen; Lu, Hongjian


    An iridium-catalyzed C-H amination of arenes with a wide substrate scope is reported. Benzamides with electron-donating and -withdrawing groups and linear, branched, and cyclic alkyl azides are all applicable. Cesium carboxylate is crucial for both reactivity and regioselectivity of the reactions. Many biologically relevant molecules, such as amino acid, peptide, steroid, sugar, and thymidine derivatives can be introduced to arenes with high yields and 100 % chiral retention. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Iridium(iii)-catalyzed regioselective direct arylation of sp(2) C-H bonds with diaryliodonium salts. (United States)

    Gao, Pan; Liu, Li; Shi, Zhuangzhi; Yuan, Yu


    A regioselective direct arylation of arenes and olefins at the ortho position is reported. The key to the high selectivity is the appropriate choice of diaryliodonium salts as the arylating reagent in the presence of a cationic iridium(iii) catalyst. The coordination of the metal with an oxygen atom or a nitrogen atom and subsequent C-H activation allows for direct arylation with coupling partners. This reaction proceeds under mild reaction conditions and with a high tolerance of various functional groups including many halide functional groups.

  9. Palladium-Catalyzed Enantioselective C-H Olefination of Diaryl Sulfoxides through Parallel Kinetic Resolution and Desymmetrization. (United States)

    Zhu, Yu-Chao; Li, Yan; Zhang, Bo-Chao; Zhang, Feng-Xu; Yang, Yi-Nuo; Wang, Xi-Sheng


    The first example of Pd II -catalyzed enantioselective C-H olefination with non-chiral or racemic sulfoxides as directing groups was developed. A variety of chiral diaryl sulfoxides were synthesized with high enantioselectivity (up to 99 %) through both desymmetrization and parallel kinetic resolution (PKR). This is the first report of Pd II -catalyzed enantioselective C(sp 2 )-H functionalization through PKR, and it represents a novel strategy to construct sulfur chiral centers. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Exclusive Aromatic vs Aliphatic C-H Bond Functionalization by Carbene Insertion with Gold-based Catalysts


    Rivilla de la Cruz, Iván; Gómez Emeterio, Bella Pilar; Romero Fructos-Vázquez, Manuel; Díaz Requejo, María Mar; Pérez Romero, Pedro José


    The direct functionalization of aromatic C-H bonds by carbene insertion from diazocompounds catalyzed by gold complexes with N-heterocyclic ligands is described. The reaction is completely selective toward the Csp2-H bonds, other Csp3-H bonds remaining unreacted. A study with a several NHC ligands in Au(I) and Au(III) complexes has been performed. A potential application in profen derivatives has also been developed DGI (CTQ2008-00042BQU and Consolider Ingenio 2010, Grant CSD2006-0003) and...

  11. Transformations of griseofulvin in strong acidic conditions--crystal structures of 2'-demethylgriseofulvin and dimerized griseofulvin. (United States)

    Leśniewska, Barbara; Jebors, Said; Coleman, Anthony W; Suwińska, Kinga


    The structure of griseofulvic acid, C16H15ClO6, at 100 K has orthorhombic (P2(1)2(1)2) symmetry. It is of interest with respect to biological activity. The structure displays intermolecular O-H...O, C-H...O hydrogen bonding as well as week C-H...pi and pi...pi interactions. In strong acidic conditions the griseofulvin undergoes dimerization. The structure of dimerized griseofulvin, C34H32C12O12 x C2H6O x H2O, at 100 K has monoclinic (P2(1)) symmetry. The molecule crystallized as a solvate with one ethanol and one water molecule. The dimeric molecules form intermolecular O-H...O hydrogen bonds to solvents molecules only but they interact via week C-H...O, C-H...pi, C-Cl...pi and pi...pi interactions with other dimerized molecules.

  12. Intrascleral outflow after deep sclerectomy with absorbable and non-absorbable implants in the rabbit eye


    Ka?u?ny, Jakub J.; Grzanka, Dariusz; Wi?niewska, Halina; Niewi?ska, Alicja; Ka?u?ny, Bart?omiej J.; Grzanka, Alina


    Summary Background The purpose of the study is an analysis of intrascleral drainage vessels formed in rabbits? eyes after non-penetrating deep sclerectomy (NPDS) with absorbable and non-absorbable implants, and comparison to eyes in which surgery was performed without implanted material. Material/Methods NPDS was carried out in 12 rabbits, with implantation of non-absorbable methacrylic hydrogel (N=10 eyes) or absorbable cross-linked sodium hyaluronate (N=6 eyes), or without any implant (N=8 ...

  13. Absorbencies of six different rodent beddings: commercially advertised absorbencies are potentially misleading. (United States)

    Burn, C C; Mason, G J


    Moisture absorbency is one of the most important characteristics of rodent beddings for controlling bacterial growth and ammonia production. However, bedding manufacturers rarely provide information on the absorbencies of available materials, and even when they do, absorption values are usually expressed per unit mass of bedding. Since beddings are usually placed into cages to reach a required depth rather than a particular mass, their volumetric absorbencies are far more relevant. This study therefore compared the saline absorbencies of sawdust, aspen woodchips, two virgin loose pulp beddings (Alpha-Dri and Omega-Dri), reclaimed wood pulp (Tek-Fresh), and corncob, calculated both by volume and by mass. Absorbency per unit volume correlated positively with bedding density, while absorbency per unit mass correlated negatively. Therefore, the relative absorbencies of the beddings were almost completely reversed depending on how absorbency was calculated. By volume, corncob was the most absorbent bedding, absorbing about twice as much saline as Tek-Fresh, the least absorbent bedding. Conversely, when calculated by mass, Tek-Fresh appeared to absorb almost three times as much saline as the corncob. Thus, in practical terms the most absorbent bedding here was corncob, followed by the loose pulp beddings; and this is generally supported by their relatively low ammonia production as seen in previous studies. Many factors other than absorbency determine whether a material is suitable as a rodent bedding, and they are briefly mentioned here. However, manufacturers should provide details of bedding absorbencies in terms of volume, in order to help predict the relative absorbencies of the beddings in practical situations.

  14. Absorbed radiation dose on LHC interconnects

    CERN Document Server

    Versaci, R; Vlachoudis, V; CERN. Geneva. ATS Department


    Here we present the results of our FLUKA simulations devoted to the evaluation of the peak dose absorbed by the busbar insulator in the LHC Interaction Region 7 interconnects. The peak dose absorbed by the cold magnet coils are also presented.

  15. Comments on liquid hydrogen absorbers for MICE

    Energy Technology Data Exchange (ETDEWEB)

    Green, Michael A.


    This report describes the heat transfer problems associatedwith a liquid hydrogen absorber for the MICE experiment. This reportdescribes a technique for modeling heat transfer from the outside world,to the abosrber case and in its vacuum vessel, to the hydrogen and theninto helium gas at 14 K. Also presented are the equation for freeconvection cooling of the liquid hydrogen in the absorber.

  16. Absorber transmissivities in 57Fe Moessbauer spectroscopy

    International Nuclear Information System (INIS)

    Ballet, O.


    Some useful relations are derived for the polarization dependent optical index of 57 Fe Moessbauer absorbers. Real rotation matrices are extensively used and, besides wave-direction dependence, their properties simplify also the treatment of texture and f-anisotropy. The derivation of absorber transmissivities from the optical index is discussed with a special emphasis on line overlapping. (Auth.)

  17. Metamaterial Resonant Absorbers for Terahertz Sensing (United States)


    process was completed in the NPS clean room for an Al/SiOx/Al metamaterial absorber . After fabrication, FTIR testing was employed to determine unlimited METAMATERIAL RESONANT ABSORBERS FOR TERAHERTZ SENSING by Eric A. Stinson December 2015 Thesis Advisor: Gamani Karunasiri...

  18. Collaborative Research: Nanopore Confinement of C-H-O Mixed Volatile Fluids Relevant to Subsurface Energy Systems

    Energy Technology Data Exchange (ETDEWEB)

    Grady, Brian P. [Univ. of Oklahoma, Norman, OK (United States)


    The scientific objective of this proposal was to obtain a fundamental atomic- to macro-scale understanding of the sorptivity, structure and dynamics of simple and complex hydrocarbon (HC) fluids at mineral surfaces or within nanoporous matrices over temperatures, pressures and compositions encountered in near-surface and shallow crustal environments. The research supported by this award was complementary to that conducted by the group of Prof. David cole at Ohio State University. The scope of the present award was to utilize molecular-level modeling to provide critically important insights into the interfacial properties of mineral-volatile systems, assist in the interpretation of experimental data and predict fluid behavior beyond the limits of current experimental capability. During the past three years the effort has focused primarily on the behavior of C-H volatiles including methane (CH4) and propane (C3H8), mixed-volatile systems including hydrocarbon - CO2 with and without H2O present. The long-range goal is to quantitatively link structure, dynamics and reactivity in complex mineral-/C-H-O systems from the atomic to the molecular to the macroscopic levels. The results are relevant to areas of growing importance such as gas shale, HC-bearing hydrothermal systems, and CO2 storage.

  19. Visible light-driven C-H activation and C-C coupling of methanol into ethylene glycol. (United States)

    Xie, Shunji; Shen, Zebin; Deng, Jiao; Guo, Pu; Zhang, Qinghong; Zhang, Haikun; Ma, Chao; Jiang, Zheng; Cheng, Jun; Deng, Dehui; Wang, Ye


    The development of new methods for the direct transformation of methanol into two or multi-carbon compounds via controlled carbon-carbon coupling is a highly attractive but challenging goal. Here, we report the first visible-light-driven dehydrogenative coupling of methanol into ethylene glycol, an important chemical currently produced from petroleum. Ethylene glycol is formed with 90% selectivity and high efficiency, together with hydrogen over a molybdenum disulfide nanofoam-modified cadmium sulfide nanorod catalyst. Mechanistic studies reveal a preferential activation of C-H bond instead of O-H bond in methanol by photoexcited holes on CdS via a concerted proton-electron transfer mechanism, forming a hydroxymethyl radical (⋅CH 2 OH) that can readily desorb from catalyst surfaces for subsequent coupling. This work not only offers an alternative nonpetroleum route for the synthesis of EG but also presents a unique visible-light-driven catalytic C-H activation with the hydroxyl group in the same molecule keeping intact.

  20. Liquid absorber experiments in ZED-2

    International Nuclear Information System (INIS)

    McDonnell, F.N.


    A set of liquid absorber experiments was performed in ZED-2 to provide data with which to test the adequacy of calculational methods for zone controller and refuelling studies associated with advanced reactor concepts. The absorber consisted of a full length aluminum tube, containing either i)H 2 O, ii)H 2 O + boron (2.5 mg/ml) or iii)H 2 O + boron (8.0 mg/ml). The tube was suspended vertically at interstitial or in-channel locations. A U-tube absorber was also simulated using two absorber tubes with appropriate spacers. Experiments were carried out at two different square lattice pitches, 22.86 and 27.94 cm. Measurements were made of the reactivity effects of the absorbers and, in some cases, of the detailed flux distribution near the perturbation. The results from one calculational method, the source-sink approach, were compared with the data from selected experiments. (author)

  1. Constructing multilayers with absorbing materials


    Larruquert, Juan Ignacio; Vidal-Dasilva, M.; García-Cortés, S.; Fernández Perea, Mónica; Méndez, José Antonio; Aznárez, José Antonio


    The strong absorption of materials in the extreme ultraviolet (EUV) above ~50 nm has precluded the development of efficient coatings. The development of novel coatings with improved EUV performance is presented. An extensive research was performed on the search and characterization of materials with moderate absorption, such as various lanthanides. Based on this research, novel multilayers based on Yb, Al, and SiO have been developed with a narrowband performance in the 50-92 nm range. Furthe...

  2. Metal–insulator–metal light absorber: a continuous structure

    International Nuclear Information System (INIS)

    Yan, M


    A type of light absorber made of continuous layers of metal and dielectric films is studied. The metal films can have thicknesses close to their skin depths in the wavelength range concerned, which allows for both light transmission and reflection. Resonances induced by multiple reflections in the structure, when combined with the inherent lossy nature of metals, result in strong absorption spectral features. An eigen-mode analysis is carried out for the plasmonic multilayer nanostructures which provides a generic understanding of the absorption features. Experimentally, the calculation is verified by a reflection measurement with a representative structure. Such an absorber is simple to fabricate. The highly efficient absorption characteristics can be potentially deployed for optical filter designs, sensors, accurate photothermal temperature control in a micro-environment and even for backscattering reduction of small particles, etc. (paper)

  3. PREFACE: Strongly correlated electron systems Strongly correlated electron systems (United States)

    Saxena, Siddharth S.; Littlewood, P. B.


    make use of 'small' electrons packed to the highest possible density. These are by definition 'strongly correlated'. For example: good photovoltaics must be efficient optical absorbers, which means that photons will generate tightly bound electron-hole pairs (excitons) that must then be ionised at a heterointerface and transported to contacts; efficient solid state refrigeration depends on substantial entropy changes in a unit cell, with large local electrical or magnetic moments; efficient lighting is in a real sense the inverse of photovoltaics; the limit of an efficient battery is a supercapacitor employing mixed valent ions; fuel cells and solar to fuel conversion require us to understand electrochemistry on the scale of a single atom; and we already know that the only prospect for effective high temperature superconductivity involves strongly correlated materials. Even novel IT technologies are now seen to have value not just for novel function but also for efficiency. While strongly correlated electron systems continue to excite researchers and the public alike due to the fundamental science issues involved, it seems increasingly likely that support for the science will be leveraged by its impact on energy and sustainability. Strongly correlated electron systems contents Strongly correlated electron systemsSiddharth S Saxena and P B Littlewood Magnetism, f-electron localization and superconductivity in 122-type heavy-fermion metalsF Steglich, J Arndt, O Stockert, S Friedemann, M Brando, C Klingner, C Krellner, C Geibel, S Wirth, S Kirchner and Q Si High energy pseudogap and its evolution with doping in Fe-based superconductors as revealed by optical spectroscopyN L Wang, W Z Hu, Z G Chen, R H Yuan, G Li, G F Chen and T Xiang Structural investigations on YbRh2Si2: from the atomic to the macroscopic length scaleS Wirth, S Ernst, R Cardoso-Gil, H Borrmann, S Seiro, C Krellner, C Geibel, S Kirchner, U Burkhardt, Y Grin and F Steglich Confinement of chiral magnetic

  4. Constrained Optimal Stochastic Control of Non-Linear Wave Energy Point Absorbers

    DEFF Research Database (Denmark)

    Sichani, Mahdi Teimouri; Chen, Jian-Bing; Kramer, Morten


    are enforced on the motion of the floater to prevent it from hitting the bottom of the sea or to make unacceptable jumps out of the water. The applied control law, which is of the feedback type with feedback from the displacement, velocity, and acceleration of the floater, contains two unprovided gain......The paper deals with the stochastic optimal control of a wave energy point absorber with strong nonlinear buoyancy forces using the reactive force from the electric generator on the absorber as control force. The considered point absorber has only one degree of freedom, heave motion, which is used...

  5. Thin films of hydrogenated amorphous carbon (a-C:H) obtained through chemical vapor deposition assisted by plasma; Peliculas delgadas de carbono amorfo hidrogenado (a-C:H) obtenidas mediante deposito quimico de vapores asistido por plasma

    Energy Technology Data Exchange (ETDEWEB)

    Mejia H, J.A.; Camps C, E.E.; Escobar A, L.; Romero H, S.; Chirino O, S. [ININ, 52045 Ocoyoacac, Estado de Mexico (Mexico); Muhl S, S. [IIM-UNAM, 04510 Mexico D.F. (Mexico)


    Films of hydrogenated amorphous carbon (a-C:H) were deposited using one source of microwave plasma with magnetic field (type ECR), using mixtures of H{sub 2}/CH{sub 4} in relationship of 80/20 and 95/05 as precursory gases, with work pressures of 4X10{sup -4} to 6x10{sup -4} Torr and an incident power of the discharge of microwaves with a constant value of 400 W. It was analyzed the influence among the properties of the films, as the deposit rate, the composition and the bonding types, and the deposit conditions, such as the flow rates of the precursory gases and the polarization voltage of the sample holders. (Author)

  6. Compound A and carbon monoxide production from sevoflurane and seven different types of carbon dioxide absorbent in a patient model

    NARCIS (Netherlands)

    Keijzer, C.; Perez, R. S. G. M.; de Lange, J. J.


    BACKGROUND: The degradation of sevoflurane can lead to the production of compound A (CA) and carbon monoxide (CO) and an increase in temperature of the absorbent. CA is known to be nephrotoxic in rats. These reactions depend on the strong base and water contents of the carbon dioxide absorbent used.

  7. Method of absorbing UF6 from gaseous mixtures in alkamine absorbents

    International Nuclear Information System (INIS)

    Lafferty, R.H.; Smiley, S.H.; Radimer, K.J.


    A method is described for recovering UF 6 from gaseous mixtures by absorption in a liquid. The liquid absorbent must have a relatively low viscosity and at least one component of the absorbent is an alkamine having less than 3 carbon atoms bonded to the amino nitrogen, less than 2 of the carbon atoms other than those bonded to the amino nitrogen are free of the hydroxy radical and precipitate the absorbed uranium from the absorbent. At least one component of the absorbent is chosen from the group consisting of ethanolamine, diethanolamine, and 3-methyl-3-amino-propane-diol-1,2

  8. In-line phase-contrast imaging for strong absorbing objects

    Energy Technology Data Exchange (ETDEWEB)

    De Caro, Liberato; Giannini, Cinzia [Istituto di Cristallografia, Consiglio Nazionale delle Ricerche (IC-CNR), via Amendola 122/O, I-70125 Bari (Italy); Cedola, Alessia; Bukreeva, Inna; Lagomarsino, Stefano [Istituto di Fotonica e Nanotecnologie, Consiglio Nazionale delle Ricerche (IFN-CNR), via Cinto Romano 42, I-00156 Roma (Italy)


    Phase-contrast imaging is one of the most important emerging x-ray imaging techniques. In this work we analyse, from a theoretical point of view, the in-line phase-contrast image formation under general assumptions. The approach is based on wave-optical theory (Fresnel/Kirchoff diffraction integrals) and on the formalism of the mutual coherence function for the evolution of the coherence wavefield properties. Our theoretical model can be applied to phase-contrast imaging realized both by using highly coherent synchrotron radiation and micro-focus x-ray laboratory sources. Thus, the model is suitable for widespread applications, ranging from material science to medical imaging of human body parts. However, it cannot be applied to polychromatic sources, although the validity of the model does not require particularly demanding characteristics of monochromaticity. In addition, for moderate phase gradients, a useful analytical formula of the phase-contrast visibility is derived, based on the a priori knowledge of source size and distance, pixel detector size, defocus distance, material/tissue dielectric susceptibility and characteristic scales of transversal and longitudinal non-uniformities of the material/tissue dielectric susceptibility. Comparisons both with experimental results published by other authors and with simulations based on a Fourier optics approach have been reported, to confirm the validity of the proposed analytical formula.

  9. High Resolution Rovibrational Spectroscopy of Jet-Cooled Phenyl Radical: the ν_{19} Out-Of Symmetric C-H Stretch (United States)

    Buckingham, Grant T.; Chang, Chih-Hsuan; Nesbitt, David J.


    Phenyl radical has been studied via sub-Doppler infrared spectroscopy in a slit supersonic discharge expansion source, with assignments for the highest frequency b_{2} out-of-phase C-H symmetric stretch vibration (ν_{19}) unambiguously confirmed by ≤ 6 MHz (0.0002 cm^{-1}) agreement with microwave ground state combination differences of McMahon et al. [Astrophys. J. 590, L61-64 (2003)]. Least squares analysis of > 100 resolved rovibrational peaks in the sub-Doppler spectrum to a Watson Hamiltonian yields precision exited-state rotational constants and a vibrational band origin (ν_{0} = 3071.8915(4) cm^{-1}) consistent with a surprisingly small red-shift (0.9 cm^{-1}) with respect to Ar matrix isolation studies of Ellison and coworkers [J. Am. Chem. Soc. 123, 1977 (2001)]. Nuclear spin weights and inertial defects confirm the vibrationally averaged planarity and ^{2}A_{1} rovibronic symmetry of phenyl radical, with analysis of the rotational constants consistent with a modest C_{2v} distortion of the carbon backbone frame due to partial sp rehybridization of the σ C radical-center. Most importantly, despite the number of atoms (N = 11) and vibrational modes (3N-6 = 27), phenyl radical exhibits a remarkably clean jet cooled high resolution IR spectrum that shows no evidence of intramolecular vibrational relaxation (IVR) phenomena such as local or non-local perturbations due to strongly coupled nearby dark states. This provides strong support for the feasibility of high resolution infrared spectroscopy in other cyclic aromatic hydrocarbon radical systems.

  10. Strongly Correlated Topological Insulators (United States)


    Strongly Correlated Topological Insulators In the past year, the grant was used for work in the field of topological phases, with emphasis on finding...surface of topological insulators. In the past 3 years, we have started a new direction, that of fractional topological insulators. These are which a topologically nontrivial quasi-flat band is fractionally filled and then subject to strong interactions. The views, opinions and/or

  11. Vibration analysis on compact car shock absorber (United States)

    Tan, W. H.; Cheah, J. X.; Lam, C. K.; Lim, E. A.; Chuah, H. G.; Khor, C. Y.


    Shock absorber is a part of the suspension system which provides comfort experience while driving. Resonance, a phenomenon where forced frequency is coinciding with the natural frequency has significant effect on the shock absorber itself. Thus, in this study, natural frequencies of the shock absorber in a 2 degree-of-freedom system were investigated using Wolfram Mathematica 11, CATIA, and ANSYS. Both theoretical and simulation study how will the resonance affect the car shock absorber. The parametric study on the performance of shock absorber also had been conducted. It is found that the failure tends to occur on coil sprung of the shock absorber before the body of the shock absorber is fail. From mathematical modelling, it can also be seen that higher vibration level occurred on un-sprung mass compare to spring mass. This is due to the weight of sprung mass which could stabilize as compared with the weight of un-sprung mass. Besides that, two natural frequencies had been obtained which are 1.0 Hz and 9.1 Hz for sprung mass and un-sprung mass respectively where the acceleration is recorded as maximum. In conclusion, ANSYS can be used to validate with theoretical results with complete model in order to match with mathematical modelling.

  12. Sequential meta-C-H olefination of synthetically versatile benzyl silanes: effective synthesis of meta-olefinated toluene, benzaldehyde and benzyl alcohols. (United States)

    Patra, Tuhin; Watile, Rahul; Agasti, Soumitra; Naveen, Togati; Maiti, Debabrata


    Tremendous progress has been made towards ortho-selective C-H functionalization in the last three decades. However, the activation of distal C-H bonds and their functionalization has remained fairly underdeveloped. Herein, we report sequential meta-C-H functionalization by performing selective mono-olefination and bis-olefination with late stage modification of the C-Si as well as Si-O bonds. Temporary silyl connection was found to be advantageous due to its easy installation, easy removal and wide synthetic diversification.

  13. Thiocarbamate-Directed Tandem Olefination-Intramolecular Sulfuration of Two Ortho C-H Bonds: Application to Synthesis of a COX-2 Inhibitor. (United States)

    Li, Wendong; Zhao, Yingwei; Mai, Shaoyu; Song, Qiuling


    A palladium-catalyzed dual ortho C-H bond activation of aryl thiocarbamates is developed. This tandem reaction initiates by thiocarbamate-directed ortho C-H palladation, which leads to favorable olefin insertion rather than reductive elimination. The oxidative Heck reaction followed by another C-H activation and sulfuration affords the dual-functionalized products. This reaction provides a concise route to the S,O,C multisubstituted benzene skeleton which could be successfully applied for the synthesis of a COX-2 inhibitor.

  14. Strong Cosmic Censorship (United States)

    Isenberg, James


    The Hawking-Penrose theorems tell us that solutions of Einstein's equations are generally singular, in the sense of the incompleteness of causal geodesics (the paths of physical observers). These singularities might be marked by the blowup of curvature and therefore crushing tidal forces, or by the breakdown of physical determinism. Penrose has conjectured (in his `Strong Cosmic Censorship Conjecture`) that it is generically unbounded curvature that causes singularities, rather than causal breakdown. The verification that ``AVTD behavior'' (marked by the domination of time derivatives over space derivatives) is generically present in a family of solutions has proven to be a useful tool for studying model versions of Strong Cosmic Censorship in that family. I discuss some of the history of Strong Cosmic Censorship, and then discuss what is known about AVTD behavior and Strong Cosmic Censorship in families of solutions defined by varying degrees of isometry, and discuss recent results which we believe will extend this knowledge and provide new support for Strong Cosmic Censorship. I also comment on some of the recent work on ``Weak Null Singularities'', and how this relates to Strong Cosmic Censorship.

  15. C-H activation with elemental sulfur: synthesis of cyclic thioureas from formaldehyde aminals and S8. (United States)

    Denk, M K; Gupta, S; Brownie, J; Tajammul, S; Lough, A J


    The C-H activation of cyclic formaldehyde aminals LCH2 (L = RN-CH2CH2CH2-NR and RNCH2CH2-NR, R = Me, Et, iPr, tBu, or Ph) with S8 proceeds at unusually low temperatures (TS8 was investigated. 1,3-Dithiolane is cleanly converted into 1,3-dithiolane-2-thione (S8, 14 d, 190 degrees C) and resembles the cyclic formaldehyde aminals in this respect. 1,3-Dioxolane (L = OCH2CH2O) is completely inert towards sulfur even under forceful reaction conditions (190 degrees C, 14 d). The formation of thioureas from aminals was investigated at the CBS-4 and B3LYP/6-31G(d) levels of theory.

  16. Fields, particles and analyticity: recent results or 30 goldberg (ER) variations on B.A.C.H

    International Nuclear Information System (INIS)

    Bros, J.


    As it is known, Axiomatic Field Theory (A) implies double analyticity of the η-point functions in space-time and energy-momentum Complex Variables (C), with various interconnections by Fourier-Laplace analysis. When the latter is replaced by. Harmonic Analysis (H) on spheres and hyperboloids, a new kind of double analyticity results from (A) (i.e. from locality, spectral condition, temperateness and invariance): complex angular momentum is thereby introduced (a missing chapter in (A)). Exploitation of Asymptotic Completeness via Bethe-Salpeter-type equations (B) leads to new developments of the previous theme on (A, C, H) (complex angular momentum) and of other themes on (A,C) (crossing, Haag-Swieca property etc...). Various aspects of (A) + (B) have been implemented in Constructive Field Theory (composite spectrum, asymptotic properties etc...) by a combination of specific techniques and of model-independent methods

  17. Thin films of hydrogenated amorphous carbon (a-C:H) obtained through chemical vapor deposition assisted by plasma

    International Nuclear Information System (INIS)

    Mejia H, J.A.; Camps C, E.E.; Escobar A, L.; Romero H, S.; Chirino O, S.; Muhl S, S.


    Films of hydrogenated amorphous carbon (a-C:H) were deposited using one source of microwave plasma with magnetic field (type ECR), using mixtures of H 2 /CH 4 in relationship of 80/20 and 95/05 as precursory gases, with work pressures of 4X10 -4 to 6x10 -4 Torr and an incident power of the discharge of microwaves with a constant value of 400 W. It was analyzed the influence among the properties of the films, as the deposit rate, the composition and the bonding types, and the deposit conditions, such as the flow rates of the precursory gases and the polarization voltage of the sample holders. (Author)

  18. Activation of the C-H bond in benzene in the presence of vanadium and titanium complexes

    International Nuclear Information System (INIS)

    Grigoryan, Eh.A.; D'yachkovskij, F.S.; Zhuk, S.Ya.; Papoyan, A.T.; Vyshinskaya, L.I.


    A multiple deuterium hydrogen exchange between benzene and deuterated ethylene and methanol in the presence of bis-cyclopentadienylvanadium (CPsub(d)V) and deuterium is found. The reaction is carried out in glass ampules at the temperature of 70 deg C pressure of 0.3-40.0 atm and CP 2 V catalyst concentrations of 0.007-0.035 mol/l during 80-100 hrs under conditions of constant mixing. It is shown that deuterium hydrogen exchange takes place between benzene and deuterium molecules, in the presence of V(2). The deuterium hydrogen exchange under experimental conditions is only possible as a result of activation of the C-H bond in benzene molecules in V coordination sphere and is considerably accelerated in the presence of ethylene

  19. Electronic and Steric Tuning of a Prototypical Piano Stool Complex: Rh(III) Catalysis for C-H Functionalization. (United States)

    Piou, Tiffany; Rovis, Tomislav


    The history of transition metal catalysis is heavily steeped in ligand design, clearly demonstrating the importance of this approach. The intimate relationship between metal and ligand can profoundly affect the outcome of a reaction, often impacting selectivity, physical properties, and the lifetime of a catalyst. Importantly, this metal-ligand relationship can provide near limitless opportunities for reaction discovery. Over the past several years, transition-metal-catalyzed C-H bond functionalization reactions have been established as a critical foundation in organic chemistry that provides new bond forming strategies. Among the d-block elements, palladium is arguably one of the most popular metals to accomplish such transformations. One possible explanation for this achievement could be the broad set of phosphine and amine based ligands available in the chemist's toolbox compatible with palladium. In parallel, other metals have been investigated for C-H bond functionalization. Among them, pentamethylcyclopentadienyl (Cp*) Rh(III) complexes have emerged as a powerful mode of catalysis for such transformations providing a broad spectrum of reactivity. This approach possesses the advantage of often very low catalyst loading, and reactions are typically performed under mild conditions allowing broad functional group tolerance. Cp*Rh(III) is considered as a privileged catalyst and a plethora of reactions involving a C-H bond cleavage event have been developed. The search for alternative cyclopentadienyl based ligands has been eclipsed by the tremendous effort devoted to exploring the considerable scope of reactions catalyzed by Cp*Rh(III) complexes, despite the potential of this strategy for enabling reactivity. Thus, ligand modification efforts in Rh(III) catalysis have been an exception and research directed toward new rhodium catalysts has been sparse. Recently, chiral cyclopentadienyl ligands have appeared allowing enantioselective Rh(III)-catalyzed C-H

  20. Activation of C-H bond in methane by Pd atom from the bonding evolution theory perspective. (United States)

    Nizovtsev, Anton S


    We report detailed study focused on the electron density redistribution during the simple oxidative addition reaction being the crucial stage of various catalytic processes. The bonding evolution theory based on the electron localization function and Thom's catastrophe theory shows that activation of methane's C-H bond by Pd atom consist of six elementary steps. The important feature revealed is the pronounced reorganization of Pd's outer core maxima corresponding to N-shell electrons of metal. Electronic rearrangements identified in this model reaction are likely to be the case in the more complex reactions of the same type involving transition metal compounds and, in principle, can be observed by modern ultrafast spectroscopy and diffraction techniques. Copyright © 2013 Wiley Periodicals, Inc.

  1. Palladium-Catalyzed Zinc-Amide-Mediated C-H Arylation of Fluoroarenes and Heteroarenes with Aryl Sulfides. (United States)

    Otsuka, Shinya; Yorimitsu, Hideki; Osuka, Atsuhiro


    C-H arylation of polyfluoroarenes and heteroarenes with aryl sulfides proceeds smoothly with the aid of a palladium-N-heterocyclic carbene catalyst. A bulky zinc amide, TMPZnCl⋅LiCl, plays a key role as an effective base to generate the corresponding arylzinc species in situ. This arylation protocol is practically much easier to perform than our previous method, which necessitates preparation of the arylzinc reagents in advance from the corresponding aryl halides. Aryl sulfides that are prepared through sulfur-specific reactions, such as SN Ar sulfanylation and extended Pummerer reactions, undergo this direct arylation, offering interesting transformations that are otherwise difficult to achieve with conventional halogen-based organic synthesis. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Regioselective C-H hydroxylation of omeprazole sulfide by Bacillus megaterium CYP102A1 to produce a human metabolite. (United States)

    Jang, Hyun-Hee; Ryu, Sang-Hoon; Le, Thien-Kim; Doan, Tiep Thi My; Nguyen, Thi Huong Ha; Park, Ki Deok; Yim, Da-Eun; Kim, Dong-Hyun; Kang, Choong-Kyung; Ahn, Taeho; Kang, Hyung-Sik; Yun, Chul-Ho


    To find a simple enzymatic strategy for the efficient synthesis of the expensive 5'-hydroxyomeprazole sulfide, a recently identified minor human metabolite, from omeprazole sulfide, which is an inexpensive substrate. The practical synthetic strategy for the 5'-OH omeprazole sulfide was accomplished with a set of highly active CYP102A1 mutants, which were obtained by blue colony screening from CYP102A1 libraries with a high conversion yield. The mutant and even the wild-type enzyme of CYP102A1 catalyzed the high regioselective (98 %) C-H hydroxylation of omeprazole sulfide to 5'-OH omeprazole sulfide with a high conversion yield (85-90 %). A highly efficient synthesis of 5'-OH omeprazole sulfide was developed using CYP102A1 from Bacillus megaterium as a biocatalyst.

  3. Mechanistic Insights of a Selective C-H Alkylation of Alkenes by a Ru-based Catalyst and Alcohols

    KAUST Repository

    Poater, Albert


    Density functional theory calculations have been used to investigate the reaction mechanism for [(C6H6)(PCy3)(CO) RuH](+) (1; Cy, cyclohexyl) mediated alkylation of indene substrate using ethanol as solvent. According to Yi et al. [ Science 2011, 333, 1613] the plausible reaction mechanism involves a cationic Rualkenyl species, which is initially formed from 1 with two equivalents of the olefin substrate via the vinylic C-H activation and an alkane elimination step. Once the active catalytic species is achieved the oxidative addition step is faced. The latter step together with the next C-C bond formation might display the upper barrier of the catalytic cycle. Having these experimental insights at hand, we investigated in detail the whole reaction pathway using several computational DFT approaches including alternative pathways, higher in energy.

  4. Microwave-assisted extraction and a new determination method for total steroid saponins from Dioscorea zingiberensis C.H. Wright. (United States)

    Ren, Yao; Chen, Yu; Hu, Bohan; Wu, Hui; Lai, Furao; Li, Xiaofeng


    An efficient microwave-assisted extraction (MAE) technique was applied to isolate total steroid saponins from Dioscorea zingiberensis C.H. Wright (DZW). The optimal extracting conditions were established as 75% ethanol as solvent, ratio of solid/liquid 1:20 (g/ml), temperature 75 °C, irradiation power 600 W and three extraction cycles of 6 min each. Scanning electron microscopy (SEM) images of DZW processed by four different extractions provided visual evidence of the disruption effect on DZW. Diosgenin was quantified by HPLC and examined further by LC-ESI/MS after acid hydrolysis. Total steroid saponins were calculated using diosgenin from total steroid saponins. The MAE procedure was optimized, validated and compared with other conventional extraction processes. This report provides a convenient technology for the extraction and quantification of total saponins of DZW combining MAE with HPLC and LC-ESI/MS for the first time. Copyright © 2015 Elsevier Inc. All rights reserved.

  5. Graphene and Graphene Metamaterials for Terahertz Absorbers

    DEFF Research Database (Denmark)

    Andryieuski, Andrei; Pizzocchero, Filippo; Booth, Tim


    Graphene, due to the possibility to tune its conductivity, is the promising material for a range of the terahertz (THz) applications, such as tunable reflectors, absorbers, modulators, filters and polarization converters. Subwavelength structuring of graphene in order to form metamaterials allows...... for even more control over the THz waves. In this poster presentation I will show an elegant way to describe the graphene metamaterials and the design of graphene based absorbers. I will also present our recent experimental results on the graphene absorbers characterization....

  6. Chemistry of Titan's Aerosols : Correlation of The C/n &C/h Ratios To Pressure and Temperature (United States)

    Bernard, J.-M.; Coll, P.; Raulin, F.

    The gas present in Titan's atmosphere are forming organics aerosols under action of the solar radiations and of electrons from Saturn's magnetosphere. Many experimental simulations are been realised by irradiating N2/CH4 gas mixtures with different en- ergy sources in order to reproduce the chemistry of gas and particulate phases (Thomp- son et al, 1991; Mc Donald et al, 1994; de Vanssay et al, 1995; McKay, 1996; Coll et al, 1997, 1998a,b; and Refs. included). Until very recently, only one organics re- mains detected in Titan but not in laboratory simulation : C4N2. A full program of experimental research has been developed at LISA, which was able to provide a com- plete identification of a wide range of compounds, proposed to be present in Titan's atmosphere, including C4N2. The composition of aerosol on Titan is not known, due to its complexity. Especially its building molecules are difficult to identify. Only functional groups of analogues have been determined using spectroscopy and pyrolysis. However this chemical composi- tion is a key parameter for Cassini-Huygens experiments and atmospheric modeling : even the optical properties of aerosols are related to C/N and C/H ratios. We will present the results of the variation of C/N and C/H ratios according to the temperature and the pressure in Titan's atmosphere simulations. This data will allow to constraint photochemical models, in order for them to be more realistic. Then the comprehension of the mechanism of aerosols formation on Titan as function of altitude will be easier.

  7. Spacesuit Evaporator-Absorber-Radiator (SEAR) (United States)

    National Aeronautics and Space Administration — The primary goal is to build and test a rigid Lithium Chloride Absorber Radiator (LCAR) coupon based on honeycomb geometry that would be applicable for EVA and...

  8. Absorbed dose uncertainty estimation for proton therapy

    Directory of Open Access Journals (Sweden)

    Spasić-Jokić Vesna


    Full Text Available Successful radiotherapy treatment depends on the absorbed dose evaluation and the possibility to define metrological characteristics of the therapy beam. Radiotherapy requires tumor dose delivery with expanded uncertainty less than ±5 %. It is particularly important to reduce uncertainty during therapy beam calibration as well as to apply all necessary ionization chamber correction factors. Absorbed dose to water was determined using ionometric method. Calibration was performed in reference cobalt beam. Combined standard uncertainty of the calculated absorbed dose to water in 65 MeV proton beam was ±1.97% while the obtained expanded uncertainty of absorbed dose for the same beam quality was ±5.02%. The uncertainty estimation method has been developed within the project TESLA.

  9. Energy absorber uses expanded coiled tube (United States)

    Johnson, E. F.


    Mechanical shock mitigating device, based on working material to its failure point, absorbs mechanical energy by bending or twisting tubing. It functions under axial or tangential loading, has no rebound, is area independent, and is easy and inexpensive to build.

  10. Space Compatible Radar Absorbing Materials Project (United States)

    National Aeronautics and Space Administration — This SBIR Phase 1 project shall investigate novel radar absorbing materials (RAM) for use in space or simulated space environments. These materials are lightweight...

  11. Quantitative neutron radiography using neutron absorbing honeycomb

    International Nuclear Information System (INIS)

    Tamaki, Masayoshi; Oda, Masahiro; Takahashi, Kenji; Ohkubo, Kohei; Tasaka, Kanji; Tsuruno, Akira; Matsubayashi, Masahito.


    This investigation concerns quantitative neutron radiography and computed tomography by using a neutron absorbing honeycomb collimator. By setting the neutron absorbing honeycomb collimator between object and imaging system, neutrons scattered in the object were absorbed by the honeycomb material and eliminated before coming to the imaging system, but the neutrons which were transmitted the object without interaction could reach the imaging system. The image by purely transmitted neutrons gives the quantitative information. Two honeycombs were prepared with coating of boron nitride and gadolinium oxide and evaluated for the quantitative application. The relation between the neutron total cross section and the attenuation coefficient confirmed that they were in a fairly good agreement. Application to quantitative computed tomography was also successfully conducted. The new neutron radiography method using the neutron-absorbing honeycomb collimator for the elimination of the scattered neutrons improved remarkably the quantitativeness of the neutron radiography and computed tomography. (author)

  12. An ultra-broadband multilayered graphene absorber

    KAUST Repository

    Amin, Muhammad


    An ultra-broadband multilayered graphene absorber operating at terahertz (THz) frequencies is proposed. The absorber design makes use of three mechanisms: (i) The graphene layers are asymmetrically patterned to support higher order surface plasmon modes that destructively interfere with the dipolar mode and generate electromagnetically induced absorption. (ii) The patterned graphene layers biased at different gate voltages backedup with dielectric substrates are stacked on top of each other. The resulting absorber is polarization dependent but has an ultra-broadband of operation. (iii) Graphene\\'s damping factor is increased by lowering its electron mobility to 1000cm 2=Vs. Indeed, numerical experiments demonstrate that with only three layers, bandwidth of 90% absorption can be extended upto 7THz, which is drastically larger than only few THz of bandwidth that can be achieved with existing metallic/graphene absorbers. © 2013 Optical Society of America.

  13. Optically Modulated Multiband Terahertz Perfect Absorber

    DEFF Research Database (Denmark)

    Seren, Huseyin R.; Keiser, George R.; Cao, Lingyue


    response of resonant metamaterials continues to be a challengingendeavor. Resonant perfect absorbers have flourished as one of the mostpromising metamaterial devices with applications ranging from power har-vesting to terahertz imaging. Here, an optically modulated resonant perfectabsorber is presented...

  14. Strong Arcwise Connectedness


    Espinoza, Benjamin; Gartside, Paul; Kovan-Bakan, Merve; Mamatelashvili, Ana


    A space is `n-strong arc connected' (n-sac) if for any n points in the space there is an arc in the space visiting them in order. A space is omega-strong arc connected (omega-sac) if it is n-sac for all n. We study these properties in finite graphs, regular continua, and rational continua. There are no 4-sac graphs, but there are 3-sac graphs and graphs which are 2-sac but not 3-sac. For every n there is an n-sac regular continuum, but no regular continuum is omega-sac. There is an omega-sac ...

  15. Abortion: Strong's counterexamples fail

    DEFF Research Database (Denmark)

    Di Nucci, Ezio


    This paper shows that the counterexamples proposed by Strong in 2008 in the Journal of Medical Ethics to Marquis's argument against abortion fail. Strong's basic idea is that there are cases--for example, terminally ill patients--where killing an adult human being is prima facie seriously morally......'s scenarios have some valuable future or admitted that killing them is not seriously morally wrong. Finally, if "valuable future" is interpreted as referring to objective standards, one ends up with implausible and unpalatable moral claims....

  16. Actual behaviour of a ball vibration absorber

    Czech Academy of Sciences Publication Activity Database

    Pirner, Miroš


    Roč. 90, č. 8 (2002), s. 987-1005 ISSN 0167-6105 R&D Projects: GA ČR(CZ) GV103/96/K034 Institutional support: RVO:68378297 Keywords : TV towers * wind-excited vibrations * vibration absorbers * pendulum absorber Subject RIV: JM - Building Engineering Impact factor: 0.513, year: 2002

  17. Multilayer Radar Absorbing Non-Woven Material (United States)

    Dedov, A. V.; Nazarov, V. G.


    We study the electrical properties of multilayer radar absorbing materials obtained by adding nonwoven sheets of dielectric fibers with an intermediate layer of electrically conductive carbon fibers. Multilayer materials that absorb electromagnetic radiation in a wide frequency range are obtained by varying the content of the carbon fibers. The carbon-fiber content dependent mechanism of absorption of electromagnetic radiation by sheets and multilayer materials is considered.

  18. A Wedge Absorber Experiment at MICE

    Energy Technology Data Exchange (ETDEWEB)

    Neuffer, David [Fermilab; Mohayai, Tanaz [IIT, Chicago; Rogers, Chris [Rutherford; Snopok, Pavel [IIT, Chicago; Summers, Don [Mississippi U.


    Emittance exchange mediated by wedge absorbers is required for longitudinal ionization cooling and for final transverse emittance minimization for a muon collider. A wedge absorber within the MICE beam line could serve as a demonstration of the type of emittance exchange needed for 6-D cooling, including the configurations needed for muon colliders, as well as configurations for low-energy muon sources. Parameters for this test are explored in simulation and possible experimental configurations with simulated results are presented.

  19. Energy-Absorbing Passenger Seat for Aircraft (United States)

    Eichelberger, C. P.; Alfaro-Bou, E.; Fasanella, E. L.


    Development of energy-absorbing passenger seat, designed to minimize injury in commercial-aircraft crash, part of joint FAA/NASA controlledimpact flight test of transport-category commercial aircraft. Modified seat mechanism collapses under heavy load to absorb impact energy and thereby protect passenger. Results of simulation tests indicate probability of passenger survival high. Proposed seat mechanism mitigates passenger injuries by reducing impact forces in crash.

  20. Semiconductor saturable absorbers for ultrafast THz signals

    DEFF Research Database (Denmark)

    Hoffmann, Matthias C.; Turchinovich, Dmitry

    We demonstrate saturable absorber behavior of n-type semiconductors in the THz frequency range using nonlinear THz spectroscopy. Further, we observe THz pulse shortening and increase of the group refractive index at high field strengths.......We demonstrate saturable absorber behavior of n-type semiconductors in the THz frequency range using nonlinear THz spectroscopy. Further, we observe THz pulse shortening and increase of the group refractive index at high field strengths....

  1. Phase Space Exchange in Thick Wedge Absorbers

    Energy Technology Data Exchange (ETDEWEB)

    Neuffer, David [Fermi National Accelerator Lab. (FNAL), Batavia, IL (United States)


    The problem of phase space exchange in wedge absorbers with ionization cooling is discussed. The wedge absorber exchanges transverse and longitudinal phase space by introducing a position-dependent energy loss. In this paper we note that the wedges used with ionization cooling are relatively thick, so that single wedges cause relatively large changes in beam phase space. Calculation methods adapted to such “thick wedge” cases are presented, and beam phase-space transformations through such wedges are discussed.

  2. Comprehensive Mechanistic Insight into Cooperative Lewis Acid/Cp*CoIII-Catalyzed C-H/N-H Activation for the Synthesis of Isoquinolin-3-ones. (United States)

    Wang, Qiong; Huang, Fang; Jiang, Langhuan; Zhang, Chuanxue; Sun, Chuanzhi; Liu, Jianbiao; Chen, Dezhan


    The mechanism of B(C 6 F 5 ) 3 promoted Cp*Co III -catalyzed C-H functionalization was investigated in detail employing density functional theory (DFT). The formation free energy of every possible species in the multicomponent complex system was explored and the optimal active catalyst was screened out. The results uncover the role of B(C 6 F 5 ) 3 played in forming active catalyst is from the coordination with OAc - , but not from the formation of [I(C 6 F 5 ) 3 B] - , and no acceleration effect is found in C-H activation as well as the formation of Co III -carbene intermediate. Moreover, present theoretical results elucidate the Cp*Co III -catalyzed C-H activation is mediated by imine N-coordination other than general proposed the sequence of N-deprotonation directed C-H activation. The metal-controlled C-H/N-H selectivity was then elucidated by insighting into [Cp*Co III OAc] + /[Cp*Rh III OAc] + -catalyzed C-H and N-H activations, respectively.

  3. A strong comeback

    International Nuclear Information System (INIS)

    Marier, D.


    This article presents the results of a financial rankings survey which show a strong economic activity in the independent energy industry. The topics of the article include advisor turnover, overseas banks, and the increase in public offerings. The article identifies the top project finance investors for new projects and restructurings and rankings for lenders

  4. Spectral radiation balance of absorbing aerosols over clouds (United States)

    Stammes, Piet; de Graaf, Martin; Deneke, Hartwig


    Absorption by aerosols, like smoke and desert dust, may lead to strong atmospheric warming, surface cooling, and cloud dynamical responses. Therefore, detection of absorbing aerosols and assessment of their radiative effects is important. However, absorbing aerosols are difficult to detect, especially in cloudy scenes. Here we use a satellite detection technique which can be used to determine the spectral absorption effects of smoke aerosols over clouds, using the fact that aerosols have a much stronger effect at UV and visible wavelengths than at longer wavelengths. We also analyse the shortwave radiative balance of absorbing aerosols over clouds. We have developed a technique of measuring aerosols from their absorption effect using multi-spectral satellite data (De Graaf et al., JGR, 2012). Using a wide spectral range, from the UV (300-400 nm) up to the shortwave (SW) IR (1000-1750 nm), it is possible to distinguish the absorption by aerosols from the scattering by clouds. No microphysical assumptions are needed for the aerosols, except that their absorption must vanish at long wavelengths. With this method, called the Differential Aerosol Absorption (DAA) technique, which was applied to SCIAMACHY satellite data, we measured the direct radiative effect of absorbing biomass burning aerosols over clouds in the South-East Atlantic. We measured instantaneous direct radiative effects by the aerosols of the order of 100 W/m2 at top-of-atmosphere. The spectral radiation balance at both top-of-atmosphere and surface is needed to estimate the amount of absorption inside the aerosol layer. We therefore perform a simulation study, using accurate spectral RT modelling, in which we compute the profile of absorption in the aerosol layer. We find that the atmospheric absorption characteristics cannot be measured only from satellite by using reflected light, also the transmission at the surface has to be measured. Therefore, field campaigns are needed in addition to satellite

  5. Strong Electroweak Symmetry Breaking

    CERN Document Server

    Grinstein, Benjamin


    Models of spontaneous breaking of electroweak symmetry by a strong interaction do not have fine tuning/hierarchy problem. They are conceptually elegant and use the only mechanism of spontaneous breaking of a gauge symmetry that is known to occur in nature. The simplest model, minimal technicolor with extended technicolor interactions, is appealing because one can calculate by scaling up from QCD. But it is ruled out on many counts: inappropriately low quark and lepton masses (or excessive FCNC), bad electroweak data fits, light scalar and vector states, etc. However, nature may not choose the minimal model and then we are stuck: except possibly through lattice simulations, we are unable to compute and test the models. In the LHC era it therefore makes sense to abandon specific models (of strong EW breaking) and concentrate on generic features that may indicate discovery. The Technicolor Straw Man is not a model but a parametrized search strategy inspired by a remarkable generic feature of walking technicolor,...

  6. Method of absorbance correction in a spectroscopic heating value sensor (United States)

    Saveliev, Alexei; Jangale, Vilas Vyankatrao; Zelepouga, Sergeui; Pratapas, John


    A method and apparatus for absorbance correction in a spectroscopic heating value sensor in which a reference light intensity measurement is made on a non-absorbing reference fluid, a light intensity measurement is made on a sample fluid, and a measured light absorbance of the sample fluid is determined. A corrective light intensity measurement at a non-absorbing wavelength of the sample fluid is made on the sample fluid from which an absorbance correction factor is determined. The absorbance correction factor is then applied to the measured light absorbance of the sample fluid to arrive at a true or accurate absorbance for the sample fluid.

  7. Plasmons in strong superconductors

    International Nuclear Information System (INIS)

    Baldo, M.; Ducoin, C.


    We present a study of the possible plasmon excitations that can occur in systems where strong superconductivity is present. In these systems the plasmon energy is comparable to or smaller than the pairing gap. As a prototype of these systems we consider the proton component of Neutron Star matter just below the crust when electron screening is not taken into account. For the realistic case we consider in detail the different aspects of the elementary excitations when the proton, electron components are considered within the Random-Phase Approximation generalized to the superfluid case, while the influence of the neutron component is considered only at qualitative level. Electron screening plays a major role in modifying the proton spectrum and spectral function. At the same time the electron plasmon is strongly modified and damped by the indirect coupling with the superfluid proton component, even at moderately low values of the gap. The excitation spectrum shows the interplay of the different components and their relevance for each excitation modes. The results are relevant for neutrino physics and thermodynamical processes in neutron stars. If electron screening is neglected, the spectral properties of the proton component show some resemblance with the physical situation in high-T c superconductors, and we briefly discuss similarities and differences in this connection. In a general prospect, the results of the study emphasize the role of Coulomb interaction in strong superconductors.

  8. Optical Characterization of Amorphous Hydrogenated Carbon (a-C:H) Thin Films Prepared by Single RF Plasma Method (United States)

    Dogan, Mansuroglu; Kadir, Goksen; Sinan, Bilikmen


    Methane (CH4) plasma was used to produce amorphous hydrogenated carbon (a-C:H) films by a single capacitively coupled radio frequency (RF) powered plasma system. The system consists of two parallel electrodes: the upper electrode is connected to 13.56 MHz RF power and the lower one is connected to the ground. Thin films were deposited on glass slides with different sizes and on silicon wafers. The influence of the plasma species on film characteristics was studied by changing the plasma parameters. The changes of plasma species during the deposition were investigated by optical emission spectroscopy (OES). The structural and optical properties were analyzed via Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD) and UV-visible spectroscopy, and the thicknesses of the samples were measured by a profilometer. The sp3/sp2 ratio and the existing H atoms play a significant role in the determination of the chemical properties of thin films in the plasma. The film quality and deposition rate were both increased by raising the power and the flow rate.

  9. Durability-enhanced two-dimensional hole gas of C-H diamond surface for complementary power inverter applications. (United States)

    Kawarada, Hiroshi; Yamada, Tetsuya; Xu, Dechen; Tsuboi, Hidetoshi; Kitabayashi, Yuya; Matsumura, Daisuke; Shibata, Masanobu; Kudo, Takuya; Inaba, Masafumi; Hiraiwa, Atsushi


    Complementary power field effect transistors (FETs) based on wide bandgap materials not only provide high-voltage switching capability with the reduction of on-resistance and switching losses, but also enable a smart inverter system by the dramatic simplification of external circuits. However, p-channel power FETs with equivalent performance to those of n-channel FETs are not obtained in any wide bandgap material other than diamond. Here we show that a breakdown voltage of more than 1600 V has been obtained in a diamond metal-oxide-semiconductor (MOS) FET with a p-channel based on a two-dimensional hole gas (2DHG). Atomic layer deposited (ALD) Al 2 O 3 induces the 2DHG ubiquitously on a hydrogen-terminated (C-H) diamond surface and also acts as both gate insulator and passivation layer. The high voltage performance is equivalent to that of state-of-the-art SiC planar n-channel FETs and AlGaN/GaN FETs. The drain current density in the on-state is also comparable to that of these two FETs with similar device size and V B .

  10. Hydrogen spillover in Pt-single-walled carbon nanotube composites: formation of stable C-H bonds. (United States)

    Bhowmick, Ranadeep; Rajasekaran, Srivats; Friebel, Daniel; Beasley, Cara; Jiao, Liying; Ogasawara, Hirohito; Dai, Hongjie; Clemens, Bruce; Nilsson, Anders


    Using in situ electrical conductivity and ex situ X-ray photoelectron spectroscopy (XPS) measurements, we have examined how the hydrogen uptake of single-walled carbon nanotubes (SWNTs) is influenced by the addition of Pt nanoparticles. The conductivity of platinum-sputtered single-walled carbon nanotubes (Pt-SWNTs) during molecular hydrogen exposure decreased more rapidly than that of the corresponding pure SWNTs, which supports a hydrogenation mechanism facilitated by "spillover" of dissociated hydrogen from the Pt nanoparticles. C 1s XPS spectra indicate that the Pt-SWNTs store hydrogen by means of chemisorption, that is, covalent C-H bond formation: molecular hydrogen charging at elevated pressure (8.27 bar) and room temperature yielded Pt-SWNTs with up to 16 ± 1.5 at. % sp(3)-hybridized carbon atoms, which corresponds to a hydrogen-storage capacity of 1.2 wt % (excluding the weight of Pt nanoparticles). Pt-SWNTs prepared by the Langmuir-Blodgett (LB) technique exhibited the highest Pt/SWNT ratio and also the best hydrogen uptake. © 2011 American Chemical Society

  11. Copper-promoted methylene C-H oxidation to a ketone derivative by O2

    DEFF Research Database (Denmark)

    Deville, Claire; McKee, Vickie; McKenzie, Christine J.


    The methylene group of the ligand 1,2-di(pyridin-2-yl)-ethanone oxime (dpeo) is slowly oxygenated by the O2 in air under ambient conditions when [Cu(dpeo)2](ClO4)2 is dissolved in ethanol or acetonitrile. An initial transient ketone product, 2-(hydroxyimino)-1,2-di(pyridine-2-yl)ethanone, (hidpe......) was characterized in the heteroleptic copper(ii) complex [Cu(bpca)(hidpe)](ClO4). The co-ligand in this complex, N-(2′-pyridylcarbonyl)pyridine-2-carboximidate (bpca−), is derived from a copper-promoted Beckmann rearrangement of hidpe. In the presence of bromide only [Cu(bpca)Br] is isolated. When significant water...... of C-H activation are produced from the dpeo-Cu/Mn systems and specifically O2. The metastable copper complexes [Cu(dpeo)2](ClO4)2 and [Cu(bpca)(hidpe)](ClO4), along with [NiX2(dpeo)2] (X = Cl, Br), [Ni(dpeo)3](ClO4)2, [Co(dpeo)3](ClO4)3 and the mixed valence complex [FeIIIFeII2(dpeo-H)3(dpeo)3](PF6...

  12. Copper-mediated C-H activation/C-S cross-coupling of heterocycles with thiols

    KAUST Repository

    Ranjit, Sadananda


    We report the synthesis of a series of aryl- or alkyl-substituted 2-mercaptobenzothiazoles by direct thiolation of benzothiazoles with aryl or alkyl thiols via copper-mediated aerobic C-H bond activation in the presence of stoichiometric CuI, 2,2′-bipyridine and Na 2CO 3. We also show that the approach can be extended to thiazole, benzimidazole, and indole substrates. In addition, we present detailed mechanistic investigations on the Cu(I)-mediated direct thiolation reactions. Both computational studies and experimental results reveal that the copper-thiolate complex [(L)Cu(SR)] (L: nitrogen-based bidentate ligand such as 2,2′-bipyridine; R: aryl or alkyl group) is the first reactive intermediate responsible for the observed organic transformation. Furthermore, our computational studies suggest a stepwise reaction mechanism based on a hydrogen atom abstraction pathway, which is more energetically feasible than many other possible pathways including β-hydride elimination, single electron transfer, hydrogen atom transfer, oxidative addition/reductive elimination, and σ-bond metathesis. © 2011 American Chemical Society.

  13. Pyrroloindolone synthesis via a Cp*Co(III)-catalyzed redox-neutral directed C-H alkenylation/annulation sequence. (United States)

    Ikemoto, Hideya; Yoshino, Tatsuhiko; Sakata, Ken; Matsunaga, Shigeki; Kanai, Motomu


    A unique synthetic utility of a Cp*Co(III) catalyst in comparison with related Cp*Rh(III) catalysts is described. A C2-selective indole alkenylation/annulation sequence proceeded smoothly with catalytic amount of a [Cp*Co(III)(C6H6)](PF6)2 complex and KOAc. Intramolecular addition of an alkenyl-Cp*Co species to a carbamoyl moiety gave pyrroloindolones in 58-89% yield in one pot. Clear difference was observed between the catalytic activity of the Cp*Co(III) complex and those of Cp*Rh(III) complexes, highlighting the unique nucleophilic activity of the organocobalt species. The Cp*Co(III) catalysis was also suitable for simple alkenylation process of N-carbamoyl indoles, and broad range of alkynes, including terminal alkynes, were applicable to give C2-alkenylated indoles in 50-99% yield. Mechanistic studies on C-H activation step under Cp*Co(III) catalysis with the aid of an acetate unit as well as evaluation of the difference between organo-Co(III) species and organo-Rh(III) species are also described.

  14. Surface morphology and grain analysis of successively industrially grown amorphous hydrogenated carbon films (a-C:H) on silicon (United States)

    Catena, Alberto; McJunkin, Thomas; Agnello, Simonpietro; Gelardi, Franco M.; Wehner, Stefan; Fischer, Christian B.


    Silicon (1 0 0) has been gradually covered by amorphous hydrogenated carbon (a-C:H) films via an industrial process. Two types of these diamond-like carbon (DLC) coatings, one more flexible (f-DLC) and one more robust (r-DLC), have been investigated. Both types have been grown by a radio frequency plasma-enhanced chemical vapor deposition (RF-PECVD) technique with acetylene plasma. Surface morphologies have been studied in detail by atomic force microscopy (AFM) and Raman spectroscopy has been used to investigate the DLC structure. Both types appeared to have very similar morphology and sp2 carbon arrangement. The average height and area for single grains have been analyzed for all depositions. A random distribution of grain heights was found for both types. The individual grain structures between the f- and r-type revealed differences: the shape for the f-DLC grains is steeper than for the r-DLC grains. By correlating the average grain heights to the average grain areas for all depositions a limited region is identified, suggesting a certain regularity during the DLC deposition mechanisms that confines both values. A growth of the sp2 carbon entities for high r-DLC depositions is revealed and connected to a structural rearrangement of carbon atom hybridizations and hydrogen content in the DLC structure.

  15. A novel glycosylated solution from Dioscorea zingiberensis C.H. Wright significantly improves the solvent productivity of Clostridium beijerinckii. (United States)

    Xiao, Chuan; Fan, Wei; Du, Shengjie; Liu, Laizhuang; Wang, Changli; Guo, Mengzhen; Zhang, Liwei; Zhang, Meng; Yu, Longjiang


    The economics of bio-solvent production are largely dependent on the cost of the fermentation substrate. Dioscorea zingiberensis C.H. Wright (DZW), the main raw material used to produce saponin, contains 13-18% starch which can be directly saccharified to a saccharification liquid of DZW starch (SLDS) that contains abundant nutrients. In this study, the water-soluble micromolecule compounds in SLDS were quantified through 1 H NMR. Using SLDS as the substrate to conduct ABE fermentation by Clostridium beijerinckii, the fermentation cycle was shortened 24h, the maximum biomass and consumption rate of the glucose significantly increased, and the productivity of total solvents were increased by 0.244±0.010g/L/h compared to standard P 2 medium. Expression analysis of genes encoding key enzymes involved in acetone and butanol production and glucose consumption showed that they were induced by SLDS. Taken together, SLDS is a useful and renewable glycosylated solution for ABE fermentation. Copyright © 2017. Published by Elsevier Ltd.

  16. Warm Absorber Diagnostics of AGN Dynamics (United States)

    Kallman, Timothy

    Warm absorbers and related phenomena are observable manifestations of outflows or winds from active galactic nuclei (AGN) that have great potential value. Understanding AGN outflows is important for explaining the mass budgets of the central accreting black hole, and also for understanding feedback and the apparent co-evolution of black holes and their host galaxies. In the X-ray band warm absorbers are observed as photoelectric absorption and resonance line scattering features in the 0.5-10 keV energy band; the UV band also shows resonance line absorption. Warm absorbers are common in low luminosity AGN and they have been extensively studied observationally. They may play an important role in AGN feedback, regulating the net accretion onto the black hole and providing mechanical energy to the surroundings. However, fundamental properties of the warm absorbers are not known: What is the mechanism which drives the outflow?; what is the gas density in the flow and the geometrical distribution of the outflow?; what is the explanation for the apparent relation between warm absorbers and the surprising quasi-relativistic 'ultrafast outflows' (UFOs)? We propose a focused set of model calculations that are aimed at synthesizing observable properties of warm absorber flows and associated quantities. These will be used to explore various scenarios for warm absorber dynamics in order to answer the questions in the previous paragraph. The guiding principle will be to examine as wide a range as possible of warm absorber driving mechanisms, geometry and other properties, but with as careful consideration as possible to physical consistency. We will build on our previous work, which was a systematic campaign for testing important class of scenarios for driving the outflows. We have developed a set of tools that are unique and well suited for dynamical calculations including radiation in this context. We also have state-of-the-art tools for generating synthetic spectra, which are

  17. Distributed Absorber for Noise and Vibration Control

    Directory of Open Access Journals (Sweden)

    Michel Azoulay


    Full Text Available An approach to a wide-band frequency passive vibration attenuation is introduced in this paper. This aims to suppress noise and vibration of extended multimode objects like plates, panels and shells. The absorber is arranged in the form of a single-layer assembly of small inertial bodies (balls being distributed and moulded within the light visco-elastic media (e.g. silicone resin. The absorber as a whole is embedded into object face covering the critical patches of the system surface. For the purpose of characterization, the authors introduced the complex frequency response function relating the volume velocity produced by the vibrating object surface (response stimulated by a point-wise force (stimulus applied to a particular point. The simulation and optimization of the main frequency characteristics has been performed using a full scale 3-dimensional Finite Element model. These revealed some new dynamic features of absorber's structures, which can contribute to vibration attenuation. A full-scale physical experimentation with synthesised absorber's structures confirmed the main results of simulation and has shown significant noise reduction over a staggering 0–20 kHz frequency band. This was achieved with a negligible weight and volume penalty due to the addition of the absorber. The results can find multiple applications in noise and vibration control of different structures. Some examples of such applications are presented.

  18. Identifying the perfect absorption of metamaterial absorbers (United States)

    Duan, G.; Schalch, J.; Zhao, X.; Zhang, J.; Averitt, R. D.; Zhang, X.


    We present a detailed analysis of the conditions that result in unity absorption in metamaterial absorbers to guide the design and optimization of this important class of functional electromagnetic composites. Multilayer absorbers consisting of a metamaterial layer, dielectric spacer, and ground plane are specifically considered. Using interference theory, the dielectric spacer thickness and resonant frequency for unity absorption can be numerically determined from the functional dependence of the relative phase shift of the total reflection. Further, using transmission line theory in combination with interference theory we obtain analytical expressions for the unity absorption resonance frequency and corresponding spacer layer thickness in terms of the bare resonant frequency of the metamaterial layer and metallic and dielectric losses within the absorber structure. These simple expressions reveal a redshift of the unity absorption frequency with increasing loss that, in turn, necessitates an increase in the thickness of the dielectric spacer. The results of our analysis are experimentally confirmed by performing reflection-based terahertz time-domain spectroscopy on fabricated absorber structures covering a range of dielectric spacer thicknesses with careful control of the loss accomplished through water absorption in a semiporous polyimide dielectric spacer. Our findings can be widely applied to guide the design and optimization of the metamaterial absorbers and sensors.

  19. EDITORIAL: Strongly correlated electron systems Strongly correlated electron systems (United States)

    Ronning, Filip; Batista, Cristian


    -dependent Zeeman splitting in strontium ruthenate Emil J Rozbicki, James F Annett, Jean-René Souquet and Andrew P Mackenzie Thermodynamics of itinerant metamagnetic transitions A M Berridge Magnon-mediated pairing and isotope effect in iron-based superconductors Jiansheng Wu and Philip Phillips Nernst quantum oscillations in bulk semi-metals Zengwei Zhu, Huan Yang, Aritra Banerjee, Liam Malone, Benoît Fauqué and Kamran Behnia Signatures of a quantum Griffiths phase in a d-metal alloy close to its ferromagnetic quantum critical point Almut Schroeder, Sara Ubaid-Kassis and Thomas Vojta Influence of super-ohmic dissipation on a disordered quantum critical point Thomas Vojta, José A Hoyos, Priyanka Mohan and Rajesh Narayanan The van Hemmen-Kondo model for disordered cerium systems S G Magalhaes, F M Zimmer and B Coqblin Chemical pressure, dilution and disorder in the heavy fermion compounds Ce3 - xLaxPd20Si6 (x = 1/3, 2/3) H Winkler, K-A Lorenzer, S Laumann, J Custers, A Prokofiev and S Paschen Magnetism of fine particles of Kondo lattices, obtained by high-energy ball-milling E V Sampathkumaran, K Mukherjee, Kartik K Iyer, Niharika Mohapatra and Sitikantha D Das Heavy fermion scaling: uranium versus cerium and ytterbium compounds J M Lawrence, C H Wang, A D Christianson and E D Bauer Temperature dependence of hybridization gaps in metallic heavy-fermion systems Xiaodong Yang, Peter S Riseborough and Tomasz Durakiewicz Low-energy properties of the Kondo lattice model O Bodensiek, R Žitko, R Peters and T Pruschke Temperature dependence of the zero-bias anomaly in the Anderson-Hubbard model: insights from an ensemble of two-site systems R Wortis and W A Atkinson A charge density wave in the hidden order state of URu2Si2 Jung-Jung Su, Yonatan Dubi, Peter Wölfle and Alexander V Balatsky Field-induced suppression of the heavy-fermion state in YbRh2Si2 Gertrud Zwicknagl Discontinuous Hall coefficient at the quantum critical point in YbRh2Si2 Sven Friedemann, Niels Oeschler, Steffen

  20. Strong-coupling approximations

    International Nuclear Information System (INIS)

    Abbott, R.B.


    Standard path-integral techniques such as instanton calculations give good answers for weak-coupling problems, but become unreliable for strong-coupling. Here we consider a method of replacing the original potential by a suitably chosen harmonic oscillator potential. Physically this is motivated by the fact that potential barriers below the level of the ground-state energy of a quantum-mechanical system have little effect. Numerically, results are good, both for quantum-mechanical problems and for massive phi 4 field theory in 1 + 1 dimensions. 9 references, 6 figures

  1. Strong interaction and QFD

    International Nuclear Information System (INIS)

    Ebata, T.


    With an assumed weak multiplet structure for bosonic hadrons, which is consistent with the ΔI = 1/2 rule, it is shown that the strong interaction effective hamiltonian is compatible with the weak SU(2) x U(1) gauge transformation. Especially the rho-meson transforms as a triplet under SU(2)sub(w), and this is the origin of the rho-photon analogy. It is also shown that the existence of the non-vanishing Cabibbo angle is a necessary condition for the absence of the exotic hadrons. (orig.)

  2. Absorbed dose determination in water. I

    International Nuclear Information System (INIS)

    Novotny, J.


    The use of new values of physical parameters as recommended by international organizations has consequences in radiotherapy, e.g. in the determination of absorbed doses in water based on ionometric measurements. A procedure is proposed for the determination of the conversion factor K w,u between kerma in air and absorbed dose in water, and of the factor C w,u between exposure measured and absorbed dose in water, for ionization chambers and high-energy photon beams. The conversion factors depend not only on the radiation quality but also on the dimensions and composition of the chamber and of the cup used in the calibrations. Numerical values are given for conventional kinds of ionization chambers. (author). 3 tabs., 16 refs

  3. Absorbed dose determination in water. II

    International Nuclear Information System (INIS)

    Novotny, J.; Hobzova, L.; Kindlova, A.


    The use of new values of physical parameters as recommended by international organizations has consequences in radiotherapy, e.g. in the determination of absorbed doses in water based on ionometric measurements. A procedure is proposed for the determination of the conversion factor K w,e from kerma in air to absorbed dose in water, and of the conversion factor C w,e from exposure measured to dose absorbed in water, this for ionization chambers and high-energy electron beams. The conversion factors depend not only on the radiation quality and measurement depth in the phantom but also on the dimensions and composition of the chamber and of the cup used in the calibrations. Numerical values are given for two conventional kinds of ionization chambers. (author). 3 tabs., 9 refs

  4. Ferrite HOM Absorber for the RHIC ERL

    Energy Technology Data Exchange (ETDEWEB)

    Hahn,H.; Choi, E.M.; Hammons, L.


    A superconducting Energy Recovery Linac is under construction at Brookhaven National Laboratory to serve as test bed for RHIC upgrades. The damping of higher-order modes in the superconducting five-cell cavity for the Energy-Recovery linac at RHIC is performed exclusively by two ferrite absorbers. The ferrite properties have been measured in ferrite-loaded pill box cavities resulting in the permeability values given by a first-order Debye model for the tiled absorber structure and an equivalent permeability value for computer simulations with solid ring dampers. Measured and simulated results for the higher-order modes in the prototype copper cavity are discussed. First room-temperature measurements of the finished niobium cavity are presented which confirm the effective damping of higher-order modes in the ERL. by the ferrite absorbers.

  5. Properties of CGM-Absorbing Galaxies (United States)

    Hamill, Colin; Conway, Matthew; Apala, Elizabeth; Scott, Jennifer


    We extend the results of a study of the sightlines of 45 low-redshift quasars (0.06 COS that lie within the Sloan Digital Sky Survey. We have used photometric data from the SDSS DR12, along with the known absorption characteristics of the intergalactic medium and circumgalactic medium, to identify the most probable galaxy matches to absorbers in the spectroscopic dataset. Here, we use photometric data and measured galaxy parameters from SDSS DR12 to examine the distributions of galaxy properties such as virial radius, morphology, and position angle among those that match to absorbers within a specific range of impact parameters. We compare those distributions to galaxies within the same impact parameter range that are not matched to any absorber in the HST/COS spectrum in order to investigate global properties of the circumgalactic medium.

  6. Quantum walk with one variable absorbing boundary

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Feiran [Key Laboratory of Quantum Information and Quantum Optoelectronic Devices, Shaanxi Province, Xi' an Jiaotong University, Xi' an 710049 (China); Department of Applied Physics, School of Science, Xi' an Jiaotong University, Xi' an 710049 (China); Zhang, Pei, E-mail: [Key Laboratory of Quantum Information and Quantum Optoelectronic Devices, Shaanxi Province, Xi' an Jiaotong University, Xi' an 710049 (China); Department of Applied Physics, School of Science, Xi' an Jiaotong University, Xi' an 710049 (China); Wang, Yunlong; Liu, Ruifeng; Gao, Hong; Li, Fuli [Key Laboratory of Quantum Information and Quantum Optoelectronic Devices, Shaanxi Province, Xi' an Jiaotong University, Xi' an 710049 (China); Department of Applied Physics, School of Science, Xi' an Jiaotong University, Xi' an 710049 (China)


    Quantum walks constitute a promising ingredient in the research on quantum algorithms; consequently, exploring different types of quantum walks is of great significance for quantum information and quantum computation. In this study, we investigate the progress of quantum walks with a variable absorbing boundary and provide an analytical solution for the escape probability (the probability of a walker that is not absorbed by the boundary). We simulate the behavior of escape probability under different conditions, including the reflection coefficient, boundary location, and initial state. Moreover, it is also meaningful to extend our research to the situation of continuous-time and high-dimensional quantum walks. - Highlights: • A novel scheme about quantum walk with variable boundary is proposed. • The analytical results of the survival probability from the absorbing boundary. • The behavior of survival probability under different boundary conditions. • The influence of different initial coin states on the survival probability.

  7. Tribology Aspect of Rubber Shock Absorbers Development

    Directory of Open Access Journals (Sweden)

    M. Banić


    Full Text Available Rubber is a very flexible material with many desirable properties Which enable its broad use in engineering practice. Rubber or rubber-metal springs are widely used as anti-vibration or anti-shock components in technical systems. Rubber-metal springs are usually realized as a bonded assembly, however especially in shock absorbers, it is possible to realize free contacts between rubber and metal parts. In previous research it authors was observed that friction between rubber and metal in such case have a significant influence on the damping characteristics of shock absorber. This paper analyzes the development process of rubber or rubber-metal shock absorbers realized free contacts between the constitutive parts, starting from the design, construction, testing and operation, with special emphasis on the development of rubber-metal springs for the buffing and draw gear of railway vehicles.

  8. Neutron absorbing materials for reactors control; Materiaux absorbants neutroniques pour le pilotage des reacteurs

    Energy Technology Data Exchange (ETDEWEB)

    Gosset, D. [CEA Saclay, Dept. des Materiaux pour le Nucleaire (DMN), 91 - Gif sur Yvette (France); Herter, P. [CEA Saclay, Dir. de l' Energie Nucleaire (DEN), 91 - Gif sur Yvette (France)


    The different reactivity control systems allow to keep the mastery of the fission reaction inside the reactor core at any time: power control, safe shutdown, compensation of fuel burnup. These systems can be of different type: gaseous (like {sup 3}He in some experimental reactors), liquid (borated water in PWRs), and in most cases solid and combined or not with the previous types. In all cases, the constituents comprise neutron absorbing nuclides. The absorbing materials are contained in elementary absorbing elements, named control rods. This article describes the absorbing materials used in the control rods of the main nuclear power plants and also in the burnable poison rods of water cooled reactors. Content: 1 - general considerations about absorbing materials: neutron absorption cross sections, selection criteria of absorbing materials, main uses of absorbers in reactors, supply sources, wastes; 2 - description of the absorbing materials used: silver-indium-cadmium alloy (ICA), boron carbide (B{sub 4}C), dysprosium titanate, hafnium, burnable poisons and rare earths; 3 - conclusion and perspectives. (J.S.)

  9. Electrical and Optical Properties of Si-Incorporated a-C:H Films via the Radio Frequency Plasma-Enhanced Chemical Vapor Deposition Method. (United States)

    Kim, In Jun; Choi, Won Seok; Hong, Byungyou


    The optical and electrical properties of silicon-incorporated hydrogenated amorphous carbon (a-C:H:Si) films deposited via the radio frequency (RF) plasma-enhanced chemical vapor deposition (PECVD) method using a mixture of CH4, H2, and SiH4 were observed. The silane gas whose ranged from 0 to 25 vol.% [SiH4/(SiH4 + CH4) was fed into the reactor while the other deposition parameters were kept constant. The basic properties of these films were investigated via Raman spectroscopy, UV-visible spectrometry, I-V measurement, and surface profiling. The experiment results showed that the film thickness increased from 300 nm to 800 nm for the same deposition time as the silane gas increased. The Raman spectrum obtained from the silicon-incorporated a-C:H films suggested that the film property changed from graphitic-like to more diamond-like. As the silane gas increased, the optical gap, E04, slightly increased from 1.98 eV to 2.62 eV. It was shown that the Si atoms incorporated into the a-C:H films reduced the size of the sp2 clusters. As for the I-V characteristics, the Si-incorporated a-C:H films had a lower leakage current than the a-C:H films without Si.

  10. Strong Coupling Holography

    CERN Document Server

    Dvali, Gia


    We show that whenever a 4-dimensional theory with N particle species emerges as a consistent low energy description of a 3-brane embedded in an asymptotically-flat (4+d)-dimensional space, the holographic scale of high-dimensional gravity sets the strong coupling scale of the 4D theory. This connection persists in the limit in which gravity can be consistently decoupled. We demonstrate this effect for orbifold planes, as well as for the solitonic branes and string theoretic D-branes. In all cases the emergence of a 4D strong coupling scale from bulk holography is a persistent phenomenon. The effect turns out to be insensitive even to such extreme deformations of the brane action that seemingly shield 4D theory from the bulk gravity effects. A well understood example of such deformation is given by large 4D Einstein term in the 3-brane action, which is known to suppress the strength of 5D gravity at short distances and change the 5D Newton's law into the four-dimensional one. Nevertheless, we observe that the ...


    Energy Technology Data Exchange (ETDEWEB)



    Previous analyses have assumed that wedge absorbers are triangularly shaped with equal angles for the two faces. In this case, to linear order, the energy loss depends only on the position in the direction of the face tilt, and is independent of the incoming angle. One can instead construct an absorber with entrance and exit faces facing rather general directions. In this case, the energy loss can depend on both the position and the angle of the particle in question. This paper demonstrates that and computes the effect to linear order.

  12. Multilayer detector for skin absorbed dose measuring

    International Nuclear Information System (INIS)

    Osanov, D.P.; Panova, V.P.; Shaks, A.I.


    A method for skin dosimetry based on utilization of multilayer detectors and permitting to estimate distribution of absorbed dose by skin depth is described. The detector represents a set of thin sensitive elements separated by tissue-equivalent absorbers. Quantitative evaluation and forecasting the degree of radiation injury of skin are determined by the formula based on determination of the probability of the fact that cells are not destroyed and they can divide further on. The given method ensures a possibility of quantitative evaluation of radiobiological effect and forecasting clinical consequences of skin irradiation by results of corresponding measurements of dose by means of the miultilayer detector

  13. Device for absorbing seismic effects on buildings

    International Nuclear Information System (INIS)

    Xercavins, Pierre; Pompei, Michel.


    Device for absorbing seismic effects. The construction or structure to be protected rests on its foundations through at least one footing formed of a stack of metal plates interlinked by layers of adhesive material, over at least a part of their extent, this material being an elastomer that can distort, characterized in that at least part of the area of some metal plates works in association with components which are able to absorb at least some of the energy resulting from friction during the relative movements of the metal plates against the distortion of the elastomer [fr

  14. Optimization of Perfect Absorbers with Multilayer Structures (United States)

    Li Voti, Roberto


    We study wide-angle and broadband perfect absorbers with compact multilayer structures made of a sequence of ITO and TiN layers deposited onto a silver thick layer. An optimization procedure is introduced for searching the optimal thicknesses of the layers so as to design a perfect broadband absorber from 400 nm to 750 nm, for a wide range of angles of incidence from 0{°} to 50{°}, for both polarizations and with a low emissivity in the mid-infrared. We eventually compare the performances of several optimal structures that can be very promising for solar thermal energy harvesting and collectors.

  15. Ny arkitektur for nordmenn i Iowa. Arkitekt C.H. Griese, Luther College og kirker i 1860-årene

    Directory of Open Access Journals (Sweden)

    Jens Christian Eldal


    Full Text Available The Norwegian Evangelical-Lutheran Church in America decided in 1861 to build their first college close to the western frontier of The Upper Midwest. The site chosen was a bluff above Upper Iowa River, highly visible from Decorah, a small town founded only 12 years earlier, few years after the first settlers arrived. The college building became a relatively vast structure erected between 1862 and 1865, completed to its originally planned symmetrical composition in 1874. The building style and its composition were common among American colleges and universities further east in the US. It is also demonstrated how the Luther College building façade in composition and detailing shows clear influences from a specific German building. This particular building has been designated as especially typical of the German Rundbogenstil (Style of the Rounded Arch with its great mix of various stylistic elements. The architect was known as C. H. Griese from Cleveland, Ohio. He is identified as Charles Henry Griese (1821–1909, who immigrated from Germany about 1850 and was known as a mason and contractor, from now on also as an architect. In 1869, Griese also designed the three Norwegian Lutheran churches of Washington Prairie, Stavanger and Glenwood in rural Decorah. They represented a Neo Gothic style which was new to the area, and had an evident architectural character contrasting the more ordinary vernacular churches in the area. They signify a change of style and, like the college building, they demonstrate architectural ambitions new to these Norwegians, giving insight also into the general architectural and vernacular development in the area.

  16. Interexaminer reliability in clinical measurement of L*C*h* values of anterior teeth using a spectrophotometer. (United States)

    Hassel, Alexander J; Grossmann, Anne-christiane; Schmitter, Marc; Balke, Zibandeh; Buzello, Anja M


    The objective of this study was to investigate interexaminer reliability in the clinical measurement of the L*C*h* (lightness/value, chroma, hue) values of anterior teeth using a spectrophotometer (Vita Easyshade). The basic color of the maxillary right central incisors and canines of 23 subjects was spectrophotometrically determined by 4 clinicians and an experienced user (development manager) of the spectrophotometer. Also, to analyze the effect of different training with the instrument on interexaminer reliability, 2 of the clinicians were instructed in the use of the spectrophotometer by the experienced examiner, whereas the others instructed themselves by studying the operating manual. Agreement between all examiners was acceptable to excellent (intraclass coefficient > 0.4). The mean value of the measured differences for the central incisors of all subjects for L* values was 5 (for C* = 3.8, h* = 2.7 degrees) and for canines, the mean L* was 4.5 (C* = 3, h* = 1.6 degrees). Results from comparison of the 2 different training methods were inconsistent. Agreement with the experienced examiner ranged from not acceptable (C* values for incisors of self-instructed examiners) to excellent. The distribution of the measurements of 1 subject could lead to deviations in color, probably with clinical impact. For canines, the measurements were at least equally reproducible (in some cases significantly more reproducible) compared to central incisors. Because of the small number of examiners and the inconsistent results, it was not possible to reach a definite conclusion about the effect of different training methods on interexaminer reliability.

  17. LIGO: The strong belief

    CERN Multimedia

    Antonella Del Rosso


    Twenty years of designing, building and testing a number of innovative technologies, with the strong belief that the endeavour would lead to a historic breakthrough. The Bulletin publishes an abstract of the Courier’s interview with Barry Barish, one of the founding fathers of LIGO.   The plots show the signals of gravitational waves detected by the twin LIGO observatories at Livingston, Louisiana, and Hanford, Washington. (Image: Caltech/MIT/LIGO Lab) On 11 February, the Laser Interferometer Gravitational-Wave Observatory (LIGO) and Virgo collaborations published a historic paper in which they showed a gravitational signal emitted by the merger of two black holes. These results come after 20 years of hard work by a large collaboration of scientists operating the two LIGO observatories in the US. Barry Barish, Linde Professor of Physics, Emeritus at the California Institute of Technology and former Director of the Global Design Effort for the Internat...

  18. The dimers of glyoxal and acrolein with H 2O and HF: Negative intramolecular coupling and blue-shifted C-H stretch (United States)

    Karpfen, Alfred; Kryachko, Eugene S.


    The structures and the vibrational spectra of the hydrogen-bonded complexes: glyoxal-H 2O, glyoxal-HF, acrolein-H 2O, and acrolein-HF, are investigated within the MP2/aug-cc-pVTZ computational approach. It is demonstrated that the calculated blue shifts of the C-H stretching frequencies in the glyoxal-H 2O complexes are only indirectly pertinent to hydrogen bonding to the C-H group. The comparison with the glyoxal-HF and the acrolein-HF complexes reveals that these blue shifts are a direct consequence of a negative intramolecular coupling between vicinal C dbnd O and C-H bonds in the aldehyde groups of isolated glyoxal and acrolein molecules. To support this interpretation, the halogen-bonded complexes glyoxal-BrF and acrolein-BrF are discussed.

  19. Carbon monoxide production from desflurane and six types of carbon dioxide absorbents in a patient model

    NARCIS (Netherlands)

    Keijzer, C.; Perez, R. S. G. M.; de Lange, J. J.


    BACKGROUND: Desflurane is known to produce high concentrations of carbon monoxide (CO) in desiccated sodalime or Baralyme (Allied Healthcare Products, St. Louis, MO). Desiccated absorbents without strong bases like potassium hydroxide or sodium hydroxide are reported to produce less or no CO at all.

  20. Review of Plasmonic Nanocomposite Metamaterial Absorber

    Directory of Open Access Journals (Sweden)

    Mehdi Keshavarz Hedayati


    Full Text Available Plasmonic metamaterials are artificial materials typically composed of noble metals in which the features of photonics and electronics are linked by coupling photons to conduction electrons of metal (known as surface plasmon. These rationally designed structures have spurred interest noticeably since they demonstrate some fascinating properties which are unattainable with naturally occurring materials. Complete absorption of light is one of the recent exotic properties of plasmonic metamaterials which has broadened its application area considerably. This is realized by designing a medium whose impedance matches that of free space while being opaque. If such a medium is filled with some lossy medium, the resulting structure can absorb light totally in a sharp or broad frequency range. Although several types of metamaterials perfect absorber have been demonstrated so far, in the current paper we overview (and focus on perfect absorbers based on nanocomposites where the total thickness is a few tens of nanometer and the absorption band is broad, tunable and insensitive to the angle of incidence. The nanocomposites consist of metal nanoparticles embedded in a dielectric matrix with a high filling factor close to the percolation threshold. The filling factor can be tailored by the vapor phase co-deposition of the metallic and dielectric components. In addition, novel wet chemical approaches are discussed which are bio-inspired or involve synthesis within levitating Leidenfrost drops, for instance. Moreover, theoretical considerations, optical properties, and potential application of perfect absorbers will be presented.

  1. Selective mass transfer in a membrane absorber (United States)

    Okunev, A. Yu.; Laguntsov, N. I.


    A theoretical study of selective mass transfer in a plane-frame membrane absorber (contactor) has been made. A mathematical model of the process has been developed and the process of purification of a gas mixture depending on the flow parameters, the membrane, and the feeding-mixture composition has been studied with its help.

  2. Review of Plasmonic Nanocomposite Metamaterial Absorber (United States)

    Hedayati, Mehdi Keshavarz; Faupel, Franz; Elbahri, Mady


    Plasmonic metamaterials are artificial materials typically composed of noble metals in which the features of photonics and electronics are linked by coupling photons to conduction electrons of metal (known as surface _lasmon). These rationally designed structures have spurred interest noticeably since they demonstrate some fascinating properties which are unattainable with naturally occurring materials. Complete absorption of light is one of the recent exotic properties of plasmonic metamaterials which has broadened its application area considerably. This is realized by designing a medium whose impedance matches that of free space while being opaque. If such a medium is filled with some lossy medium, the resulting structure can absorb light totally in a sharp or broad frequency range. Although several types of metamaterials perfect absorber have been demonstrated so far, in the current paper we overview (and focus on) perfect absorbers based on nanocomposites where the total thickness is a few tens of nanometer and the absorption band is broad, tunable and insensitive to the angle of incidence. The nanocomposites consist of metal nanoparticles embedded in a dielectric matrix with a high filling factor close to the percolation threshold. The filling factor can be tailored by the vapor phase co-deposition of the metallic and dielectric components. In addition, novel wet chemical approaches are discussed which are bio-inspired or involve synthesis within levitating Leidenfrost drops, for instance. Moreover, theoretical considerations, optical properties, and potential application of perfect absorbers will be presented. PMID:28788511

  3. Moving core beam energy absorber and converter (United States)

    Degtiarenko, Pavel V.


    A method and apparatus for the prevention of overheating of laser or particle beam impact zones through the use of a moving-in-the-coolant-flow arrangement for the energy absorbing core of the device. Moving of the core spreads the energy deposition in it in 1, 2, or 3 dimensions, thus increasing the effective cooling area of the device.


    NARCIS (Netherlands)



    The industrially important process of formaldehyde absorption in water constitutes a case of multicomponent mass transfer with multiple reactions and considerable heat effects. A stable solution algorithm is developed to simulate the performance of industrial absorbers for this process using a

  5. Electromagnetic and microwave absorbing properties of hollow ...

    Indian Academy of Sciences (India)

    bandwidth below −10 dB and minimum RL decrease with increasing thickness of HCNSs/paraffin composites. Keywords. Nanomaterials; nanospheres; CVD; electric; magnetic; microwave absorption properties. 1. Introduction. In recent years, microwave absorbing materials have attracted considerable attention because it ...

  6. Can polar bear hairs absorb environmental energy?


    He Ji-Huan; Wang Qing-Li; Sun Jie


    A polar bear (Ursus maritimus) has superior ability to survive in harsh Arctic regions, why does the animal have such an excellent thermal protection? The present paper finds that the unique labyrinth cavity structure of the polar bear hair plays an important role. The hair can not only prevent body temperature loss but can also absorb energy from the environment.

  7. Can polar bear hairs absorb environmental energy?

    Directory of Open Access Journals (Sweden)

    He Ji-Huan


    Full Text Available A polar bear (Ursus maritimus has superior ability to survive in harsh Arctic regions, why does the animal have such an excellent thermal protection? The present paper finds that the unique labyrinth cavity structure of the polar bear hair plays an important role. The hair can not only prevent body temperature loss but can also absorb energy from the environment.

  8. Technology and assessment of neutron absorbing materials

    International Nuclear Information System (INIS)

    Kelly, B.T.; Murgatroyd, R.A.


    The present review assesses more recent developments in the technology and application of those absorber materials which are considered to be established or to have shown potential in reactor control. Emphasis is placed on physical, chemical and metallurgical properties and upon irradiation behaviour. (author)

  9. Absorbance and fluorescence studies on porphyrin Nanostructures ...

    African Journals Online (AJOL)

    The aim of this work was to study some photophysical properties of PNR for application as light harvester in dye sensitized solar cells. These properties included absorbance, fluorescence, and fluorescence quantum yield and lifetime. The results of Transmission Electron Microscope (TEM) images showed the formation of ...

  10. Rapid Access to Ortho-Alkylated Vinylarenes from Aromatic Acids by Dearomatization and Tandem Decarboxylative C-H Olefination/Rearomatization. (United States)

    Tsai, Hung-Chang; Huang, Yen-Hsiang; Chou, Chih-Ming


    A two-step straightforward method for the preparation of ortho-alkylated vinylarenes from readily available benzoic acids is described. The synthetic route involves the dearomatization of benzoic acids by Birch reduction providing alkylated cyclohexa-2,5-dienyl-1-carboxylic acids. The diene subsequently undergoes a decarboxylative C-H olefination followed by rearomatization to deliver ortho-alkylated vinylarene. Mechanistic studies suggest that a Pd/Ag bimetallic catalytic system is important in the tandem decarboxylative C-H olefination/rearomatization step.

  11. C-H Acetoxylation-Based Chemical Synthesis of 17 β-Hydroxymethyl-17 α-methyl-18-norandrost-13-ene Steroids. (United States)

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


    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. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Rapid access to the core skeleton of the [3 + 2]-type dimeric pyrrole-imidazole alkaloids by triplet ketone-mediated C-H functionalization. (United States)

    You, Lin; Chen, Chuo


    The ability of triplet ketones to abstract a hydrogen atom from hydrocarbons is reminiscent of that of the high-spin metal-oxo complexes in C-H oxidation enzymes. In practice, the reactivity of triplet ketones is easier to control and applicable to promoting a wider range of reactions. We demonstrate herein the synthetic utility of triplet ketone-mediated C -addition of methanol to cyclopentenone derivatives with an expedient synthesis of the core skeleton of the [3+2]-type dimeric pyrrole-imidazole alkaloids. Remarkably, this photochemical C-H functionalization reaction is highly regioselective and can tolerate a good range of functional groups.

  13. An experimental study of an energy absorbing restrainer for piping systems

    International Nuclear Information System (INIS)

    Sone, A.; Suzuki, K.


    Recently, in the seismic design methodology of the piping systems in nuclear power plants, new and improved design criteria and calculation techniques which will lead to more reliable and cost saving design products have been investigated. For instance, problems for reducing the snubbers in nuclear power plants which provide high costs for their inspections and maintenances and related flexible design problems for the dynamic piping systems have been investigated. Thus, in order to replace snubbers, various types of alternative supporting devices such as dynamic absorbers, gapped support and energy absorbing support devices have been proposed. A number of energy absorbing restrainers have been designed in Japan and United-States by allowing yield to occur during strong earthquakes. Advantages and disadvantages of these restrainers were examined analytically and experimentally. In order to overcome the disadvantages, the authors introduced new absorbing material LSPZ (laminated super plastic zinc) in which SPZ is expected to have reliable ductility and also efficient energy absorbability still under the normal temperature condition. This paper is devoted to an experimental works for this updated absorbing restrainer

  14. Development of optical tools for the characterization of selective solar absorber at elevated temperature (United States)

    Giraud, Philemon; Braillon, Julien; Delord, Christine; Raccurt, Olivier


    Durability of solar components for CSP (Concentrated Solar Power Plant) technologies is a key point to lower cost and ensure their large deployment. These technologies concentrated the solar radiation by means of mirrors on a receiver tube where it is collected as thermal energy. The absorbers are submitted to strong environmental constraints and the degradation of their optical properties (emittance and solar absorbance) have a direct impact on performance. The objective is to develop new optical equipment for characterization of this solar absorber in condition of use that is to say in air and at elevated temperature. In this paper we present two new optical test benches developed for optical characterization of solar absorbers in condition of use up to 800°C. The first equipment is an integrated sphere with heated sample holder which measures the hemispherical reflectance between 280 and 2500 nm to calculate the solar absorbance at high temperature. The second optical test bench measures the emittance of samples up to 1000°C in the range of 1.25 to 28.57 µm. Results of high temperature measurements on a series of metallic absorbers with selective coating and refractory material for high thermal receiver are presented.

  15. John Strong (1941 - 2006)

    CERN Multimedia

    Wickens, F

    Our friend and colleague John Strong was cruelly taken from us by a brain tumour on Monday 31st July, a few days before his 65th birthday John started his career working with a group from Westfield College, under the leadership of Ted Bellamy. He obtained his PhD and spent the early part of his career on experiments at Rutherford Appleton Laboratory (RAL), but after the early 1970s his research was focussed on experiments in CERN. Over the years he made a number of notable contributions to experiments in CERN: The Omega spectrometer adopted a system John had originally developed for experiments at RAL using vidicon cameras to record the sparks in the spark chambers; He contributed to the success of NA1 and NA7, where he became heavily involved in the electronic trigger systems; He was responsible for the second level trigger system for the ALEPH detector and spent five years leading a team that designed and built the system, which ran for twelve years with only minor interventions. Following ALEPH he tur...

  16. Stirring Strongly Coupled Plasma

    CERN Document Server

    Fadafan, Kazem Bitaghsir; Rajagopal, Krishna; Wiedemann, Urs Achim


    We determine the energy it takes to move a test quark along a circle of radius L with angular frequency w through the strongly coupled plasma of N=4 supersymmetric Yang-Mills (SYM) theory. We find that for most values of L and w the energy deposited by stirring the plasma in this way is governed either by the drag force acting on a test quark moving through the plasma in a straight line with speed v=Lw or by the energy radiated by a quark in circular motion in the absence of any plasma, whichever is larger. There is a continuous crossover from the drag-dominated regime to the radiation-dominated regime. In the crossover regime we find evidence for significant destructive interference between energy loss due to drag and that due to radiation as if in vacuum. The rotating quark thus serves as a model system in which the relative strength of, and interplay between, two different mechanisms of parton energy loss is accessible via a controlled classical gravity calculation. We close by speculating on the implicati...

  17. Strong-interaction nonuniversality

    International Nuclear Information System (INIS)

    Volkas, R.R.; Foot, R.; He, X.; Joshi, G.C.


    The universal QCD color theory is extended to an SU(3) 1 direct product SU(3) 2 direct product SU(3) 3 gauge theory, where quarks of the ith generation transform as triplets under SU(3)/sub i/ and singlets under the other two factors. The usual color group is then identified with the diagonal subgroup, which remains exact after symmetry breaking. The gauge bosons associated with the 16 broken generators then form two massive octets under ordinary color. The interactions between quarks and these heavy gluonlike particles are explicitly nonuniversal and thus an exploration of their physical implications allows us to shed light on the fundamental issue of strong-interaction universality. Nonuniversality and weak flavor mixing are shown to generate heavy-gluon-induced flavor-changing neutral currents. The phenomenology of these processes is studied, as they provide the major experimental constraint on the extended theory. Three symmetry-breaking scenarios are presented. The first has color breaking occurring at the weak scale, while the second and third divorce the two scales. The third model has the interesting feature of radiatively induced off-diagonal Kobayashi-Maskawa matrix elements

  18. Neutron absorbers and methods of forming at least a portion of a neutron absorber (United States)

    Guillen, Donna P; Porter, Douglas L; Swank, W David; Erickson, Arnold W


    Methods of forming at least a portion of a neutron absorber include combining a first material and a second material to form a compound, reducing the compound into a plurality of particles, mixing the plurality of particles with a third material, and pressing the mixture of the plurality of particles and the third material. One or more components of neutron absorbers may be formed by such methods. Neutron absorbers may include a composite material including an intermetallic compound comprising hafnium aluminide and a matrix material comprising pure aluminum.

  19. Absorbing Aerosols Workshop, January 20-21, 2016

    Energy Technology Data Exchange (ETDEWEB)

    Nasiri, Shaima [Brookhaven National Lab. (BNL), Upton, NY (United States); Williamson, Ashley [Brookhaven National Lab. (BNL), Upton, NY (United States); Cappa, Christopher D. [Univ. of California, Berkeley, CA (United States); Kotamarthi, Davis Rao [Argonne National Lab. (ANL), Argonne, IL (United States); Sedlacek, Arthur J. [Brookhaven National Lab. (BNL), Upton, NY (United States); Flynn, Conner [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Lewis, Ernie [Brookhaven National Lab. (BNL), Upton, NY (United States); McComiskey, Allison [National Oceanic and Atmospheric Administration (NOAA), Boulder, CO (United States); Riemer, Nicole [Univ. of Illinois, Chicago, IL (United States)


    A workshop was held at DOE Headquarters on January 20-21, 2016 during which experts within and outside DOE were brought together to identify knowledge gaps in modeling and measurement of the contribution of absorbing aerosols (AA) to radiative forcing. Absorbing aerosols refer to those aerosols that absorb light, whereby they both reduce the amount of sunlight reaching the surface (direct effect) and heat their surroundings. By doing so, they modify the vertical distribution of heat in the atmosphere and affect atmospheric thermodynamics and stability, possibly hastening cloud drop evaporation, and thereby affecting cloud amount, formation, dissipation and, ultimately, precipitation. Deposition of AA on snow and ice reduces surface albedo leading to accelerated melt. The most abundant AA type is black carbon (BC), which results from combustion of fossil fuel and biofuel. The other key AA types are brown carbon (BrC), which also results from combustion of fossil fuel and biofuel, and dust (crustal material). Each of these sources may result from, and be strongly influenced by, anthropogenic activities. The properties and amounts of AA depend upon various factors, primarily fuel source and burn conditions (e.g., internal combustion engine, flaming or smoldering wildfire), vegetation type (in the case of BC and BrC), and in the case of dust, soil type and ground cover (i.e., vegetation, snow, etc.). After emission, AA undergo chemical processing in the atmosphere that affects their physical and chemical properties. Thus, attribution of sources of AA, and understanding processes AA undergo during their atmospheric lifetimes, are necessary to understand how they will behave in a changing climate.

  20. Absorbed dose thresholds and absorbed dose rate limitations for studies of electron radiation effects on polyetherimides (United States)

    Long, Edward R., Jr.; Long, Sheila Ann T.; Gray, Stephanie L.; Collins, William D.


    The threshold values of total absorbed dose for causing changes in tensile properties of a polyetherimide film and the limitations of the absorbed dose rate for accelerated-exposure evaluation of the effects of electron radiation in geosynchronous orbit were studied. Total absorbed doses from 1 kGy to 100 MGy and absorbed dose rates from 0.01 MGy/hr to 100 MGy/hr were investigated, where 1 Gy equals 100 rads. Total doses less than 2.5 MGy did not significantly change the tensile properties of the film whereas doses higher than 2.5 MGy significantly reduced elongation-to-failure. There was no measurable effect of the dose rate on the tensile properties for accelerated electron exposures.

  1. TEM characterization of a Cr/Ti/TiC graded interlayer for magnetron-sputtered TiC/a-C : H nanocomposite coatings

    NARCIS (Netherlands)

    Galvan, D.; Pei, Y.T.; Hosson, J.Th.M. De

    A TiC/a-C:H nanocomposite coating is deposited on top of a Cr/Ti/TiC graded interlayer. Cross-section transmission electron microscopy is employed to investigate the detailed structure of the interlayer and the coating. Five different phases are formed as a consequence of the compositional gradient

  2. A Design Case of the T.E.C.H. Playground: Decisions and Challenges in Creating a Space/Place to Transform Education through Creative Habits (United States)

    Stansberry, Susan L.


    This design case (Boling, 2010) includes the challenges, considerations, and decisions associated with the design and development of a learning space/place (Dourish, 2006; Harrison & Dourish, 1996) focused on innovative, creative, and imaginative ways to transform teaching and learning with technology. The T.E.C.H. Playground in the College of…

  3. Additional Value of CH4 Measurement in a Combined 13C/H2 Lactose Malabsorption Breath Test: A Retrospective Analysis (United States)

    Houben, Els; De Preter, Vicky; Billen, Jaak; Van Ranst, Marc; Verbeke, Kristin


    The lactose hydrogen breath test is a commonly used, non-invasive method for the detection of lactose malabsorption and is based on an abnormal increase in breath hydrogen (H2) excretion after an oral dose of lactose. We use a combined 13C/H2 lactose breath test that measures breath 13CO2 as a measure of lactose digestion in addition to H2 and that has a better sensitivity and specificity than the standard test. The present retrospective study evaluated the results of 1051 13C/H2 lactose breath tests to assess the impact on the diagnostic accuracy of measuring breath CH4 in addition to H2 and 13CO2. Based on the 13C/H2 breath test, 314 patients were diagnosed with lactase deficiency, 138 with lactose malabsorption or small bowel bacterial overgrowth (SIBO), and 599 with normal lactose digestion. Additional measurement of CH4 further improved the accuracy of the test as 16% subjects with normal lactose digestion and no H2-excretion were found to excrete CH4. These subjects should have been classified as subjects with lactose malabsorption or SIBO. In conclusion, measuring CH4-concentrations has an added value to the 13C/H2 breath test to identify methanogenic subjects with lactose malabsorption or SIBO. PMID:26371034

  4. Additional Value of CH4 Measurement in a Combined 13C/H2 Lactose Malabsorption Breath Test: A Retrospective Analysis

    Directory of Open Access Journals (Sweden)

    Els Houben


    Full Text Available The lactose hydrogen breath test is a commonly used, non-invasive method for the detection of lactose malabsorption and is based on an abnormal increase in breath hydrogen (H2 excretion after an oral dose of lactose. We use a combined 13C/H2 lactose breath test that measures breath 13CO2 as a measure of lactose digestion in addition to H2 and that has a better sensitivity and specificity than the standard test. The present retrospective study evaluated the results of 1051 13C/H2 lactose breath tests to assess the impact on the diagnostic accuracy of measuring breath CH4 in addition to H2 and 13CO2. Based on the 13C/H2 breath test, 314 patients were diagnosed with lactase deficiency, 138 with lactose malabsorption or small bowel bacterial overgrowth (SIBO, and 599 with normal lactose digestion. Additional measurement of CH4 further improved the accuracy of the test as 16% subjects with normal lactose digestion and no H2-excretion were found to excrete CH4. These subjects should have been classified as subjects with lactose malabsorption or SIBO. In conclusion, measuring CH4-concentrations has an added value to the 13C/H2 breath test to identify methanogenic subjects with lactose malabsorption or SIBO.

  5. Tribological Behavior of TiC/a-C : H-Coated and Uncoated Steels Sliding Against Phenol-Formaldehyde Composite Reinforced with PTFE and Glass Fibers

    NARCIS (Netherlands)

    Shen, J.T.; Pei, Y.T.; Hosson, J.Th.M. De


    Tribological experiments on phenol-formaldehyde composite reinforced with polytetrafluoroethylene (PTFE) and glass fibers were performed against 100Cr6 steel and TiC/a-C:H thin film-coated 100Cr6 steel. In both cases, the coefficient of friction increases with increasing sliding distance until a

  6. Tribological properties of nc-TiC/a-C : H coatings prepared by magnetron sputtering at low and high ion bombardment of the growing film

    NARCIS (Netherlands)

    Souček, Pavel; Schmidtová, Tereza; Buršíková, Vilma; Vašina, Petr; Pei, Y.T.; Hosson, J.Th.M. De; Caha, Ondřej; Peřina, Vratislav; Mikšová, Romana; Malinský, Petr


    Two series of nc-TiC/a-C:H coatings were deposited by a hybrid PVD–PECVD process of titanium sputtering in argon/acetylene atmosphere at two configurations of magnetic field resulting in different impinging ion fluxes on the growing film. The composition of the coatings was varied by changing the

  7. Mechanistic insight into conjugated N-N bond cleavage by Rh(III)-catalyzed redox-neutral C-H activation of pyrazolones. (United States)

    Wu, Weirong; Liu, Yuxia; Bi, Siwei


    Density functional theory (DFT) calculations have been performed to investigate the detailed mechanism of Rh(III)-catalyzed redox-neutral C-H activation of pyrazolones with PhC≡CPh. It is found that (1) the methylene C-H activation is prior to the phenyl C-H activation, (2) the N-N bond cleavage is realized via Rh(III) → Rh(I) → Rh(III) rather than via Rh(III) → Rh(V) → Rh(III). The zwitterionic Rh(I) complex is identified to be a key intermediate in promoting the N-N bond cleavage. (3) Different from the Rh(III)-catalyzed hydrazine-directed C-H activation for indole synthesis, the rate-determining step of the reaction studied in this work is the Rh(III) → Rh(I) → Rh(III) process resulting in the N-N bond cleavage rather than the alkyne insertion step. The present theoretical study provides new insight into the mechanism of the conjugated N-N bond cleavage.

  8. Infrared and Raman spectroscopy and quantum chemistry calculation studies of C-H...O hydrogen bondings and thermal behavior of biodegradable polyhydroxyalkanoate

    Czech Academy of Sciences Publication Activity Database

    Sato, H.; Dybal, Jiří; Murakami, R.; Noda, I.; Ozaki, Y.

    744-747, - (2005), s. 35-46 ISSN 0022-2860 R&D Projects: GA AV ČR IAA4050208 Keywords : infrared and Raman spectroscopy * quantum chemical calculation * C-H...O hydrogen bonding Subject RIV: CD - Macromolecular Chemistry Impact factor: 1.440, year: 2005

  9. Optimization of the contact resistance in the interface structure of n-type Al/a-SiC:H by thermal annealing for optoelectronics applications

    Energy Technology Data Exchange (ETDEWEB)

    Ambrosio, Roberto; Mireles, Jose Jr. [Technology and Engineering Institute, Ciudad Juarez University UACJ, Av. Del Charro 450N, 32310, Chihuahua (Mexico); Torres, Alfonso; Zuniga, Carlos; Moreno, Mario [National Institute for Astrophysics Optics and Electronics INAOE, Luis E. Erro 1, PO Box 51 and 216, 7200, Puebla (Mexico)


    The presented work meets the requirements for integration of amorphous silicon carbon films with silicon technology in order to obtain a complete optoelectronic system such as light emitting diodes and its electronic readout circuits. The key enabler for this integration scheme is the low temperature of deposition of a-SiC:H films and an ohmic behavior in the interface metal/a-SiC:H. In this work, the optimization of the interface Al/a-SiC:H films are performed by means of thermal annealing timing. The a-SiC:H films were deposited by enhanced chemical vapor deposition from CH{sub 4}/SiH{sub 4} and C{sub 2}H{sub 2}/SiH{sub 4} mixtures. The structural and optical properties of the deposited films are presented. An implantation phosphorous dose was used for doping before fabrication of patterned aluminum contacts. The implanted films were electrically characterized by the transfer length method (TLM) measuring a sheet resistance value as low as 171 M{omega}/square. The Schottky behavior was improved to ohmic behavior after several hours in thermal annealing treatments at 350 C, which allows to obtain a reasonable contact resistance values in the range from 8.6 to 26.8 k{omega}. (Abstract Copyright [2010], Wiley Periodicals, Inc.)

  10. A Role for Pd(IV) in Catalytic Enantioselective C-H Functionalization with Monoprotected Amino Acid Ligands under Mild Conditions. (United States)

    Plata, R Erik; Hill, David E; Haines, Brandon E; Musaev, Djamaladdin G; Chu, Ling; Hickey, David P; Sigman, Matthew S; Yu, Jin-Quan; Blackmond, Donna G


    Kinetic and mechanistic studies of the desymmetrization of benzhydrylamine using Pd/monoprotected amino acid ligands (Pd/MPAA) via C-H functionalization with molecular iodine provide mechanistic insight into the rate-determining step and the oxidation state of Pd in the C-H functionalization step. Enantiomeric excess is strikingly insensitive to temperature from ambient temperature up to over 70 °C, and reaction rate is insensitive to the electronic characteristics of the ligand's benzoyl protecting group. The reaction is highly robust with no evidence of catalyst deactivation. Intriguingly, C-H bond breaking does not occur prior to the addition of I 2 to the reaction mixture. Electrochemical experiments demonstrate the viability of oxidative addition of I 2 to Pd(II). Together with 19 F NMR studies, these observations suggest that iodine oxidizes Pd prior to addition of the amine substrate. This work may lead to a better general understanding of the subtle variations in the reaction mechanisms for C-H functionalization reactions that may be extant for this ligand class depending on substrate, amino acid ligand and protecting group, and reaction conditions.

  11. Ag1 Pd1 Nanoparticles-Reduced Graphene Oxide as a Highly Efficient and Recyclable Catalyst for Direct Aryl C-H Olefination. (United States)

    Hu, Qiyan; Liu, Xiaowang; Wang, Guoliang; Wang, Feifan; Li, Qian; Zhang, Wu


    The efficient and selective palladium-catalyzed activation of C-H bonds is of great importance for the construction of diverse bioactive molecules. Despite significant progress, the inability to recycle palladium catalysts and the need for additives impedes the practical applications of these reactions. Ag 1 Pd 1 nanoparticles-reduced graphene oxide (Ag 1 Pd 1 -rGO) was used as highly efficient and recyclable catalyst for the chelation-assisted ortho C-H bond olefination of amides with acrylates in good yields with a broad substrate scope. The catalyst can be recovered and reused at least 5 times without losing activity. A synergistic effect between the Ag and Pd atoms on the catalytic activity was found, and a plausible mechanism for the AgPd-rGO catalyzed C-H olefination is proposed. These findings suggest that the search for such Pd-based bimetallic alloy nanoparticles is a new method towards the development of superior recyclable catalysts for direct aryl C-H functionalization under mild conditions. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Process control by optical emission spectroscopy during growth of a-C:H from a CH4 plasma by plasma-enhanced chemical vapour deposition

    DEFF Research Database (Denmark)

    Barholm-Hansen, C; Bentzon, MD; Vigild, Martin Etchells


    During the growth of a-C:H thin films for tribological applications, the characteristic optical emission from a CH4 plasma was used to estimate growth conditions such as the degree of dissociation of the feed gas, the deposition rate and the presence of impurities. Films were fabricated with vari...

  13. Synthesis of 2,3-Benzodiazepines via Rh(III)-Catalyzed C-H Functionalization of N-Boc Hydrazones with Diazoketoesters. (United States)

    Wang, Jie; Wang, Lili; Guo, Shan; Zha, Shanke; Zhu, Jin


    An efficient Rh(III)-catalyzed C-H activation protocol has been developed for the synthesis of 2,3-benzodiazepines with use of N-Boc hydrazones and diazoketoesters as substrates. The reaction features retention of the C═N and N-N bonds and selective cleavage of the N-Boc moiety.

  14. C-H activation of imidazolium salts by Pt(0) at ambient temperature: synthesis of hydrido platinum bis(carbene) compounds. (United States)

    Duin, Marcel A; Clement, Nicolas D; Cavell, Kingsley J; Elsevier, Cornelis J


    A zerovalent platinum(carbene) complex with two monoalkene ligands, which is able to activate C-H bonds of imidazolium salts at room temperature to yield isolable hydrido platinum(II) bis(carbene) compounds, has been synthesised for the first time.

  15. Birge-Sponer Estimation of the C-H Bond Dissociation Energy in Chloroform Using Infrared, Near-Infrared, and Visible Absorption Spectroscopy: An Experiment in Physical Chemistry (United States)

    Myrick, M. L.; Greer, A. E.; Nieuwland, A. A.; Priore, R. J.; Scaffidi, J.; Andreatta, Danielle; Colavita, Paula


    The fundamental and overtone vibrational absorption spectroscopy of the C-H unit in CHCl[subscript 3] is measured for transitions from the v = 0 energy level to v = 1 through v = 5 energy levels. The energies of the transitions exhibit a linearly-decreasing spacing between adjacent vibrational levels as the vibrational quantum number increases.…

  16. Intrascleral outflow after deep sclerectomy with absorbable and non-absorbable implants in the rabbit eye. (United States)

    Kałużny, Jakub J; Grzanka, Dariusz; Wiśniewska, Halina; Niewińska, Alicja; Kałużny, Bartłomiej J; Grzanka, Alina


    The purpose of the study is an analysis of intrascleral drainage vessels formed in rabbits' eyes after non-penetrating deep sclerectomy (NPDS) with absorbable and non-absorbable implants, and comparison to eyes in which surgery was performed without implanted material. NPDS was carried out in 12 rabbits, with implantation of non-absorbable methacrylic hydrogel (N=10 eyes) or absorbable cross-linked sodium hyaluronate (N=6 eyes), or without any implant (N=8 eyes). All the animals were euthanized 1 year after surgery. Twenty-one eyeballs were prepared for light microscopy and 3 were prepared for transmission electron microscope (TEM) analysis. Aqueous humour pathways were stained with ferritin in 6 eyeballs. By light microscopy, small vessels adjacent to the areas of scarring were the most common abnormality. Vessel density was significantly higher in operated sclera compared to normal, healthy tissue, regardless of the type of implant used. The average vessel densities were 2.18±1.48 vessels/mm2 in non-implanted sclera, 2.34±1.69 vessels/mm2 in eyes with absorbable implants, and 3.64±1.78 vessels/mm2 in eyes with non-absorbable implants. Analysis of iron distribution in ferritin-injected eyes showed a positive reaction inside new aqueous draining vessels in all groups. TEM analysis showed that the ultrastructure of new vessels matched the features of the small veins. Aqueous outflow after NPDS can be achieved through the newly formed network of small intrascleral veins. Use of non-absorbable implants significantly increases vessel density in the sclera adjacent to implanted material compared to eyes in which absorbable implants or no implants were used.

  17. Quantification of the selective activation of C--H bonds in short chain alkanes: The reactivity of ethane, propane, isobutane, n-butane, and neopentane on Ir(111)

    International Nuclear Information System (INIS)

    Johnson, D.F.; Weinberg, W.H.


    The initial probabilities of precursor-mediated, dissociative chemisorption of the saturated hydrocarbons 13 C-labeled ethane, propane, isobutane, n-butane, and neopentane on the close-packed Ir(111) surface have been measured. The selective activation of primary (1 degree), secondary (2 degree), and tertiary (3 degree) C--H bonds has been quantified by examining the reactivities of the selectively deuterated isotopomers of propane, C 3 H 8 , CH 3 CD 2 CH 3 , and C 3 D 8 , and of isobutane, (CH 3 ) 3 CH, (CH 3 ) 3 CD, and (CD 3 ) 3 CH. With respect to the bottom of the physically adsorbed well for each hydrocarbon, the apparent C--H bond activation energies have been found to be 10.4±0.3 kcal/mol (ethane), 11.4±0.3 kcal/mol (propane), 11.5±0.3 kcal/mol (n-butane), 11.3±0.3 kcal/mol (i-butane), and 11.3±0.3 kcal/mol (neopentane). For all the alkanes examined, the ratios of the preexponential factors of the rate coefficients of reaction and desorption are 1x10 -2 . The C--D bond activation energies are higher than the corresponding C--H bond activation energies by 480 cal/mol (ethane), 630 cal/mol (propane), and 660 cal/mol (i-butane). By analyzing the primary kinetic isotope effects for the selectively deuterated isotopomers of propane and isobutane, the 2 degree C--H bond activation energy is found to be 310±160 cal/mol less than the 1 degree C--H bond activation energy on this surface, and similarly, 3 degree C--H bond cleavage is less by 80±70 cal/mol. The quantification of the branching ratios within the C--H bond activation channel for propane and isobutane on this surface shows that the formation of 1 degree-alkyl intermediates is, in general, favored over the formation of either 2 degree- or 3 degree-alkyl intermediates. (Abstract Truncated)

  18. Effect of the bio-absorbent on the microwave absorption property of the flaky CIPs/rubber absorbers

    Energy Technology Data Exchange (ETDEWEB)

    Cheng, Yang; Xu, Yonggang, E-mail:; Cai, Jun; Yuan, Liming; Zhang, Deyuan


    Microwave absorbing composites filled with flaky carbonyl iron particles (CIPs) and the bio-absorbent were prepared by using a two-roll mixer and a vulcanizing machine. The electromagnetic (EM) parameters were measured by a vector network analyzer and the reflection loss (RL) was measured by the arch method in the frequency range of 1–4 GHz. The uniform dispersion of the absorbents was verified by comparing the calculated RL with the measured one. The results confirm that as the bio-absorbent was added, the permittivity was increased due to the volume content of absorbents, and the permeability was enlarged owing to the volume content of CIPs and interactions between the two absorbents. The composite filled with bio-absorbents achieved an excellent absorption property at a thickness of 1 mm (minimum RL reaches −7.8 dB), and as the RL was less than −10 dB the absorption band was widest (2.1–3.8 GHz) at a thickness of 2 mm. Therefore, the bio-absorbent is a promising additive candidate on fabricating microwave absorbing composites with a thinner thickness and wider absorption band. - Graphical abstract: Morphology of composites filled with flaky CIPs and the bio-absorbent. The enhancement of bio-absorbent on the electromagnetic absorption property of composites filled with flaky carbonyl iron particles (CIPs) is attributed to the interaction of the two absorbents. The volume content of the FCMPs with the larger shape CIPs play an important role in this effects, the composites filled with irons and bio-absorbents can achieve wider-band and thinner-thickness absorbing materials. - Highlights: • Absorbers filled with bio-absorbents and CIPs was fabricated. • Bio-absorbents enhanced the permittivity and permeability of the composites. • The absorbent interactions play a key role in the enhancement mechanism. • Bio-absorbents enhanced the composite RL in 1–4 GHz.

  19. Disposable Diaper Absorbency: Improvements via Advanced Designs. (United States)

    Helmes, C Tucker; O'Connor, Robert; Sawyer, Larry; Young, Sharon


    Absorbency effectiveness in diapers has improved significantly in recent years with the advent of new ingredient combinations and advanced design features. With these features, many leading products maintain their dryness performance overnight. Considering the importance of holding liquid away from the skin, ongoing research in diaper construction focuses on strategies to increase the effectiveness to capture liquid and help avoid rewetting of infant skin. The layout and design of a disposable diaper allows for distribution of absorbency features where they can provide the optimal benefit. Clinical evidence indicates materials can keep moisture away from the skin in the diapered area, helping maintain proper skin hydration, minimizing irritation, and contributing to reduced rates of diaper rash. © The Author(s) 2014.

  20. Use of Wedge Absorbers in MICE

    Energy Technology Data Exchange (ETDEWEB)

    Neuffer, D. [Fermi National Accelerator Lab. (FNAL), Batavia, IL (United States); Summers, D. [Univ. of Mississippi, Oxford, MS (United States); Mohayai, T. [Fermi National Accelerator Lab. (FNAL), Batavia, IL (United States); IIT, Chicago, IL (United States); Snopok, P. [Fermi National Accelerator Lab. (FNAL), Batavia, IL (United States); IIT, Chicago, IL (United States); Rogers, C. [Science and Technology Facilities Council (STFC), Oxford (United Kingdom). Rutherford Appleton Lab. (RAL)


    Wedge absorbers are needed to obtain longitudinal cooling in ionization cooling. They also can be used to obtain emittance exchanges between longitudinal and transverse phase space. There can be large exchanges in emittance, even with single wedges. In the present note we explore the use of wedge absorbers in the MICE experiment to obtain transverse–longitudinal emittance exchanges within present and future operational conditions. The same wedge can be used to explore “direct” and “reverse” emittance exchange dynamics, where direct indicates a configuration that reduces momentum spread and reverse is a configuration that increases momentum spread. Analytical estimated and ICOOL and G4BeamLine simulations of the exchanges at MICE parameters are presented. Large exchanges can be obtained in both reverse and direct configurations.

  1. Absorbing Software Testing into the Scrum Method (United States)

    Tuomikoski, Janne; Tervonen, Ilkka

    In this paper we study, how to absorb software testing into the Scrum method. We conducted the research as an action research during the years 2007-2008 with three iterations. The result showed that testing can and even should be absorbed to the Scrum method. The testing team was merged into the Scrum teams. The teams can now deliver better working software in a shorter time, because testing keeps track of the progress of the development. Also the team spirit is higher, because the Scrum team members are committed to the same goal. The biggest change from test manager’s point of view was the organized Product Owner Team. Test manager don’t have testing team anymore, and in the future all the testing tasks have to be assigned through the Product Backlog.

  2. Theory of metasurface based perfect absorbers (United States)

    Alaee, Rasoul; Albooyeh, Mohammad; Rockstuhl, Carsten


    Based on an analytic approach, we present a theoretical review on the absorption, scattering, and extinction of both dipole scatterers and regular arrays composed of such scatterers i.e. metasurfaces. Besides offering a tutorial by outlining the maximum absorption limit for electrically/magnetically resonant dipole particles/metasurfaces, we give an educative analytical approach to their analysis. Moreover, we put forward the analysis of two known alternatives in providing perfect absorbers out of electrically and or magnetically resonant metasurfaces; one is based on the simultaneous presence of both electric and magnetic responses in so called Huygens metasurfaces while the other is established upon the presence of a back reflector in so called Salisbury absorbers. Our work is supported by several numerical examples to clarify the discussions in each stage.

  3. Microstructured extremely thin absorber solar cells

    DEFF Research Database (Denmark)

    Biancardo, Matteo; Krebs, Frederik C


    In this paper we present the realization of extremely thin absorber (ETA) solar cells employing conductive glass substrates functionalized with TiO2 microstructures produced by embossing. Nanocrystalline or compact TiO2 films on Indium doped tin oxide (ITO) glass substrates were embossed by press......In this paper we present the realization of extremely thin absorber (ETA) solar cells employing conductive glass substrates functionalized with TiO2 microstructures produced by embossing. Nanocrystalline or compact TiO2 films on Indium doped tin oxide (ITO) glass substrates were embossed...... by pressing a silicon stamp containing a mu m size raised grid structure into the TiO2 by use of a hydraulic press (1 ton/50 cm(2)). The performance of these microstructured substrates in a ETA cell sensitized by a thermally evaporated or chemical bath deposited PbS film and completed by a PEDOT:PSS hole...

  4. Room Modal Equalisation with Electroacoustic Absorbers


    Rivet, Etienne Thierry Jean-Luc


    The sound quality in a room is of fundamental importance for both recording and reproducing processes. Because of the room modes, the distributions in space and frequency of the sound field are largely altered. Excessive rise and decay times caused by the resonances might even mask some details at higher frequencies, and these irregularities may be heard as a coloration of the sound. To address this problem, passive absorbers are bulky and too inefficient to significantly improve the listen...

  5. Absorbed Doses to Patients in Nuclear Medicine

    International Nuclear Information System (INIS)

    Leide-Svegborn, Sigrid; Mattsson, Soeren; Nosslin, Bertil; Johansson, Lennart


    The work with a Swedish catalogue of radiation absorbed doses to patients undergoing nuclear medicine investigations has continued. After the previous report in 1999, biokinetic data and dose estimates (mean absorbed dose to various organs and tissues and effective dose) have been produced for a number of substances: 11 C- acetate, 11 C- methionine, 18 F-DOPA, whole antibody labelled with either 99m Tc, 111 In, 123 I or 131 I, fragment of antibody, F(ab') 2 labelled with either 99m Tc, 111 In, 123 I or 131 I and fragment of antibody, Fab' labelled with either 99m Tc, 111 In, 123 I or 131 I. The absorbed dose estimates for these substances have been made from published biokinetic information. For other substances of interest, e.g. 14 C-urea (children age 3-6 years), 14 C-glycocholic acid, 14 C-xylose and 14 C-triolein, sufficient literature data have not been available. Therefore, a large number of measurements on patients and volunteers have been carried out, in order to determine the biokinetics and dosimetry for these substances. Samples of breast milk from 50 mothers, who had been subject to nuclear medicine investigations, have been collected at various times after administration of the radiopharmaceutical to the mother. The activity concentration in the breast milk samples has been measured. The absorbed dose to various organs and tissues and the effective dose to the child who ingests the milk have been determined for 17 different radiopharmaceuticals. Based on these results revised recommendations for interruption of breast-feeding after nuclear medicine investigations are suggested

  6. On the comparison of absorbing regions methods


    Ke , Weina; Yaacoubi , Slah; Mckeon , Peter


    International audience; Numerical simulation methods are very useful in Non Destructive Testing because they save time, lower cost and allow for the investigation of diverse experimental configurations. However, these methods consume relatively long CPU time and system memory. Different solutions exist to minimize these limitations. Absorbing region methods are among them when it’s possible. These kinds of regions are also made to minimize or eliminate the spurious reflections at the boundari...

  7. 2D Saturable Absorbers for Fibre Lasers

    Directory of Open Access Journals (Sweden)

    Robert I. Woodward


    Full Text Available Two-dimensional (2D nanomaterials are an emergent and promising platform for future photonic and optoelectronic applications. Here, we review recent progress demonstrating the application of 2D nanomaterials as versatile, wideband saturable absorbers for Q-switching and mode-locking fibre lasers. We focus specifically on the family of few-layer transition metal dichalcogenides, including MoS2, MoSe2 and WS2.

  8. Strain-enhanced optical absorbance of topological insulator films

    DEFF Research Database (Denmark)

    Brems, Mathias Rosdahl; Paaske, Jens; Lunde, Anders Mathias


    Topological insulator films are promising materials for optoelectronics due to a strong optical absorption and a thickness-dependent band gap of the topological surface states. They are superior candidates for photodetector applications in the THz-infrared spectrum, with a potential performance...... higher than graphene. Using a firstprinciples k.p Hamiltonian, incorporating all symmetry-allowed terms to second order in the wave vector k, first order in the strain c, and of order ck, we demonstrate a significantly improved optoelectronic performance due to strain. For Bi2Se3 films of variable...... thickness, the surface-state band gap, and thereby the optical absorption, can be effectively tuned by the application of uniaxial strain epsilon(zz), leading to a divergent band-edge absorbance for epsilon(zz) greater than or similar to 6%. Shear strain breaks the crystal symmetry and leads...

  9. Heaving buoys, point absorbers and arrays. (United States)

    Falnes, Johannes; Hals, Jørgen


    Absorption of wave energy may be considered as a phenomenon of interference between incident and radiated waves generated by an oscillating object; a wave-energy converter (WEC) that displaces water. If a WEC is very small in comparison with one wavelength, it is classified as a point absorber (PA); otherwise, as a 'quasi-point absorber'. The latter may be a dipole-mode radiator, for instance an immersed body oscillating in the surge mode or pitch mode, while a PA is so small that it should preferably be a source-mode radiator, for instance a heaving semi-submerged buoy. The power take-off capacity, the WEC's maximum swept volume and preferably also its full physical volume should be reasonably matched to the wave climate. To discuss this matter, two different upper bounds for absorbed power are applied in a 'Budal diagram'. It appears that, for a single WEC unit, a power capacity of only about 0.3 MW matches well to a typical offshore wave climate, and the full physical volume has, unfortunately, to be significantly larger than the swept volume, unless phase control is used. An example of a phase-controlled PA is presented. For a sizeable wave-power plant, an array consisting of hundreds, or even thousands, of mass-produced WEC units is required.

  10. An absorbed dose calorimeter for IMRT dosimetry

    International Nuclear Information System (INIS)

    Duane, S.; Aldehaybes, M.; Bailey, M.; Lee, N.D.; Thomas, C.G.; Palmans, H.


    A new calorimeter for dosimetry in small and complex fields has been built. The device is intended for the direct determination of absorbed dose to water in moderately small fields and in composite fields such as IMRT treatments, and as a transfer instrument calibrated against existing absorbed dose standards in conventional reference conditions. The geometry, materials and mode of operation have been chosen to minimize detector perturbations when used in a water phantom, to give a reasonably isotropic response and to minimize the effects of heat transfer when the calorimeter is used in non-reference conditions in a water phantom. The size of the core is meant to meet the needs of measurement in IMRT treatments and is comparable to the size of the air cavity in a type NE2611 ionization chamber. The calorimeter may also be used for small field dosimetry. Initial measurements in reference conditions and in an IMRT head and neck plan, collapsed to gantry angle zero, have been made to estimate the thermal characteristics of the device, and to assess its performance in use. The standard deviation (estimated repeatability) of the reference absorbed dose measurements was 0.02 Gy (0.6%). (authors)

  11. Thermal expansion absorbing structure for pipeline

    International Nuclear Information System (INIS)

    Nagata, Takashi; Yamashita, Takuya.


    A thermal expansion absorbing structure for a pipeline is disposed to the end of pipelines to form a U-shaped cross section connecting a semi-circular torus shell and a short double-walled cylindrical tube. The U-shaped longitudinal cross-section is deformed in accordance with the shrinking deformation of the pipeline and absorbs thermal expansion. Namely, since the central lines of the outer and inner tubes of the double-walled cylindrical tube deform so as to incline, when the pipeline is deformed by thermal expansion, thermal expansion can be absorbed by a simple configuration thereby enabling to contribute to ensure the safety. Then, the entire length of the pipeline can greatly be shortened by applying it to the pipeline disposed in a high temperature state compared with a method of laying around a pipeline using only elbows, which has been conducted so far. Especially, when it is applied to a pipeline for an FBR-type reactor, the cost for the construction of a facility of a primary systems can greater be reduced. In addition, it can be applied to a pipeline for usual chemical plants and any other structures requiring absorption of deformation. (N.H.)

  12. CO2 Absorbing Capacity of MEA

    Directory of Open Access Journals (Sweden)

    José I. Huertas


    Full Text Available We describe the use of a gas bubbler apparatus in which the gas phase is bubbled into a fixed amount of absorbent under standard conditions as a uniform procedure for determining the absorption capacity of solvents. The method was systematically applied to determine the CO2 absorbing capacity of MEA (Ac at several aqueous MEA (β and gas-phase CO2 concentrations. Ac approached the nominal CO2 absorbing capacity of MEA (720 g CO2/kg MEA at very low β levels, increasing from 447.9±18.1 to 581.3±32.3 g CO2/kg MEA as β was reduced from 30 to 2.5% (w/w. Ac did not depend on the CO2 concentration in the inlet gas stream as long as the gas stream did not include other amine sensitive components. During the bubbling tests the outlet CO2 concentration profiles exhibited a sigmoidal shape that could be described by an exponential equation characterized by an efficiency factor (a and a form factor (n. Statistical analysis based on correlation analysis indicated that in all cases the experimental data fit the equation well when a was 6.1±0.35 and n was 2.5±0.12. The results of these experiments may be used to optimize scrubber designs for CO2 sequestration from fossil fuel derived flue gases.

  13. Wide band cryogenic ultra-high vacuum microwave absorber (United States)

    Campisi, I.E.


    An absorber waveguide assembly for absorbing higher order modes of microwave energy under cryogenic ultra-high vacuum conditions, that absorbs wide-band multi-mode energy. The absorber is of a special triangular shape, made from flat tiles of silicon carbide and aluminum nitride. The leading sharp end of the absorber is located in a corner of the waveguide and tapers to a larger cross-sectional area whose center is located approximately in the center of the wave guide. The absorber is relatively short, being of less height than the maximum width of the waveguide. 11 figs.

  14. Homolytic bond dissociation energies for C-H bonds adjacent to sulfur and aromatic moieties: The effects of substituents of C-H bond strengths of the benzylic positions in coal model compounds

    Energy Technology Data Exchange (ETDEWEB)

    Alnajjar, M.S.; Franz, J.A. [Pacific Northwest Lab., Richland, WA (United States); Gleicher, G.J.; Truksa, S. [Oregon State Univ., Corvallis, OR (United States). Dept. of Chemistry; Bordwell, F.; Zhang, Xian-Man [Northwestern Univ., Evanston, IL (United States). Dept. of Chemistry


    Sulfur-containing compounds are precursors for thiyl radicals at coal liquefaction temperatures due to the weakness of The and S-S bonds. Thiyl radicals play important roles in hydrogen atom shuttling between benzylic positions and catalyze the cleavage and the formation of strong C-C bonds. Although many reactions of thiyl and other sulfur-containing radicals are qualitatively understood, the homolytic bond dissociation energies (EDE`s) and the thermochemistry associated with many key high molecular weight hydrocarbon and sulfur-containing organic structures important to coal is lacking because they are inappropriate for gas-phase techniques. The measurement of BDE`s has been proven to be difficult even in the simplest of molecules.

  15. Lidar remote sensing of laser-induced incandescence on light absorbing particles in the atmosphere. (United States)

    Miffre, Alain; Anselmo, Christophe; Geffroy, Sylvain; Fréjafon, Emeric; Rairoux, Patrick


    Carbon aerosol is now recognized as a major uncertainty on climate change and public health, and specific instruments are required to address the time and space evolution of this aerosol, which efficiently absorbs light. In this paper, we report an experiment, based on coupling lidar remote sensing with Laser-Induced-Incandescence (LII), which allows, in agreement with Planck's law, to retrieve the vertical profile of very low thermal radiation emitted by light-absorbing particles in an urban atmosphere over several hundred meters altitude. Accordingly, we set the LII-lidar formalism and equation and addressed the main features of LII-lidar in the atmosphere by numerically simulating the LII-lidar signal. We believe atmospheric LII-lidar to be a promising tool for radiative transfer, especially when combined with elastic backscattering lidar, as it may then allow a remote partitioning between strong/less light absorbing carbon aerosols.

  16. Inorganic UV absorbers for the photostabilisation of wood-clearcoating systems: Comparison with organic UV absorbers (United States)

    Aloui, F.; Ahajji, A.; Irmouli, Y.; George, B.; Charrier, B.; Merlin, A.


    Inorganic UV absorbers which are widely used today were originally designed neither as a UV blocker in coatings applications, nor for wood protection. In recent years however, there has been extensive interest in these compounds, especially with regard to their properties as a UV blocker in coating applications. In this work, we carried out a comparative study to look into some inorganic and organic UV absorbers used in wood coating applications. The aim of this study is to determine the photostabilisation performances of each type of UV absorbers, to seek possible synergies and the influences of different wood species. We have also searched to find eventual correlation between these performances and the influence of UV absorbers on the film properties. Our study has compared the performances of the following UV absorbers: hombitec RM 300, hombitec RM 400 from the Sachtleben Company; transparent yellow and red iron oxides from Sayerlack as inorganic UV absorbers; organic UV absorbers Tinuvin 1130 and Tinuvin 5151 from Ciba Company. The study was carried out on three wood species: Abies grandis, tauari and European oak. The environmental constraints (in particular the limitation of the emission of volatile organic compounds VOCs) directed our choice towards aqueous formulations marketed by the Sayerlack Arch Coatings Company. The results obtained after 800 h of dry ageing showed that the Tinuvins and the hombitecs present better wood photostabilisations. On the other hand in wet ageing, with the hombitec, there are appearances of some cracks and an increase in the roughness of the surface. This phenomenon is absent when the Tinuvins are used. With regard to these results, the thermomechanical analyses relating to the follow-up of the change of the glass transition temperature ( Tg) of the various coating systems, show a different behaviour between the two types of absorbers. However, contrary to organic UV absorbers, inorganic ones tend to increase Tg during ageing

  17. On the radiative effects of light-absorbing impurities on snowpack evolution (United States)

    Dumont, M.; Tuzet, F.; Lafaysse, M.; Arnaud, L.; Picard, G.; Lejeune, Y.; Lamare, M.; Morin, S.; Voisin, D.; Di Mauro, B.


    The presence of light absorbing impurities in snow strongly decreases snow reflectance leading to an increase in the amount of solar energy absorbed by the snowpack. This effect is also known as impurities direct radiative effect. The change in the amount of energy absorbed by the snowpack modifies the temperature profile inside the snowpack and in turn snow metamorphism (impurities indirect radiative effects). In this work, we used the detailed snowpack model SURFEX/ISBA-Crocus with an explicit representation of snow light-absorbing impurities content (Tuzet et al., 2017) fed by medium-resolution ALADIN-Climate atmospheric model to represent dust and black carbon atmospheric deposition fluxes. The model is used at two sites: Col de Porte (medium elevation site in the French Alps) and Torgnon (high elevation site in the Italian Alps). The simulations are compared to in-situ observations and used to quantify the effects of light-absorbing impurities on snow melt rate and timing. The respective parts of the direct and indirect radiative effects of light-absorbing impurities in snow are also computed for the two sites, emphasizing the need to account for the interactions between snow metamorphism and LAI radiative properties, to accurately predict the effects of light-absorbing impurities in snow. Moreover, we describe how automated hyperspectral reflectance can be used to estimate effective impurities surface content in snow. Finally we demonstrate how these reflectances measurements either from in situ or satellite data can be used via an assimilation scheme to constrain snowpack ensemble simulations and better predict the snowpack state and evolution.

  18. Effect of inclusions' distribution on microwave absorbing properties of composites

    International Nuclear Information System (INIS)

    Qin, Siliang; Wang, Qingguo; Qu, Zhaoming


    Effect of inclusions' spatial distributions on the permeability and permittivity of composites is studied using the generalized Maxwell-Garnett equations. The result indicates that inclusions' orientation distribution can increase the longitudinal electromagnetic parameters. For inclusions' random and orientation distribution, single and three-layer absorbers are designed and optimized using genetic algorithm. The result shows that under a given absorbing requirement, absorber with inclusions' orientation distribution is lighter and thinner than absorber with inclusions' random distribution.

  19. Absorbent material for type a radioactive materials packaging containing liquids

    International Nuclear Information System (INIS)

    Saunders, G.A.


    The application of absorbent materials to the packaging and transport of liquid radioactive materials in Type A packages has not been reported in the literature. However, a significant body of research exists on absorbent materials for personal hygiene products such as diapers. Absorption capacity is dependent on both the absorbent material and the liquid being absorbed. Theoretical principles for capillary absorption in both the horizontal and the vertical plane indicate that small contact angle between the absorbent fibre and the liquid, and a small inter-fibre pore size are important. Some fluid parameters such as viscosity affect the rate of absorption but not the final absorption capacity. There appears to be little comparability between results obtained for the same absorbent and fluid using different test procedures. Test samples of materials from several classes of potential absorbents have been evaluated in this study, and shown to have a wide range of absorbent capacities. Foams, natural fibres, artificial fibres and granular materials are all potentially useful absorbents, with capacities ranging from as little as 0.86 to as much as 40.6 grams of distilled water per gram of absorbent. Two experimental procedures for evaluating the absorbent capacity of these materials have been detailed in this report, and found suitable for evaluating granular, fibrous or foam materials. Compression of the absorbent material reduces its capacity, but parameters such as relative humidity, pH, temperature, and viscosity appear to have little significant influence on capacity. When the materials were loaded to 50% of their one-minute absorbency, subsequent loss of the absorbed liquid was generally minimal. All of the absorbent materials rapidly lost their absorbed water through evaporation within twenty-four hours in still air at 21 degrees C and 50% relative humidity

  20. On (m, n)-absorbing ideals of commutative rings

    Indian Academy of Sciences (India)

    with respect to various ring theoretic constructions and study (m, n)-absorbing ideals in several commutative rings. For example, in a Bézout ring or a Boolean ring, an ideal is an (m, n)-absorbing ideal if and only if it is an n-absorbing ideal, and in an almost. Dedekind domain every (m, n)-absorbing ideal is a product of at ...

  1. 21 CFR 880.5300 - Medical absorbent fiber. (United States)


    ... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Medical absorbent fiber. 880.5300 Section 880.5300 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED... Devices § 880.5300 Medical absorbent fiber. (a) Identification. A medical absorbent fiber is a device...

  2. 21 CFR 868.5310 - Carbon dioxide absorber. (United States)


    ... breathing circuit as a container for carbon dioxide absorbent. It may include a canister and water drain. (b... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Carbon dioxide absorber. 868.5310 Section 868.5310...) MEDICAL DEVICES ANESTHESIOLOGY DEVICES Therapeutic Devices § 868.5310 Carbon dioxide absorber. (a...

  3. 21 CFR 886.3300 - Absorbable implant (scleral buckling method). (United States)


    ... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Absorbable implant (scleral buckling method). 886... SERVICES (CONTINUED) MEDICAL DEVICES OPHTHALMIC DEVICES Prosthetic Devices § 886.3300 Absorbable implant (scleral buckling method). (a) Identification. An absorbable implant (scleral buckling method) is a device...

  4. Application of Taguchi Method to the Optimization of a-C:H Coatings Deposited Using Ion Beam Assisted Physical Vapor Deposition

    Directory of Open Access Journals (Sweden)

    W. H. Kao


    Full Text Available The Taguchi design method is used to optimize the adhesion, hardness, and wear resistance properties of a-C:H coatings deposited on AISI M2 steel substrates using the ion beam assisted physical vapor deposition method. The adhesion strength of the coatings is evaluated by means of scratch tests, while the hardness is measured using a nanoindentation tester. Finally, the wear resistance is evaluated by performing cyclic ball-on-disc wear tests. The Taguchi experimental results show that the optimal deposition parameters are as follows: a substrate bias voltage of 90 V, an ion beam voltage of 1 kV, an acetylene flow rate of 21 sccm, and a working distance of 7 cm. Given these optimal processing conditions, the a-C:H coating has a critical load of 99.8 N, a hardness of 25.5 GPa, and a wear rate of 0.4 × 10−6 mm3/Nm.

  5. A General Cp*CoIII-Catalyzed Intramolecular C-H Activation Approach for the Efficient Total Syntheses of Aromathecin, Protoberberine, and Tylophora Alkaloids. (United States)

    Lerchen, Andreas; Knecht, Tobias; Koy, Maximilian; Daniliuc, Constantin G; Glorius, Frank


    Herein, we report a Cp*Co III -catalyzed C-H activation approach as the key step to create highly valuable isoquinolones and pyridones as building blocks that can readily be applied in the total syntheses of a variety of aromathecin, protoberberine, and tylophora alkaloids. This particular C-H activation/annulation reaction was achieved with several terminal as well as internal alkyne coupling partners delivering a broad scope with excellent functional group tolerance. The synthetic applicability of this protocol reported herein was demonstrated in the total syntheses of two Topo-I-Inhibitors and two 8-oxyprotoberberine cores that can be further elaborated into the tetrahydroprotoberberine and the protoberberine alkaloid core. Moreover these building blocks were also transformed to six different tylophora alkaloids in expedient fashion. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Assessment of the intermediacy of arylpalladium carboxylate complexes in the direct arylation of benzene: evidence for C-H bond cleavage by "ligandless" species. (United States)

    Tan, Yichen; Hartwig, John F


    Palladium-catalyzed direct arylations of benzene have been proposed to occur by the generation of a phosphine-ligated arylpalladium pivalate complex LPd(Ar)(OPiv) and reaction of this complex with benzene. We have isolated an example of the proposed intermediate and evaluated whether this complex does react with benzene to form the biaryl products of direct arylation. In contrast to the proposed mechanism, no biaryl product was formed from cleavage of the benzene C-H bond by LPd(Ar)(OPiv). However, reactions of LPd(Ar)(OPiv) with benzene and additives that displace or consume the phosphine ligand formed the arylated products in good yield, suggesting that a "ligandless" arylpalladium(II) carboxylate complex undergoes the C-H cleavage step. Consistent with this conclusion, we found that reactions catalyzed by Pd(OAc)(2) without a ligand occur faster than, and with comparable selectivities to, reactions catalyzed by Pd(OAc)(2) and a phosphine ligand.

  7. Detailed Mechanistic Studies on Palladium-Catalyzed Selective C-H Olefination with Aliphatic Alkenes: A Significant Influence of Proton Shuttling. (United States)

    Deb, Arghya; Hazra, Avijit; Peng, Qian; Paton, Robert S; Maiti, Debabrata


    Directing group-assisted regioselective C-H olefination with electronically biased olefins is well studied. However, the incorporation of unactivated olefins has remained largely unsuccessful. A proper mechanistic understanding of olefination involving unactivated alkenes is therefore essential for enhancing their usage in future. In this Article, detailed experimental and computational mechanistic studies on palladium catalyzed C-H olefination with unactivated, aliphatic alkenes are described. The isolation of Pd(II) intermediates is shown to be effective for elucidating the elementary steps involved in catalytic olefination. Reaction rate and order determination, control experiments, isotopic labeling studies, and Hammett analysis have been used to understand the reaction mechanism. The results from these experimental studies implicate β-hydride elimination as the rate-determining step and that a mechanistic switch occurs between cationic and neutral pathway. Computational studies support this interpretation of the experimental evidence and are used to uncover the origins of selectivity.

  8. Recent advances in the ruthenium(ii)-catalyzed chelation-assisted C-H olefination of substituted aromatics, alkenes and heteroaromatics with alkenes via the deprotonation pathway. (United States)

    Manikandan, Rajendran; Jeganmohan, Masilamani


    The transition-metal-catalyzed chelation-assisted alkenylation at the inert C-H bond of aromatics with alkenes is one of the efficient methods to synthesize substituted vinylarenes in a highly regio- and stereoselective manner. Palladium, rhodium and ruthenium complexes are frequently used as catalysts for this type of transformation. The present review describes the recent advances in the ruthenium-catalyzed chelation-assisted alkenylation at the C-H bond of aromatics, alkenes and heteroaromatics with alkenes via the deprotonation pathway. Several directing groups including 2-pyridyl, carbonyl, amidine, amide, amine, imidate, sulphonic acid, triazole, cyano, oxazolidinone and hydontoin are widely used in the reaction. The scope, limitation and mechanistic investigation of the alkenylation reactions are discussed elaborately. This feature article includes all the reported ruthenium-catalyzed alkenylation reactions via the deprotonation pathway until the end of March 2017.

  9. Synthetic applications of Pd(II)-catalyzed C-H carboxylation and mechanistic insights: expedient routes to anthranilic acids, oxazolinones, and quinazolinones. (United States)

    Giri, Ramesh; Lam, Jonathan K; Yu, Jin-Quan


    A Pd(II)-catalyzed reaction protocol for the carboxylation of ortho-C-H bonds in anilides to form N-acyl anthranilic acids has been developed. This reaction procedure provides a novel and efficient strategy for the rapid assembly of biologically and pharmaceutically significant molecules, such as benzoxazinones and quinazolinones, from simple anilides without installing and removing an external directing group. The reaction conditions are also amenable to the carboxylation of N-phenyl pyrrolidinones. A monomeric palladacycle containing p-toluenesulfonate as an anionic ligand has been characterized by X-ray crystallography, and the crucial role of p-toluenesulfonic acid in the activation of C-H bonds in the presence of carbon monoxide is discussed. Identification of two key intermediates, a mixed anhydride and benzoxazinone formed by reductive elimination from organometallic Ar(CO)Pd(II)-OTs species, provides mechanistic evidence for a dual-reaction pathway.

  10. Analysis of the reactivities of protein C-H bonds to H atom abstraction by OH radical. (United States)

    Scheiner, Steve; Kar, Tapas


    Ab initio and density functional theory calculations are used to monitor the process wherein a OH· radical is allowed to approach the various CH groups of a Leu dipeptide, with its CH(2)CH(CH(3))(2) side chain. After forming an encounter complex, the OH· abstracts the pertinent H atom, and the resulting HOH is then dissociated from the complex. The energy barriers for H· abstraction from the β, γ, and δ CH groups are all less than 8 kcal/mol, but a significantly higher barrier is computed for the C(α)H removal. This higher barrier is the result of the strong H-bonds formed in the encounter complex between the OH· and the NH and C═O groups of the peptide units that surround the C(α) atom. This low-energy complex represents a kinetic trap which raises the energy needed to surmount the ensuing H· transfer barrier.

  11. Organ absorbed doses in intraoral dental radiography. (United States)

    Lecomber, A R; Faulkner, K


    A dental radiography unit operating at 70 kV (nominal) and 20 cm focus-skin distance was used to irradiate an anthropomorphic phantom loaded with lithium fluoride thermoluminescent dosemeters, in order to assess the variation in organ absorbed dose with intraoral periapical radiographic view. 14 views using the bisecting-angle technique and four views using the paralleling technique were studied. The results are presented and the doses and dose distributions examined. Doses for the paralleling and bisecting-angle techniques are compared, and the effects of focus-skin distance and beam collimation upon patient dosimetry discussed. Sources of uncertainty in dental dosimetry studies using phantoms are also considered.

  12. Acoustical model of a Shoddy fibre absorber (United States)

    Manning, John Peter

    Shoddy fibres or "Shoddies" are a mixture of post-consumer and post-industrial fibres diverted from textile waste streams and recycled into their raw fibre form. They have found widespread use as a raw material for manufacturing sound absorbers that include, but are not limited to: automotive, architectural and home appliance applications. The purpose of this project is to develop a simple acoustic model to describe the acoustic behaviour of sound absorbers composed primarily of Shoddy fibres. The model requires knowledge of the material's bulk density only. To date, these materials have not been the focus of much published research and acoustical designers must rely on models that were developed for other materials or are overly complex. For modelling purposes, an equivalent fluid approach is chosen to balance complexity and accuracy. In deriving the proposed model, several popular equivalent fluid models are selected and the required input parameters for each model identified. The models are: the model of Delaney and Bazley, two models by Miki, the model of Johnson in conjunction with the model of Champoux and Allard and the model of Johnson in conjunction with the model of Lafarge. Characterization testing is carried out on sets of Shoddy absorbers produced using three different manufacturing methods. The measured properties are open porosity, tortuosity, airflow resistivity, the viscous and thermal characteristic lengths and the static thermal permeability. Empirical relationships between model parameters and bulk density are then derived and used to populate the selected models. This yields several 'simplified' models with bulk density as the only parameter. The most accurate model is then selected by comparing each model's prediction to the results of normal incidence sound absorption tests. The model of Johnson-Lafarge populated with the empirical relations is the most accurate model over the range of frequencies considered (approx. 300 Hz - 4000 Hz

  13. Liquid holdup in turbulent contact absorber

    International Nuclear Information System (INIS)

    Haq, A.; Zaman, M.; Inayat, M.H.; Chughtai, I.R.


    Dynamic liquid holdup in a turbulent contact absorber was obtained through quick shut off valves technique. Experiments were carried out in a Perspex column. Effects of liquid velocity, gas velocity, packing diameter packing density and packing height on dynamic liquid holdup were studied. Hollow spherical high density polyethylene (HDPE) balls were used as inert fluidized packing. Experiments were performed at practical range of liquid and gas velocities. Holdup was calculated on the basis of static bed height. Liquid holdup increases with increasing both liquid and gas velocities both for type 1 and type 2 modes of fluidization. Liquid holdup increases with packing density. No effect of dia was observed on liquid holdup. (author)

  14. Fabrication of high efficacy selective solar absorbers

    CSIR Research Space (South Africa)

    Tile, N


    Full Text Available Peer-Reviewed Journal Papers: K.T. Roro, N. Tile, B.W. Mwakikunga, B. Yalisi, A. Forbes (2012). Solar absorption and thermal emission properties of Multiwall carbonnanotube/nickel oxide nanocomposite thin films synthesized by sol-gel process..., Materials Science and Engineering B 177,581? 587. K.T. Roro, N. Tile, A. Forbes (2012), Preparation and characterization of carbon/nickel oxide nanocomposite coatings for solar absorber applications, Applied Surface Science 258, 7174? 7180. K.T. Roro...

  15. DHCAL with Minimal Absorber: Measurements with Positrons

    CERN Document Server

    Freund, B; Repond, J.; Schlereth, J.; Xia, L.; Dotti, A.; Grefe, C.; Ivantchenko, V.; Antequera, J.Berenguer; Calvo Alamillo, E.; Fouz, M.C.; Marin, J.; Puerta-Pelayo, J.; Verdugo, A.; Brianne, E.; Ebrahimi, A.; Gadow, K.; Göttlicher, P.; Günter, C.; Hartbrich, O.; Hermberg, B.; Irles, A.; Krivan, F.; Krüger, K.; Kvasnicka, J.; Lu, S.; Lutz, B.; Morgunov, V.; Provenza, A.; Reinecke, M.; Sefkow, F.; Schuwalow, S.; Tran, H.L.; Garutti, E.; Laurien, S.; Matysek, M.; Ramilli, M.; Schroeder, S.; Bilki, B.; Norbeck, E.; Northacker, D.; Onel, Y.; Cvach, J.; Gallus, P.; Havranek, M.; Janata, M.; Kovalcuk, M.; Kvasnicka, J.; Lednicky, D.; Marcisovsky, M.; Polak, I.; Popule, J.; Tomasek, L.; Tomasek, M.; Sicho, P.; Smolik, J.; Vrba, V.; Zalesak, J.; van Doren, B.; Wilson, G.W.; Kawagoe, K.; Hirai, H.; Sudo, Y.; Suehara, T.; Sumida, H.; Takada, S.; Tomita, T.; Yoshioka, T.; Bilokin, S.; Bonis, J.; Cornebise, P.; Pöschl, R.; Richard, F.; Thiebault, A.; Zerwas, D.; Hostachy, J.Y.; Morin, L.; Besson, D.; Chadeeva, M.; Danilov, M.; Markin, O.; Popova, E.; Gabriel, M.; Goecke, P.; Kiesling, C.; Kolk, N.van der; Simon, F.; Szalay, M.; Corriveau, F.; Blazey, G.C.; Dyshkant, A.; Francis, K.; Zutshi, V.; Kotera, K.; Ono, H.; Takeshita, T.; Ieki, S.; Kamiya, Y.; Ootani, W.; Shibata, N.; Jeans, D.; Komamiya, S.; Nakanishi, H.


    In special tests, the active layers of the CALICE Digital Hadron Calorimeter prototype, the DHCAL, were exposed to low energy particle beams, without being interleaved by absorber plates. The thickness of each layer corresponded approximately to 0.29 radiation lengths or 0.034 nuclear interaction lengths, defined mostly by the copper and steel skins of the detector cassettes. This paper reports on measurements performed with this device in the Fermilab test beam with positrons in the energy range of 1 to 10 GeV. The measurements are compared to simulations based on GEANT4 and a standalone program to emulate the detailed response of the active elements.

  16. Impedance matched thin metamaterials make metals absorbing. (United States)

    Mattiucci, N; Bloemer, M J; Aközbek, N; D'Aguanno, G


    Metals are generally considered good reflectors over the entire electromagnetic spectrum up to their plasma frequency. Here we demonstrate an approach to tailor their absorbing characteristics based on the effective metamaterial properties of thin, periodic metallo-dielectric multilayers by exploiting a broadband, inherently non-resonant, surface impedance matching mechanism. Based on this mechanism, we design, fabricate and test omnidirectional, thin ( 99%) over a frequency range spanning from the UV to the IR. Our approach opens new venues to design cost effective materials for many applications such as thermo-photovoltaic energy conversion devices, light harvesting for solar cells, flat panel display, infrared detectors, stray light reduction, stealth and others.

  17. DHCAL with minimal absorber: measurements with positrons

    International Nuclear Information System (INIS)

    Freund, B.; Neubüser, C.; Repond, J.; Schlereth, J.; Xia, L.; Dotti, A.; Grefe, C.; Ivantchenko, V.; Antequera, J. Berenguer; Alamillo, E. Calvo; Fouz, M.-C.; Marin, J.; Puerta-Pelayo, J.; Verdugo, A.; Brianne, E.; Ebrahimi, A.; Gadow, K.; Göttlicher, P.; Günter, C.; Hartbrich, O.


    In special tests, the active layers of the CALICE Digital Hadron Calorimeter prototype, the DHCAL, were exposed to low energy particle beams, without being interleaved by absorber plates. The thickness of each layer corresponded approximately to 0.29 radiation lengths or 0.034 nuclear interaction lengths, defined mostly by the copper and steel skins of the detector cassettes. This paper reports on measurements performed with this device in the Fermilab test beam with positrons in the energy range of 1 to 10 GeV. The measurements are compared to simulations based on GEANT4 and a standalone program to emulate the detailed response of the active elements.

  18. An electromechanical low frequency panel sound absorber. (United States)

    Chang, Daoqing; Liu, Bilong; Li, Xiaodong


    The sound absorbing properties of a thin micro-perforated plate (MPP) coated with piezoelectric material with shunt damping technology is investigated. First a theoretical model is presented to predict the sound absorption coefficients of a thin plate attached with a piezoelectric patch and electrical circuits. Then the model is extended to analyze the sound absorption for a thin plate with micro perforations and piezoelectric material. Measurements are also carried out in an impedance tube and found to be in good agreements with the theoretical model. The sound absorption of the constructions can be much improved by tuning the electrical circuits.

  19. High energy model for irregular absorbing particles

    International Nuclear Information System (INIS)

    Chiappetta, Pierre.


    In the framework of a high energy formulation of relativistic quantum scattering a model is presented which describes the scattering functions and polarization of irregular absorbing particles, whose dimensions are greater than the incident wavelength. More precisely in the forward direction an amplitude parametrization of eikonal type is defined which generalizes the usual diffraction theory, and in the backward direction a reflective model is used including a shadow function. The model predictions are in good agreement with the scattering measurements off irregular compact and fluffy particles performed by Zerull, Giese and Weiss (1977)

  20. Absorbency of Superabsorbent Polymers in Cementitious Environments

    DEFF Research Database (Denmark)

    Esteves, Luis Pedro; Jensen, Ole Mejlhede


    Optimal use of superabsorbent polymers (SAP) in cement-based materials relies on knowledge on how SAP absorbency is influenced by different physical and chemical parameters. These parameters include salt concentration in the pore fluid, temperature of the system and SAP particle size. The present...... work shows experimental results on this and presents a new technique to measure the swelling of SAP particles. This new technique is compared with existing techniques that have been recently proposed for the measurement of pore fluid absorption by superabsorbent polymers. It is seen...

  1. Optical Pulsing in an Absorbing Liquid (United States)

    Barnes, Jacob; Evans, Dean; Guha, Shekhar


    A continuous-wave laser can be converted into a series of repetitive pulses by focusing the laser beam into an absorbing liquid (e.g. nigrosine dissolved in a solvent), where the mechanism responsible for the pulses is the scattering of light off of photo-generated bubbles. The dependence of the pulsation frequency on the solvent, power, and cell thickness will be shown. The authors would like to acknowledge the contributions made by Prof. Daniel Lathrop (University of Maryland, Department of Physics) at the APS March 2002 meeting.

  2. Exposure testing of solar absorber surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Moore, S.W.


    The Los Alamos National Laboratory has been involved in supporting, monitoring and conducting exposure testing of solar materials for approximately ten years. The Laboratory has provided technical monitoring of the IITRI, DSET, Lockheed, and Berry contracts and has operated the Los Alamos exposure Facility for over five years. This report will outline some of the past exposure testing, the testing still in progress, and describe some of the major findings. While this report will primarily emphasize solar absorber surfaces, some of the significant findings relative to advanced glazing will be discussed.

  3. Absorbed Energy in Ship Collisions and Grounding

    DEFF Research Database (Denmark)

    Pedersen, Preben Terndrup; Zhang, Shengming


    Minorsky's well-known empirical formula, which relates the absorbed energy to the destroyed material volume, has been widely used in analyses of high energy collision and grounding accidents for nearly 40 years. The advantage of the method is its apparent simplcity. Obviously, its drawback...... collisions and grounding. The developed expressions reflect the structural arrangement, the material properties and different damage patterns.The present method is validated against a large number of existing experimental results and detailed numerical simulation results. Applications to full-sale ship...

  4. Direct C-H arylation of purines: Development of methodology and its use in regioselective synthesis of 2,6,8-trisubstituted purines

    Czech Academy of Sciences Publication Activity Database

    Čerňa, Igor; Pohl, Radek; Klepetářová, Blanka; Hocek, Michal


    Roč. 8, č. 23 (2006), s. 5389-5392 ISSN 1523-7060 R&D Projects: GA ČR(CZ) GA203/05/0043; GA MŠk(CZ) LC06077 Institutional research plan: CEZ:AV0Z40550506 Keywords : purines * cross-coupling * C-H activation * arylation Subject RIV: CC - Organic Chemistry Impact factor: 4.659, year: 2006

  5. Linear antenna microwave plasma CVD diamond deposition at the edge of no-growth region of C-H-O ternary diagram

    Czech Academy of Sciences Publication Activity Database

    Potocký, Štěpán; Babchenko, Oleg; Hruška, Karel; Kromka, Alexander


    Roč. 249, č. 12 (2012), s. 2612-2615 ISSN 0370-1972 R&D Projects: GA ČR(CZ) GBP108/12/G108; GA ČR GAP205/12/0908 Institutional research plan: CEZ:AV0Z10100521 Keywords : C-H-O phase diagram * nanocrystalline diamond * plasma enhanced CVD * Raman spectroscopy * SEM Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.489, year: 2012

  6. A neutron and X-ray diffraction study of the influence of deposition conditions on the structure of a-C:H


    Walters, J.K.; Algar, C.D.; Burke, Terry; Rigden, Jane S.; Newport, Robert J.; Bushnell-Wye, Graham; Howells, W.S.; Sattel, S.; Weiler, M.; Ehrhardt, H.


    The atomic scale structure of amorphous hydrogenated carbon (a-C:H) films prepared from an acetylene precursor by plasma enhanced chemical vapour deposition (PECVD) and a fast-atom source (FAS) have been studied by neutron and X-ray diffraction. The effect of beam energy on the structure of the film is investigated, and comparison is made to samples prepared using at fast atom (neutral particle) source, also using acetylene as the precursor, The results show that, in both deposition methods, ...

  7. Palladium-catalyzed intramolecular asymmetric C-H functionalization/cyclization reaction of metallocenes: an efficient approach toward the synthesis of planar chiral metallocene compounds. (United States)

    Deng, Ruixian; Huang, Yunze; Ma, Xinna; Li, Gencheng; Zhu, Rui; Wang, Bin; Kang, Yan-Biao; Gu, Zhenhua


    A palladium-catalyzed asymmetric synthesis of planar chiral metallocene compounds is reported. The reaction stereoselectively functionalized one of the ortho C-H bonds of Cp rings by intramolecular cyclization to form indenone derivatives in high yields with excellent enantioselectivity. The mild set of reaction conditions allowed a wide variety of chiral metallocene compounds to be synthesized with broad functional group tolerance. The influences of preinstalled chiralities on the other Cp-ring were also investigated.

  8. sp{sup 3} versus sp{sup 2} C-H bond activation chemistry of 2-picoline by Th(IV) and U(IV) metallocene complexes

    Energy Technology Data Exchange (ETDEWEB)

    Kiplinger, Jaqueline L. [Los Alamos National Laboratory, Mail Stop J514, Los Alamos, NM 87545 (United States)], E-mail:; Scott, Brian L.; Schelter, Eric J. [Los Alamos National Laboratory, Mail Stop J514, Los Alamos, NM 87545 (United States); Pool Davis Tournear, Jaime A


    The thorium alkyl complex (C{sub 5}Me{sub 5}){sub 2}Th(CH{sub 3}){sub 2} and 2-picoline react to give preferential sp{sup 3} C-H bond activation in the presence of a more reactive sp{sup 2} C-H bond, while the analogous uranium complex, (C{sub 5}Me{sub 5}){sub 2}U(CH{sub 3}){sub 2}, reacts with only the ortho 2-picoline sp{sup 2} C-H bond, as originally expected. Herein, we describe this competitive sp{sup 3} versus sp{sup 2} C-H bond activation chemistry with 2-picoline and (C{sub 5}Me{sub 5}){sub 2}An(CH{sub 3}){sub 2} (An = Th, U) and provide experimental observations that suggest different mechanistic reaction pathways are operative for the uranium and thorium complexes. We also report the X-ray crystal structures for the thorium picolyl complex, (C{sub 5}Me{sub 5}){sub 2}Th(CH{sub 3})[{eta}{sup 2}-(N,C)-2-CH{sub 2}-NC{sub 5}H{sub 3}], and the {eta}{sup 2}-pyridyl complexes (C{sub 5}Me{sub 5}){sub 2}Th(CH{sub 3})[{eta}{sup 2}-(N,C)-6-CH{sub 3}-NC{sub 5}H{sub 3}] and (C{sub 5}Me{sub 5}){sub 2}U(CH{sub 3})[{eta}{sup 2}-(N,C)-6-CH{sub 3}-NC{sub 5}H{sub 3}].

  9. Heterometallic Pd(II)-Ni(II) complexes with meso-substituted dibenzotetraaza[14]annulene: double C-H bond activation and formation of a rectangular tetradibenzotetraaza[14]annulene. (United States)

    Khaledi, Hamid; Olmstead, Marilyn M; Fukuda, Takamitsu; Ali, Hapipah Mohd


    Three isomeric 2[Pd(II)-Ni(II)] metal complexes, derived from indoleninyl meso-substituted dibenzotetraaza[14]annulene, were synthesized. The resulting dimers feature Ni···Ni or, alternatively, Ni···π interactions in staggered or slipped cofacial structures. A remarkable insertion of palladium into two different C-H bonds yielded a 4[Pd(II)-Ni(II)] rectangular complex with dimensions of 8.73 × 10.38 Å.

  10. Tandem Rh-Catalyzed Oxidative C-H Olefination and Cyclization of Enantiomerically Enriched Benzo-1,3-Sulfamidates: Stereoselective Synthesis of trans-1,3-Disubstituted Isoindolines. (United States)

    Achary, Raghavendra; Jung, In-A; Lee, Hyeon-Kyu


    A tandem process, involving Rh(III)-catalyzed oxidative C-H olefination of enantiomerically enriched 4-aryl-benzo-1,3-sulfamidates and subsequent intramolecular aza-Michael cyclization has been developed. The reaction produces trans-benzosulfamidate-fused-1,3-disubstituted isoindolines as major products, in which the configurational integrity of the stereogenic center in the starting material is preserved. Further transformations of the benzosulfamidate-fused-1,3-disubstituted isoindolines are described.

  11. Iodine-catalyzed sp³ C-H bond activation by selenium dioxide: synthesis of diindolylmethanes and di(3-indolyl)selanides. (United States)

    Naidu, P Seetham; Majumder, Swarup; Bhuyan, Pulak J


    An efficient reaction protocol was developed for the synthesis of several diindolylmethane derivatives via the [Formula: see text] C-H bond activation of aryl methyl ketones by [Formula: see text] and indoles in the presence of catalytic amounts of [Formula: see text] at 80 [Formula: see text] using dioxane as solvent. Unexpectedly, an interesting class of di(3-indolyl)selenide compounds was isolated when the reaction was carried out at room temperature.

  12. Average [O II]nebular emission associated with Mg II absorbers: Dependence on Fe II absorption (United States)

    Joshi, Ravi; Srianand, Raghunathan; Petitjean, Patrick; Noterdaeme, Pasquier


    We investigate the effect of Fe II equivalent width (W2600) and fibre size on the average luminosity of [O II]λλ3727,3729 nebular emission associated with Mg II absorbers (at 0.55 ≤ z ≤ 1.3) in the composite spectra of quasars obtained with 3 and 2 arcsec fibres in the Sloan Digital Sky Survey. We confirm the presence of strong correlations between [O II] luminosity (L_{[O II]}) and equivalent width (W2796) and redshift of Mg II absorbers. However, we show L_{[O II]} and average luminosity surface density suffers from fibre size effects. More importantly, for a given fibre size the average L_{[O II]} strongly depends on the equivalent width of Fe II absorption lines and found to be higher for Mg II absorbers with R ≡W2600/W2796 ≥0.5. In fact, we show the observed strong correlations of L_{[O II]} with W2796 and z of Mg II absorbers are mainly driven by such systems. Direct [O II] detections also confirm the link between L_{[O II]} and R. Therefore, one has to pay attention to the fibre losses and dependence of redshift evolution of Mg II absorbers on W2600 before using them as a luminosity unbiased probe of global star formation rate density. We show that the [O II] nebular emission detected in the stacked spectrum is not dominated by few direct detections (i.e., detections ≥3σ significant level). On an average the systems with R ≥0.5 and W2796 ≥2Å are more reddened, showing colour excess E(B - V) ˜ 0.02, with respect to the systems with R <0.5 and most likely traces the high H I column density systems.

  13. Access to the meta position of arenes through transition metal catalysed C-H bond functionalisation: a focus on metals other than palladium. (United States)

    Mihai, Madalina T; Genov, Georgi R; Phipps, Robert J


    The elaboration of simple arenes in order to access more complex substitution patterns is a crucial endeavor for synthetic chemists, given the central role that aromatic rings play in all manner of important molecules. Classical methods are now routinely used alongside stoichiometric organometallic approaches and, most recently, transition metal catalysis in the range of methodologies that are available to elaborate arene C-H bonds. Regioselectivity is an important consideration when selecting a method and, of all those available, it is arguably those that target the meta position that are fewest in number. The rapid development of transition metal-catalysed C-H bond functionalisation over the last few decades has opened new possibilities for meta-selective C-H functionalisation through the diverse reactivity of transition metals and their compatibility with a wide range of directing groups. The pace of discovery of such processes has grown rapidly in the last five years in particular and it is the purpose of this review to examine these but in doing so to place the focus on metals other than palladium, the specific contributions of which have been very recently reviewed elsewhere. It is hoped this will serve to highlight to the reader the breadth of current strategies and mechanisms that have been used to tackle this challenge, which may inspire further progress in the field.

  14. Density functional theory study of Rh(III)-catalyzed C-H activations and intermolecular annulations between benzamide derivatives and allenes. (United States)

    Xing, Zhong; Huang, Fang; Sun, Chuanzhi; Zhao, Xue; Liu, Jianbiao; Chen, Dezhan


    Density functional theory has been applied to gain insight into the Cp*Rh(OAc)2-catalyzed C-H activation and intermolecular annulation of benzamide derivatives with allenes. The study shows that the reactions proceed in three steps: (1) C-H activation induced by Rh catalyst reacting with benzamide derivatives, (2) carborhodation of allene, and (3) regeneration of Rh catalyst. The results indicate that the N-H deprotonation makes the following C-H activation much easier. The regio- and stereoselectivities of 1a (N-pivaloyloxy benzamide)/2a (cyclohexylallene) and 1b (N-pivaloyloxy-4-methyl-benzamide)/2b (1,1-dimethyl allene) depend on the allene carborhodation step. The steric hindrance effect is the dominant factor. We also discuss the reaction mechanism of 1c (N-methoxy benzamide)/2a. The chemoselectivity between 1c/2a is determined by the N-O cleavage step. Replacement of OPiv by OMe leads to loss of the stabilization effect provided by C=O in OPiv. Additionally, Cp*Rh(OAc)(OPiv) is produced in the Cp*Rh(OAc)2 regeneration step, which can work as catalyst as well.

  15. Chemical and morphological difference between TiN/DLC and a-C:H/DLC grown by pulsed vacuum arc techniques

    Energy Technology Data Exchange (ETDEWEB)

    Castillo, H.A. [Laboratorio de Fisica del Plasma, Universidad Nacional de Colombia Sede Manizales, Manizales (Colombia); Restrepo-Parra, E., E-mail: [Laboratorio de Fisica del Plasma, Universidad Nacional de Colombia Sede Manizales, Manizales (Colombia); Arango-Arango, P.J. [Laboratorio de Fisica del Plasma, Universidad Nacional de Colombia Sede Manizales, Manizales (Colombia)


    In order to improve the adherence of DLC films, interlayers of amorphous hydrogenated carbon (a-C:H) and titanium nitride (TiN) were deposited by means of the pulsed vacuum arc technique. Bilayers were obtained by using a carbon target of 99.98% of purity in mixtures of (Ar + CH{sub 4}) and (Ar + H{sub 2}) for producing a-C and DLC, respectively and a target of titanium of 99.999% in a mixture of (Ar + N{sub 2}) for growing TiN. After the deposition, chemical and morphological differences between TiN/DLC and a-C:H/DLC bilayers grown on silicon and stainless steel 304 were studied using X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FT-IR), and scanning probe microscopy (SPM) techniques. XPS analysis showed a difference in sp{sup 3}/(sp{sup 2}+sp{sup 3}) bonds ratio for each bilayer, being 0.67 for TiN/DLC and 0.45 for a-C:H/DLC bilayers. sp{sup 3} and sp{sup 2} bonds were also observed by the FTIR technique. SPM images, in atomic force microscopy (AFM) and lateral force microscopy (LFM) modes were carried out for illustrating the comparison between TiN/DLC and a-C/DLC morphologic characteristics. Roughness and grain size were studied as a function of the H{sub 2} concentration for both bilayers.

  16. Promotional effects of chemisorbed oxygen and hydroxide in the activation of C-H and O-H bonds over transition metal surfaces (United States)

    Hibbitts, David; Neurock, Matthew


    Electronegative coadsorbates such as atomic oxygen (O*) and hydroxide (OH*) can act as Brønsted bases when bound to Group 11 as well as particular Group 8-10 metal surfaces and aid in the activation of X-H bonds. First-principle density functional theory calculations were carried out to systematically explore the reactivity of the C-H bonds of methane and surface methyl intermediates as well as the O-H bond of methanol directly and with the assistance of coadsorbed O* and OH* intermediates over Group 11 (Cu, Ag, and Au) and Group 8-10 transition metal (Ru, Rh, Pd, Os, Ir, and Pt) surfaces. C-H as well as O-H bond activation over the metal proceeds via a classic oxidative addition type mechanism involving the insertion of the metal center into the C-H or O-H bond. O* and OH* assist C-H and O-H activation over particular Group 11 and Group 8-10 metal surfaces via a σ-bond metathesis type mechanism involving the oxidative addition of the C-H or O-H bond to the metal along with a reductive deprotonation of the acidic C-H and O-H bond over the M-O* or M-OH* site pair. The O*- and OH*-assisted C-H activation paths are energetically preferred over the direct metal catalyzed C-H scission for all Group 11 metals (Cu, Ag, and Au) with barriers that are 0.4-1.5 eV lower than those for the unassisted routes. The barriers for O*- and OH*-assisted C-H activation of CH4 on the Group 8-10 transition metals, however, are higher than those over the bare transition metal surfaces by as much as 1.4 eV. The C-H activation of adsorbed methyl species show very similar trends to those for CH4 despite the differences in structure between the weakly bound methane and the covalently adsorbed methyl intermediates. The activation of the O-H bond of methanol is significantly promoted by O* as well as OH* intermediates over both the Group 11 metals (Cu, Ag, and Au) as well as on all Group 8-10 metals studied (Ru, Rh, Pd, Os, Ir, and Pt). The O*- and OH*-assisted CH3O-H barriers are 0.6 to 2

  17. Dependence of electrical and optical properties of amorphous SiC:H thin films grown by rf plasma enhanced chemical vapor deposition on annealing temperature

    CERN Document Server

    Park, M G; Hong, B; Kim, Y T; Yoon, D H


    In this article, we investigated the dependence of optical and electrical properties of hydrogenated amorphous silicon carbide (a-SiC:H) films on annealing temperature (T sub a) and radio frequency (rf) power. The substrate temperature (T sub s) was 250 deg. C, the rf power was varied from 30 to 400 W, and the range of T sub a was from 400 to 600 deg. C. The a-SiC:H films were deposited by using the plasma enhanced chemical vapor deposition system on Corning 7059 glasses and p-type Si (100) wafers with a SiH sub 4 +CH sub 4 gas mixture. The experimental results have shown that the optical bandgap energy (E sub g) of the a-SiC:H thin films changed little on the annealing temperature while E sub g increased with the rf power. The Raman spectrum of the thin films annealed at high temperatures showed that graphitization of carbon clusters and microcrystalline silicon occurs. The current-voltage characteristics have shown good electrical properties in relation to the annealed films.

  18. Aligned metal absorbers and the ultraviolet background at the end of reionization (United States)

    Doughty, Caitlin; Finlator, Kristian; Oppenheimer, Benjamin D.; Davé, Romeel; Zackrisson, Erik


    We use observations of spatially aligned C II, C IV, Si II, Si IV, and O I absorbers to probe the slope and intensity of the ultraviolet background (UVB) at z ˜ 6. We accomplish this by comparing observations with predictions from a cosmological hydrodynamic simulation using three trial UVBs applied in post-processing: a spectrally soft, fluctuating UVB calculated using multifrequency radiative transfer; a soft, spatially uniform UVB; and a hard, spatially uniform `quasars-only' model. When considering our paired high-ionization absorbers (C IV/Si IV), the observed statistics strongly prefer the hard, spatially uniform UVB. This echoes recent findings that cosmological simulations generically underproduce strong C IV absorbers at z > 5. A single low/high ionization pair (Si II/Si IV), by contrast, shows a preference for the HM12 UVB, whereas two more (C II/C IV and O I/C IV) show no preference for any of the three UVBs. Despite this, future observations of specific absorbers, particularly Si IV/C IV, with next-generation telescopes probing to lower column densities should yield tighter constraints on the UVB.

  19. Erbium concentration dependent absorbance in tellurite glass

    Energy Technology Data Exchange (ETDEWEB)

    Sazali, E. S., E-mail: mdsupar@utm; Rohani, M. S., E-mail: mdsupar@utm; Sahar, M. R., E-mail: mdsupar@utm; Arifin, R., E-mail: mdsupar@utm; Ghoshal, S. K., E-mail: mdsupar@utm; Hamzah, K., E-mail: mdsupar@utm [Advanced Optical Material Research Group, Department of Physics, Faculty of Science, Universiti Teknologi Malaysia, 81310, Skudai, Johor Bahru, Johor (Malaysia)


    Enhancing the optical absorption cross-section in topically important rare earth doped tellurite glasses is challenging for photonic devices. Controlled synthesis and detailed characterizations of the optical properties of these glasses are important for the optimization. The influence of varying concentration of Er{sup 3+} ions on the absorbance characteristics of lead tellurite glasses synthesized via melt-quenching technique are investigated. The UV-Vis absorption spectra exhibits six prominent peaks centered at 490, 526, 652, 800, 982 and 1520 nm ascribed to the transitions in erbium ion from the ground state to the excited states {sup 4}F{sub 7/2}, {sup 2}H{sub 11/2}, {sup 4}F{sub 9/2}, {sup 4}I{sub 9/2}, {sup 2}H{sub 11/2} and {sup 4}I{sub 13/2}, respectively. The results are analyzed by means of optical band gap E{sub g} and Urbach energy E{sub u}. The values of the energy band gap are found decreased from 2.82 to 2.51 eV and the Urbach energy increased from 0.15 to 0.24 eV with the increase of the Er{sub 2}O{sub 3} concentration from 0 to 1.5 mol%. The excellent absorbance of the prepared tellurite glasses makes them suitable for fabricating solid state lasers.

  20. Wave energy extraction by coupled resonant absorbers. (United States)

    Evans, D V; Porter, R


    In this article, a range of problems and theories will be introduced that will build towards a new wave energy converter (WEC) concept, with the acronym 'ROTA' standing for resonant over-topping absorber. First, classical results for wave power absorption for WECs constrained to operate in a single degree of freedom will be reviewed and the role of resonance in their operation highlighted. Emphasis will then be placed on how the introduction of further resonances can improve power take-off characteristics by extending the range of frequencies over which the efficiency is close to a theoretical maximum. Methods for doing this in different types of WECs will be demonstrated. Coupled resonant absorbers achieve this by connecting a WEC device equipped with its own resonance (determined from a hydrodynamic analysis) to a new system having separate mass/spring/damper characteristics. It is shown that a coupled resonant effect can be realized by inserting a water tank into a WEC, and this idea forms the basis of the ROTA device. In essence, the idea is to exploit the coupling between the natural sloshing frequencies of the water in the internal tank and the natural resonance of a submerged buoyant circular cylinder device that is tethered to the sea floor, allowing a rotary motion about its axis of attachment.

  1. Fuel with burnable absorber for RBMK-1500

    International Nuclear Information System (INIS)

    Krivosein, G.


    Following the accident at the Chernobyl Unit 4, the priority measures to improve RBMK's safety were developed. Under this program, the measures to reduce the void reactivity coefficient were executed on the stage-by-stage terms: As a result of these measures, the void reactivity coefficient was reduced below +1.0β. But there was decrease in fuel burnup to 14.0/14.5 MW.d/kg (design value ∼21/22 MW.d/kg). High power level of a fresh fuel assembly did not allow to employ fuel with higher enrichment without any compensatory measures. The different types of burnable absorbers were considered to be used. From the results of the anticipated calculations, it was specified that the most efficient power neutron flax flattening between fuel channels could be achieved when erbium was used. Ignalina NPP has used 2.4 % enriched fuel assemblies with burnable absorber since 1995. The fuel burnup has been increased by 60 %. The obtained experimental results are analyzed. (author)

  2. Pregnant woman mode for absorbed fraction calculations

    International Nuclear Information System (INIS)

    Cloutier, R.J.; Snyder, W.S.; Watson, E.E.


    The most radiation-sensitive segment of our population is the developing fetus. Until recently, methods available for calculating the dose to the fetus were inadequate because a model for the pregnant woman was not available. Instead, the Snyder and Fisher model of Reference Man, which includes a uterus, was frequently used to calculate absorbed fractions when the source was in various organs of the body and the nongravid uterus was the target. These values would be representative of the dose to the embryo during the early stages of pregnancy. Unfortunately, Reference Man is considerable larger than Reference Woman. The authors recently reported on the design of a Reference Woman phantom that has dimensions quite similar to the ICRP Reference Woman. This phantom was suitable for calculating the dose to the embryo during early stages of pregnancy (0 to 3 mo.), but was not suitable for the later stages of pregnancy because of the changing shape of the mother and the displacement of several abdominal organs brought about by the growth of the uterus and fetus. The models of Reference Woman that were subsequently developed for each month of pregnancy are described. The models take into account the growth of the uterus and fetus and the repositioning of the various abdominal organs. These models have been used to calculate absorbed fractions for the fetus as a target and the gastrointestinal tract as a source of radiation for twelve photon energies ranging from 10 keV to 4 MeV

  3. High-efficiency ventilated metamaterial absorber at low frequency (United States)

    Wu, Xiaoxiao; Au-Yeung, Ka Yan; Li, Xin; Roberts, Robert Christopher; Tian, Jingxuan; Hu, Chuandeng; Huang, Yingzhou; Wang, Shuxia; Yang, Zhiyu; Wen, Weijia


    We demonstrate a ventilated metamaterial absorber operating at low frequency (90%) has been achieved in both simulations and experiments. This high-efficiency absorption under the ventilation condition originates from the weak coupling of two identical split tube resonators constituting the absorber, which leads to the hybridization of the degenerate eigenmodes and breaks the absorption upper limit of 50% for conventional transmissive symmetric acoustic absorbers. The absorber can also be extended to an array and work in free space. The absorber should have potential applications in acoustic engineering where both noise reduction and ventilation are required.

  4. Graphene metamaterials based tunable terahertz absorber: effective surface conductivity approach

    DEFF Research Database (Denmark)

    Andryieuski, Andrei; Lavrinenko, Andrei


    In this paper we present the efficient design of functional thin-film metamaterial devices with the effective surface conductivity approach. As an example, we demonstrate a graphene based perfect absorber. After formulating the requirements to the perfect absorber in terms of surface conductivity...... we investigate the properties of graphene wire medium and graphene fishnet metamaterials and demonstrate both narrowband and broadband tunable absorbers.......In this paper we present the efficient design of functional thin-film metamaterial devices with the effective surface conductivity approach. As an example, we demonstrate a graphene based perfect absorber. After formulating the requirements to the perfect absorber in terms of surface conductivity...

  5. Computational Study of Pincer Iridium Catalytic Systems: C-H, N-H, and C-C Bond Activation and C-C Coupling Reactions (United States)

    Zhou, Tian

    Computational chemistry has achieved vast progress in the last decades in the field, which was considered to be only experimental before. DFT (density functional theory) calculations have been proven to be able to be applied to large systems, while maintaining high accuracy. One of the most important achievements of DFT calculations is in exploring the mechanism of bond activation reactions catalyzed by organometallic complexes. In this dissertation, we discuss DFT studies of several catalytic systems explored in the lab of Professor Alan S. Goldman. Headlines in the work are: (1) (R4PCP)Ir alkane dehydrogenation catalysts are highly selective and different from ( R4POCOP)Ir catalysts, predicting different rate-/selectivity-determining steps; (2) The study of the mechanism for double C-H addition/cyclometalation of phenanthrene or biphenyl by (tBu4PCP)Ir(I) and ( iPr4PCP)Ir illustrates that neutral Ir(III) C-H addition products can undergo a very facile second C-H addition, particularly in the case of sterically less-crowded Ir(I) complexes; (3) (iPr4PCP)Ir pure solid phase catalyst is highly effective in producing high yields of alpha-olefin products, since the activation enthalpy for dehydrogenation is higher than that for isomerization via an allyl pathway; higher temperatures favor the dehydrogenation/isomerization ratio; (4) (PCP)Ir(H)2(N2H4) complex follows a hydrogen transfer mechanism to undergo both dehydrogenation to form N 2 and H2, as well as hydrogen transfer followed by N-N bond cleavage to form NH3, N2, and H2; (5) The key for the catalytic effect of solvent molecule in CO insertion reaction for RMn(CO)5 is hydrogen bond assisted interaction. The basicity of the solvent determines the strength of the hydrogen bond interaction during the catalytic path and determines the catalytic power of the solvent; and (6) Dehydrogenative coupling of unactivated C-H bonds (intermolecular vinyl-vinyl, intramolecular vinyl-benzyl) is catalyzed by precursors of the

  6. Absorber Alignment Measurement Tool for Solar Parabolic Trough Collectors: Preprint

    Energy Technology Data Exchange (ETDEWEB)

    Stynes, J. K.; Ihas, B.


    As we pursue efforts to lower the capital and installation costs of parabolic trough solar collectors, it is essential to maintain high optical performance. While there are many optical tools available to measure the reflector slope errors of parabolic trough solar collectors, there are few tools to measure the absorber alignment. A new method is presented here to measure the absorber alignment in two dimensions to within 0.5 cm. The absorber alignment is measured using a digital camera and four photogrammetric targets. Physical contact with the receiver absorber or glass is not necessary. The alignment of the absorber is measured along its full length so that sagging of the absorber can be quantified with this technique. The resulting absorber alignment measurement provides critical information required to accurately determine the intercept factor of a collector.

  7. Transition-metal-catalyzed C-N bond forming reactions using organic azides as the nitrogen source: a journey for the mild and versatile C-H amination. (United States)

    Shin, Kwangmin; Kim, Hyunwoo; Chang, Sukbok


    Owing to the prevalence of nitrogen-containing compounds in functional materials, natural products and important pharmaceutical agents, chemists have actively searched for the development of efficient and selective methodologies allowing for the facile construction of carbon-nitrogen bonds. While metal-catalyzed C-N cross-coupling reactions have been established as one of the most general protocols for C-N bond formation, these methods require starting materials equipped with functional groups such as (hetero)aryl halides or their equivalents, thus generating stoichiometric amounts of halide salts as byproducts. To address this aspect, a transition-metal-catalyzed direct C-H amination approach has emerged as a step- and atom-economical alternative to the conventional C-N cross-coupling reactions. However, despite the significant recent advances in metal-mediated direct C-H amination reactions, most available procedures need harsh conditions requiring stoichiometric external oxidants. In this context, we were curious to see whether a transition-metal-catalyzed mild C-H amination protocol could be achieved using organic azides as the amino source. We envisaged that a dual role of organic azides as an environmentally benign amino source and also as an internal oxidant via N-N2 bond cleavage would be key to develop efficient C-H amination reactions employing azides. An additional advantage of this approach was anticipated: that a sole byproduct is molecular nitrogen (N2) under the perspective catalytic conditions. This Account mainly describes our research efforts on the development of rhodium- and iridium-catalyzed direct C-H amination reactions with organic azides. Under our initially optimized Rh(III)-catalyzed amination conditions, not only sulfonyl azides but also aryl- and alkyl azides could be utilized as facile amino sources in reaction with various types of C(sp(2))-H bonds bearing such directing groups as pyridine, amide, or ketoxime. More recently, a new

  8. Neutron Absorbing Ability Variation in Neutron Absorbing Material Caused by the Neutron Irradiation in Spent Fuel Storage Facility

    International Nuclear Information System (INIS)

    Sohn, Hee Dong; Han, Seul Gi; Lee, Sang Dong; Kim, Ki Hong; Ryu, Eag Hyang; Park, Hwa Gyu


    In spent fuel storage facility like high density spent fuel storage racks and dry storage casks, spent fuels are stored with neutron absorbing materials installed as a part of those facilities, and they are used for absorbing neutrons emitted from spent fuels. Usually structural material with neutron absorbing material of racks and casks are located around spent fuels, so it is irradiated by neutrons for long time. Neutron absorbing ability could be changed by the variation of nuclide composition in neutron absorbing material caused by the irradiation of neutrons. So, neutron absorbing materials are continuously faced with spent fuels with boric acid solution or inert gas environment. Major nuclides in neutron absorbing material are Al 27 , C 12 , B 11 , B 10 and they are changed to numerous other ones as radioactive decay or neutron absorption reaction. The B 10 content in neutron absorbing material dominates the neutron absorbing ability, so, the variation of nuclide composition including the decrease of B 10 content is the critical factor on neutron absorbing ability. In this study, neutron flux in spent fuel, the activation of neutron absorbing material and the variation of nuclide composition are calculated. And, the minimum neutron flux causing the decrease of B 10 content is calculated in spent fuel storage facility. Finally, the variation of neutron multiplication factor is identified according to the one of B 10 content in neutron absorbing material. The minimum neutron flux to impact the neutron absorbing ability is 10 10 order, however, usual neutron flux from spent fuel is 10 8 order. Therefore, even though neutron absorbing material is irradiated for over 40 years, B 10 content is little decreased, so, initial neutron absorbing ability could be kept continuously

  9. Microwave absorbing property of a hybrid absorbent with carbonyl irons coating on the graphite

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Yonggang, E-mail: [Science and Technology on Electromagnetic Scattering Laboratory, Shanghai, 200438 (China); Yan, Zhenqiang; Zhang, Deyuan [Bionic and Micro/Nano/Bio Manufacturing Technology Research Center, School of Mechanical Engineering and Automation, Beihang University, Beijing 100191 (China)


    Graphical abstract: The absorbing property could be enhanced as the CIPs coated on the graphite. - Highlights: • Absorbers filled with CIPs coating on the graphite was fabricated. • The permittivity and permeability increased as CIPs coated. • The CIP materials enhanced the electromagnetic property. • The graphite coated CIPs were effective in 2–18 GHz. - Abstract: The hybrid absorbent filled with carbonyl iron particles (CIPs) coating on the graphite was prepared using a chemical vapor decomposition (CVD) process. X-ray diffraction (XRD) patterns were done to analyze the particle crystal grain structure. The complex permittivity and permeability were measured using a vector network analyzer in the frequency range of 2–18 GHz. The results showed that α-Fe appeared in the super-lattice diffraction peaks in XRD graph. The composites added CIPs coating on the graphite had a higher permittivity and imaginary permeability due to the superior microwave dielectric loss and magnetic loss of the CIPs. The reflection loss (RL) result showed that composites filled with 5 vol% Fe-graphite had an excellent absorbing property in the 2–18 GHz, the minimum RL was −25.14 dB at 6 mm and −26.52 dB at 8 mm, respectively.

  10. A chiral microwave absorbing absorbent of Fe–CoNiP coated on spirulina

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Yonggang, E-mail: [Science and Technology on Electromagnetic Scattering Laboratory, Shanghai, 200438 (China); Yuan, Liming [Science and Technology on Electromagnetic Scattering Laboratory, Shanghai, 200438 (China); Zhang, Deyuan [School of Mechanical Engineering and Automation, Beihang University, Beijing, 100191 (China)


    A chiral bio-absorbent of Fe–CoNiP coated on the spirulina was fabricated by the electroless and chemical vapor decomposition. The scanning electron microscopy (SEM) was used to evaluate the spirulina cells particle morphology. X-ray diffraction (XRD) patterns were done to analyze the particle crystal grain structure. The permittivity and permeability was measured by a vector network analyzer in frequency 8–18 GHz, and the reflection loss (RL) was calculated. The results showed the carbonyl iron particles (CIPs) and CoNiP were bonded to the spirulina surface, the permittivity and permeability could be enlarged as Fe films coated on the particles compared with the CoNiP spirulina, it was attributed to the excellent electromagnetic property of CIPs. The chiral Fe–CoNiP composites had a better absorbing property at 8–18 GHz than the CoNiP spirulina composite, the RL was −16.26 dB at 10.48 GHz, the absorbing band was 9.5–11.5 GHz of RL less than −10 dB, which indicated the Fe–CoNiP spirulina could be an effective absorbent used in 8–18 GHz. - Highlights: • Absorbers filled with Fe–CoNiP coating on the spirulina were fabricated. • The permittivity and permeability increased as CIPs coated. • The Fe material enhanced the electromagnetic property. • The spirulina coated Fe–CoNiP was effective in 8–18 GHz.

  11. Modelling of neutron absorbers in high temperature reactors by combined transport diffusion methods


    Fen, V.; Lebedev, M.; Sarytchev, V.; Scherer, W.


    Today, the neutron-physical description of strong neutron absorbing materials for control and shut-down of nuclear power plants is performed using combined transport and diffusion methods. Two of these approaches are described and compared in this paper. The method of equivalent cross-sections has been developed at the KFA-Jülich Institute for Safety Research and Reactor Technology (ISR) and was widely used for all german HTR reactor concepts. The Obninsk Institute for Nuclear Power Engineeri...

  12. Quantum electrodynamics of strong fields

    International Nuclear Information System (INIS)

    Greiner, W.


    Quantum Electrodynamics of Strong Fields provides a broad survey of the theoretical and experimental work accomplished, presenting papers by a group of international researchers who have made significant contributions to this developing area. Exploring the quantum theory of strong fields, the volume focuses on the phase transition to a charged vacuum in strong electric fields. The contributors also discuss such related topics as QED at short distances, precision tests of QED, nonperturbative QCD and confinement, pion condensation, and strong gravitational fields In addition, the volume features a historical paper on the roots of quantum field theory in the history of quantum physics by noted researcher Friedrich Hund

  13. Corundum-based transparent infrared absorbers

    KAUST Repository

    Schwingenschlögl, Udo


    Hypothetical corundum-based compounds are studied by electronic structure calculations. One quarter of the Al atoms in Al2O3 is replaced by a 3d transition metal from the M = Ti, ..., Zn (d1, ..., d9) series. Structure optimisations are performed for all the M-Al2O3 compounds and the electronic states are evaluated. Due to the M substitutes, narrow partially filled bands are formed at the Fermi energy. Beyond, for M = Ni and M = Cu the optical properties of Al2O3 in the visible range are conserved, while for M = Ti, ..., Co the systems form high accuracy optical filters. Since the compounds absorb the infrared radiation, the M = Ni and M = Cu systems are good candidates for heat-protective coatings. © 2009 Elsevier B.V. All rights reserved.

  14. Electromagnetic radiation absorbers and modulators comprising polyaniline (United States)

    Epstein, Arthur J.; Ginder, John M.; Roe, Mitchell G.; Hajiseyedjavadi, Hamid


    A composition for absorbing electromagnetic radiation, wherein said electromagnetic radiation possesses a wavelength generally in the range of from about 1000 Angstroms to about 50 meters, wherein said composition comprises a polyaniline composition of the formula ##STR1## where y can be equal to or greater than zero, and R.sup.1 and R.sup.2 are independently selected from the group containing of H, --OCH.sub.3, --CH.sub.3, --F, --Cl, --Br, --I, NR.sup.3 .sub.2, --NHCOR.sup.3, --OH, --O.sup.-, SR.sup.3, --OCOR.sup.3, --NO.sub.2, --COOH, --COOR.sup.3, --COR.sup.3, --CHO, and --CN, where R.sup.3 is a C.sub.1 to C.sub.8 alkyl, aryl or aralkyl group.

  15. Light Absorbing Aerosols in Mexico City (United States)

    Marley, N. A.; Kelley, K. L.; Kilaparty, P. S.; Gaffney, J. S.


    The direct effects of aerosol radiative forcing has been identified by the IPCC as a major uncertainty in climate modeling. The DOE Megacity Aerosol Experiment-Mexico City (MAX-Mex), as part of the MILAGRO study in March of 2006, was undertaken to reduce these uncertainties by characterization of the optical, chemical, and physical properties of atmospheric aerosols emitted from this megacity environment. Aerosol samples collected during this study using quartz filters were characterized in the uv-visible-infrared by using surface spectroscopic techniques. These included the use of an integrating sphere approach combined with the use of Kubelka-Munk theory to obtain aerosol absorption spectra. In past work black carbon has been assumed to be the only major absorbing species in atmospheric aerosols with an broad band spectral profile that follows a simple inverse wavelength dependence. Recent work has also identified a number of other absorbing species that can also add to the overall aerosol absorption. These include primary organics from biomass and trash burning and secondary organic aerosols including nitrated PAHs and humic-like substances, or HULIS. By using surface diffuse reflection spectroscopy we have also obtained spectra in the infrared that indicate significant IR absorption in the atmospheric window-region. These data will be presented and compared to spectra of model compounds that allow for evaluation of the potential importance of these species in adding strength to the direct radiative forcing of atmospheric aerosols. This work was supported by the Office of Science (BER), U.S. Department of Energy, Grant No. DE-FG02-07ER64327 as part of the Atmospheric Science Program.

  16. Neutron absorbed dose in a pacemaker CMOS

    Energy Technology Data Exchange (ETDEWEB)

    Borja H, C. G.; Guzman G, K. A.; Valero L, C. Y.; Banuelos F, A.; Hernandez D, V. M.; Vega C, H. R. [Universidad Autonoma de Zacatecas, Unidad Academica de Estudios Nucleares, Calle Cipres No. 10, Fracc. La Penuela, 98068 Zacatecas (Mexico); Paredes G, L., E-mail: [ININ, Carretera Mexico-Toluca s/n, 52750 Ocoyoacac, Estado de Mexico (Mexico)


    The absorbed dose due to neutrons by a Complementary Metal Oxide Semiconductor (CMOS) has been estimated using Monte Carlo methods. Eventually a person with a pacemaker becomes a patient that must be treated by radiotherapy with a linear accelerator; the pacemaker has integrated circuits as CMOS that are sensitive to intense and pulsed radiation fields. When the Linac is working in Bremsstrahlung mode an undesirable neutron field is produced due to photoneutron reactions; these neutrons could damage the CMOS putting the patient at risk during the radiotherapy treatment. In order to estimate the neutron dose in the CMOS a Monte Carlo calculation was carried out where a full radiotherapy vault room was modeled with a W-made spherical shell in whose center was located the source term of photoneutrons produced by a Linac head operating in Bremsstrahlung mode at 18 MV. In the calculations a phantom made of tissue equivalent was modeled while a beam of photoneutrons was applied on the phantom prostatic region using a field of 10 x 10 cm{sup 2}. During simulation neutrons were isotropically transported from the Linac head to the phantom chest, here a 1 {theta} x 1 cm{sup 2} cylinder made of polystyrene was modeled as the CMOS, where the neutron spectrum and the absorbed dose were estimated. Main damages to CMOS are by protons produced during neutron collisions protective cover made of H-rich materials, here the neutron spectrum that reach the CMOS was calculated showing a small peak around 0.1 MeV and a larger peak in the thermal region, both connected through epithermal neutrons. (Author)

  17. X-band microwave absorbing characteristics of multicomponent composites with magnetodielectric fillers

    Energy Technology Data Exchange (ETDEWEB)

    Afghahi, Seyyed Salman Seyyed [Department of Materials Science and Engineering, Imam Hossein University, Tehran (Iran, Islamic Republic of); Jafarian, Mojtaba, E-mail: [Young Researchers and Elite Club, Science and Research Branch, Islamic Azad University, Tehran (Iran, Islamic Republic of); Stergiou, Charalampos A. [Lab. of Inorganic Materials, Centre for Research and Technology Hellas, 57001 Thermi (Greece)


    We have studied the microwave absorbing performance in the X-band (8–12.4 GHz) of epoxy composites filled with magnetic and dielectric oxides and multiwalled carbon nanotubes. To this end, pure cobalt-substituted Ba-hexaferrite and calcium titanate were synthesized with the hydrothermal method in the form of nanosized powder. Moreover, the produced powders were characterized in regard of their structural, morphological and static magnetic properties. For the electromagnetic investigation, composite samples were also prepared with various thicknesses up to 4 mm and two basic filler compositions; namely 30 wt% of BaCoFe{sub 11}O{sub 19} and 30 wt% of the mixture BaCoFe{sub 11}O{sub 19}/CaTiO{sub 3}/carbon nanotubes. The magnetic composites show strong but narrowband reflection losses up to 27.5 dB, whereas the magnetodielectric composites with maximum losses of 15.8 dB possess wider bandwidth of operation, due to improved impedance matching. Furthermore, the characteristic frequency of the maximum losses for these quarter-wavelength absorbers was verified to be in inverse proportion to the layer thickness. These findings are supported by reflectance measurements of the samples both in waveguide and free-space. - Highlights: • Single and multi-component composite absorbers with magnetodielectric fillers were synthesized. • The prepared absorbers are lightweight with 30 wt% filler content in epoxy matrix. • The microwave absorption characteristics of composites were measured by waveguide and free-space methods in the X-band. • Composites with a combination of magnetic and dielectric fillers exhibit wider reflection loss peaks. • Composite absorbers have a realistic potential as microwave absorbers in the X-band.

  18. A THz plasmonics perfect absorber and Fabry-Perot cavity mechanism (Conference Presentation) (United States)

    Zhou, Jiangfeng; Bhattarai, Khagendra; Silva, Sinhara; Jeon, Jiyeon; Kim, Junoh; Lee, Sang Jun; Ku, Zahyun


    The plasmonic metamaterial perfect absorber (MPA) is a recently developed branch of metamaterial which exhibits nearly unity absorption within certain frequency range.[1-6] The optically thin MPA possesses characteristic features of angular-independence, high Q-factor and strong field localization that have inspired a wide range of applications including electromagnetic wave absorption,[3, 7, 8] spatial[6] and spectral[5] modulation of light,[9] selective thermal emission,[9] thermal detecting[10] and refractive index sensing for gas[11] and liquid[12, 13] targets. In this work, we demonstrate a MPA working at terahertz (THz) regime and characterize it using an ultrafast THz time-domain spectroscopy (THz-TDS). Our study reveal an ultra-thin Fabry-Perot cavity mechanism compared to the impedance matching mechanism widely adopted in previous study [1-6]. Our results also shows higher-order resonances when the cavities length increases. These higher order modes exhibits much larger Q-factor that can benefit potential sensing and imaging applications. [1] C. M. Watts, X. L. Liu, and W. J. Padilla, "Metamaterial Electromagnetic Wave Absorbers," Advanced Materials, vol. 24, pp. 98-120, Jun 19 2012. [2] M. Hedayati, F. Faupel, and M. Elbahri, "Review of Plasmonic Nanocomposite Metamaterial Absorber," Materials, vol. 7, pp. 1221-1248, 2014. [3] N. I. Landy, S. Sajuyigbe, J. J. Mock, D. R. Smith, and W. J. Padilla, "Perfect metamaterial absorber," Physical Review Letters, vol. 100, p. 207402, May 23 2008. [4] H. R. Seren, G. R. Keiser, L. Cao, J. Zhang, A. C. Strikwerda, K. Fan, et al., "Optically Modulated Multiband Terahertz Perfect Absorber," Advanced Optical Materials, vol. 2, pp. 1221-1226, 2014. [5] D. Shrekenhamer, J. Montoya, S. Krishna, and W. J. Padilla, "Four-Color Metamaterial Absorber THz Spatial Light Modulator," Advanced Optical Materials, vol. 1, pp. 905-909, 2013. [6] S. Savo, D. Shrekenhamer, and W. J. Padilla, "Liquid Crystal Metamaterial Absorber Spatial

  19. Strong WW Interaction at LHC

    Energy Technology Data Exchange (ETDEWEB)

    Pelaez, Jose R


    We present a brief pedagogical introduction to the Effective Electroweak Chiral Lagrangians, which provide a model independent description of the WW interactions in the strong regime. When it is complemented with some unitarization or a dispersive approach, this formalism allows the study of the general strong scenario expected at the LHC, including resonances.

  20. Microbial adhesion on novel yttria-stabilized tetragonal zirconia (Y-TZP) implant surfaces with nitrogen-doped hydrogenated amorphous carbon (a-C:H:N) coatings. (United States)

    Schienle, Stefanie; Al-Ahmad, Ali; Kohal, Ralf Joachim; Bernsmann, Falk; Adolfsson, Erik; Montanaro, Laura; Palmero, Paola; Fürderer, Tobias; Chevalier, Jérôme; Hellwig, Elmar; Karygianni, Lamprini


    Biomaterial surfaces are at high risk for initial microbial colonization, persistence, and concomitant infection. The rationale of this study was to assess the initial adhesion on novel implant surfaces of Enterococcus faecalis, Staphylococcus aureus, Escherichia coli, Pseudomonas aeruginosa, and Candida albicans upon incubation. The tested samples were 3 mol% yttria-stabilized tetragonal zirconia polycrystal (3Y-TZP) samples with nitrogen-doped hydrogenated amorphous carbon (a-C:H:N) coating (A) and 3Y-TZP samples coated with ceria-stabilized zirconia-based (Ce-TZP) composite and a-C:H:N (B). Uncoated 3Y-TZP samples (C) and bovine enamel slabs (BES) served as controls. Once the surface was characterized, the adherent microorganisms were quantified by estimating the colony-forming units (CFUs). Microbial vitality was assessed by live/dead staining, and microbial-biomaterial surface topography was visualized by scanning electron microscopy (SEM). Overall, A and B presented the lowest CFU values for all microorganisms, while C sheltered significantly less E. faecalis, P. aeruginosa, and C. albicans than BES. Compared to the controls, B demonstrated the lowest vitality values for E. coli (54.12 %) and C. albicans (67.99 %). Interestingly, A (29.24 %) exhibited higher eradication rates for S. aureus than B (13.95 %). Within the limitations of this study, a-C:H:N-coated 3Y-TZP surfaces tended to harbor less initially adherent microorganisms and selectively interfered with their vitality. This could enable further investigation of the new multi-functional zirconia surfaces to confirm their favorable antimicrobial properties in vivo.

  1. Estimation of lower flammability limits of C-H compounds in air at atmospheric pressure, evaluation of temperature dependence and diluent effect. (United States)

    Mendiburu, Andrés Z; de Carvalho, João A; Coronado, Christian R


    Estimation of the lower flammability limits of C-H compounds at 25 °C and 1 atm; at moderate temperatures and in presence of diluent was the objective of this study. A set of 120 C-H compounds was divided into a correlation set and a prediction set of 60 compounds each. The absolute average relative error for the total set was 7.89%; for the correlation set, it was 6.09%; and for the prediction set it was 9.68%. However, it was shown that by considering different sources of experimental data the values were reduced to 6.5% for the prediction set and to 6.29% for the total set. The method showed consistency with Le Chatelier's law for binary mixtures of C-H compounds. When tested for a temperature range from 5 °C to 100 °C, the absolute average relative errors were 2.41% for methane; 4.78% for propane; 0.29% for iso-butane and 3.86% for propylene. When nitrogen was added, the absolute average relative errors were 2.48% for methane; 5.13% for propane; 0.11% for iso-butane and 0.15% for propylene. When carbon dioxide was added, the absolute relative errors were 1.80% for methane; 5.38% for propane; 0.86% for iso-butane and 1.06% for propylene. Copyright © 2014 Elsevier B.V. All rights reserved.

  2. Strong-back safety latch

    International Nuclear Information System (INIS)

    DeSantis, G.N.


    The calculation decides the integrity of the safety latch that will hold the strong-back to the pump during lifting. The safety latch will be welded to the strong-back and will latch to a 1.5-in. dia cantilever rod welded to the pump baseplate. The static and dynamic analysis shows that the safety latch will hold the strong-back to the pump if the friction clamps fail and the pump become free from the strong-back. Thus, the safety latch will meet the requirements of the Lifting and Rigging Manual for under the hook lifting for static loading; it can withstand shock loads from the strong-back falling 0.25 inch

  3. Strong-back safety latch

    Energy Technology Data Exchange (ETDEWEB)

    DeSantis, G.N.


    The calculation decides the integrity of the safety latch that will hold the strong-back to the pump during lifting. The safety latch will be welded to the strong-back and will latch to a 1.5-in. dia cantilever rod welded to the pump baseplate. The static and dynamic analysis shows that the safety latch will hold the strong-back to the pump if the friction clamps fail and the pump become free from the strong-back. Thus, the safety latch will meet the requirements of the Lifting and Rigging Manual for under the hook lifting for static loading; it can withstand shock loads from the strong-back falling 0.25 inch.

  4. Palladium-Catalyzed Direct C-H Arylations of Dioxythiophenes Bearing Reactive Functional Groups: A Step-Economical Approach for Functional π-Conjugated Oligoarenes

    KAUST Repository

    Liu, Ching-Yuan


    A Pd-catalyzed and single-step C-H arylation of dioxythiophene derivates bearing unprotected reactive functional groups (-OH, -COOH, -N3) in a phosphine-free manner has been developed. Various dioxythiopene-based oligoarenes with extended π-conjugation are obtained with good yields (up to 90%). These oligoarenes display suitable optical properties (absorption and emission maxima, quantum yields) and contain reactive functional groups suitable for further conjugations with bioactive molecules. This new methodology is step economical (fewer synthetic steps), environmental friendly (no toxic metal-containing side-poducts) and the oligoarenes synthesized are potentially applicable for bio-labeling, bioimaging, and biosensing.

  5. Teaching Old Compounds New Tricks: DDQ-Photocatalyzed C-H Amination of Arenes with Carbamates, Urea, and N-Heterocycles. (United States)

    Das, Somnath; Natarajan, Palani; König, Burkhard


    The C-H amination of benzene derivatives was achieved using DDQ as photocatalyst and BocNH 2 as the amine source under aerobic conditions and visible light irradiation. Electron-deficient and electron-rich benzenes react as substrates with moderate to good product yields. The amine scope of the reaction comprises Boc-amine, carbamates, pyrazoles, sulfonimides and urea. Preliminary mechanistic investigations indicate arene oxidation by the triplet of DDQ to radical cations with different electrophilicity and a charge transfer complex between the amine and DDQ as intermediate of the reaction. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Polycyclization Enabled by Relay Catalysis: One-Pot Manganese-Catalyzed C-H Allylation and Silver-Catalyzed Povarov Reaction. (United States)

    Chen, Shi-Yong; Li, Qingjiang; Liu, Xu-Ge; Wu, Jia-Qiang; Zhang, Shang-Shi; Wang, Honggen


    In this study, a Mn I /Ag I -based relay catalysis process is described for the one-pot synthesis of polycyclic products by a formal [3+2] and [4+2] cycloaddition reaction cascade. A manganese(I) complex catalyzed the first example of directed C-H allylation with allenes, setting the stage for an in situ Povarov cyclization catalyzed by silver(I). The reaction proceeds with high bond-forming efficiency (three C-C bonds), broad substrate scope, high regio- and stereoselectivity, and 100 % atom economy. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Palladium-catalyzed direct C-H arylations of dioxythiophenes bearing reactive functional groups: a step-economical approach for functional π-conjugated oligoarenes. (United States)

    Liu, Ching-Yuan; Chong, Hui; Lin, Hsing-An; Yamashita, Yoshiro; Zhang, Bin; Huang, Kuo-Wei; Hashizume, Daizuke; Yu, Hsiao-Hua


    A Pd-catalyzed single-step C-H arylation of dioxythiophene derivatives bearing unprotected reactive functional groups (-OH, -COOH, -N3) in a phosphine-free manner has been developed. Various dioxythiopene-based oligoarenes with extended π-conjugation are obtained with good yields (up to 90%). These oligoarenes display suitable optical properties (absorption and emission maxima, quantum yields) and contain reactive functional groups suitable for further conjugations with bioactive molecules. This new methodology is step economical (fewer synthetic steps) and environmentally friendly (no toxic metal-containing by-products) and the oligoarenes synthesized are potentially applicable for bio-labeling, bioimaging, and biosensing.

  8. Aliphatic C-H activation with aluminium trichloride-acetyl chloride: expanding the scope of the Baddeley reaction for the functionalisation of saturated hydrocarbons. (United States)

    Lyall, Catherine L; Uosis-Martin, Mario; Lowe, John P; Mahon, Mary F; Pantoş, G Dan; Lewis, Simon E


    The functionalisation of decalin by means of an "aliphatic Friedel-Crafts" reaction was reported over fifty years ago by Baddeley et al. This protocol is of current relevance in the context of C-H activation and here we demonstrate its applicability to a range of other saturated hydrocarbons. Structural elucidation of the products is described and a mechanistic rationale for their formation is presented. The "aliphatic Friedel-Crafts" procedure allows for production of novel oxygenated building blocks from abundant hydrocarbons and as such can be considered to add significant synthetic value in a single step.

  9. Atroposelective Synthesis of Axially Chiral Biaryls by Palladium-Catalyzed Asymmetric C-H Olefination Enabled by a Transient Chiral Auxiliary. (United States)

    Yao, Qi-Jun; Zhang, Shuo; Zhan, Bei-Bei; Shi, Bing-Feng


    Atroposelective synthesis of axially chiral biaryls by palladium-catalyzed C-H olefination, using tert-leucine as an inexpensive, catalytic, and transient chiral auxiliary, has been realized. This strategy provides a highly efficient and straightforward access to a broad range of enantioenriched biaryls in good yields (up to 98 %) with excellent enantioselectivities (95 to >99 % ee). Kinetic resolution of trisubstituted biaryls bearing sterically more demanding substituents is also operative, thus furnishing the optically active olefinated products with excellent selectivity (95 to >99 % ee, s-factor up to 600). © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Palladium(II)-Catalyzed meta-C-H Olefination: Constructing Multisubstituted Arenes through Homo-Diolefination and Sequential Hetero-Diolefination. (United States)

    Bera, Milan; Maji, Arun; Sahoo, Santosh K; Maiti, Debabrata


    Divinylbenzene derivatives represent an important class of molecular building blocks in organic chemistry and materials science. Reported herein is the palladium-catalyzed synthesis of divinylbenzenes by meta-C-H olefination of sulfone-based arenes. Successful sequential olefinations in a position-selective manner provided a novel route for the synthesis of hetero-dialkenylated products, which are difficult to access using conventional methods. Additionally, 1,3,5-trialkenylated compounds can be generated upon successful removal of the directing group. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Determination of Fatty Acid, C, H, N and Trace Element Composition in Grape Seed by GC/MS, FTIR, Elemental Analyzer and ICP/OES


    Seçilmiş Canbay, Hale; Bardakçı, Belgin


    Abstract: Four different methods were used for the investigation of fatty acid, C, H, N and trace element composition of grape seed oil and pulp. The fatty acid profile of the grape seed oil was measured by GC/MS. Moreover, structural analysis of the oil was carried out by FT/IR spectrometry with a Zn Se ATR accessory. The quantification of selected metals Na, K, Mg, Ca, Mn, Fe, Zn and Cu in grape seed oil and pulp was carried out using microwave assisted digestion followed by ICP/OES. Grape ...

  12. Preparation and characterization of super absorbent polymer from sugarcane bagasse

    International Nuclear Information System (INIS)

    Wiwien Andriyanti; Suyanti; Ngasifudin


    Sugarcane bagasse is a source of biomass which large enough numbers and has not been fully exploited. At this time has developed a super absorbent polymer material of sugarcane bagasse that can absorb water up to several times of its own weight and keep this water. Super absorbent polymers can be used as a soil conditioner that can be used as an absorber and storage of ground water, the giver of nutrients for plants, and can improve soil properties. The purpose of this study is to make and characterization of super absorbent polymer (PCS) from sugarcane bagasse. Preparation of super absorbent polymers (PCS) has been done by grafting method using ionizing radiation from Electron Beam Engineering (MBE) 350 mA keV/10. Irradiation process carried out with a dose variation of 20, 35, and 50 kGy. Increasing doses of radiation will increase the percentage fraction of transplantation (grafting) and the fraction of water absorption ability (swelling ratio). (author)

  13. Observation of strong leakage reduction in crystal assisted collimation of the SPS beam

    Directory of Open Access Journals (Sweden)

    W. Scandale


    Full Text Available In ideal two-stage collimation systems, the secondary collimator–absorber should have its length sufficient to exclude practically the exit of halo particles with large impact parameters. In the UA9 experiments on the crystal assisted collimation of the SPS beam a 60 cm long tungsten bar is used as a secondary collimator–absorber which is insufficient for the full absorption of the halo protons. Multi-turn simulation studies of the collimation allowed to select the position for the beam loss monitor downstream the collimation area where the contribution of particles deflected by the crystal in channeling regime but emerging from the secondary collimator–absorber is considerably reduced. This allowed observation of a strong leakage reduction of halo protons from the SPS beam collimation area, thereby approaching the case with an ideal absorber.

  14. Local Structure Analysis of Materials for Solar Cell Absorber Layer


    Jewell, Leila Elizabeth


    This dissertation examines solar cell absorber materials that have the potential to replace silicon in solar cells, including several copper-based sulfides and perovskites. Earth-abundant absorbers such as these become even more cost-effective when used in a nanostructured solar cell. Atomic layer deposition (ALD) and chemical vapor deposition (CVD) deposit highly conformal films and hence are important tools for developing extremely thin absorber solar cells with scalability. Thus, the prima...

  15. Tridimensional measurements of the Barrel absorbers (Module 0)

    CERN Document Server

    Puzo, P


    In this note we describe the principle of the measurements done on the ATLAS absorbers that have been fabricated for the module 0 of the Liquid Argon Electromagnetic Barrel Calorimeter. We explain how the measurements are used to reconstruct the tridimensional geometry of each absorber. We show the results obtained for module 0. The same kind of measurements will be done for the series absorbers

  16. Titanium: light, strong, and white (United States)

    Woodruff, Laurel; Bedinger, George


    Titanium (Ti) is a strong silver-gray metal that is highly resistant to corrosion and is chemically inert. It is as strong as steel but 45 percent lighter, and it is twice as strong as aluminum but only 60 percent heavier. Titanium dioxide (TiO2) has a very high refractive index, which means that it has high light-scattering ability. As a result, TiO2 imparts whiteness, opacity, and brightness to many products. ...Because of the unique physical properties of titanium metal and the whiteness provided by TiO2, titanium is now used widely in modern industrial societies.

  17. NASA's Bio-Inspired Acoustic Absorber Concept (United States)

    Koch, L. Danielle


    Transportation noise pollutes our worlds cities, suburbs, parks, and wilderness areas. NASAs fundamental research in aviation acoustics is helping to find innovative solutions to this multifaceted problem. NASA is learning from nature to develop the next generation of quiet aircraft.The number of road vehicles and airplanes has roughly tripled since the 1960s. Transportation noise is audible in nearly all the counties across the US. Noise can damage your hearing, raise your heart rate and blood pressure, disrupt your sleep, and make communication difficult. Noise pollution threatens wildlife when it prevents animals from hearing prey, predators, and mates. Noise regulations help drive industry to develop quieter aircraft. Noise standards for aircraft have been developed by the International Civil Aviation Organization and adopted by the US Federal Aviation Administration. The US National Park Service is working with the Federal Aviation Administration to try to balance the demand for access to the parks and wilderness areas with preservation of the natural soundscape. NASA is helping by conceptualizing quieter, more efficient aircraft of the future and performing the fundamental research to make these concepts a reality someday. Recently, NASA has developed synthetic structures that can absorb sound well over a wide frequency range, and particularly below 1000 Hz, and which mimic the acoustic performance of bundles of natural reeds. We are adapting these structures to control noise on aircraft, and spacecraft. This technology might be used in many other industrial or architectural applications where acoustic absorbers have tight constraints on weight and thickness, and may be exposed to high temperatures or liquids. Information about this technology is being made available through reports and presentations available through the NASA Technical Report Server, Organizations who would like to collaborate with NASA or commercialize NASAs technology

  18. Ultraviolet absorbance as a proxy for total dissolved mercury in streams

    International Nuclear Information System (INIS)

    Dittman, Jason A.; Shanley, James B.; Driscoll, Charles T.; Aiken, George R.; Chalmers, Ann T.; Towse, Janet E.


    Stream water samples were collected over a range of hydrologic and seasonal conditions at three forested watersheds in the northeastern USA. Samples were analyzed for dissolved total mercury (THg d ), DOC concentration and DOC composition, and UV 254 absorbance across the three sites over different seasons and flow conditions. Pooling data from all sites, we found a strong positive correlation of THg d to DOC (r 2 = 0.87), but progressively stronger correlations of THg d with the hydrophobic acid fraction (HPOA) of DOC (r 2 = 0.91) and with UV 254 absorbance (r 2 = 0.92). The strength of the UV 254 absorbance-THg d relationship suggests that optical properties associated with dissolved organic matter may be excellent proxies for THg d concentration in these streams. Ease of sample collection and analysis, the potential application of in-situ optical sensors, and the possibility for intensive monitoring over the hydrograph make this an effective, inexpensive approach to estimate THg d flux in drainage waters. - Ultraviolet absorbance measurements are a cost-effective proxy to estimate dissolved mercury concentration in stream water.

  19. Modeling X-ray Absorbers in AGNs with MHD-Driven Accretion-Disk Winds (United States)

    Fukumura, Keigo; Kazanas, D.; Shrader, C. R.; Tombesi, F.; Contopoulos, J.; Behar, E.


    We have proposed a systematic view of the observed X-ray absorbers, namely warm absorbers (WAs) in soft X-ray and highly-ionized ultra-fast outflows (UFOs), in the context of magnetically-driven accretion-disk wind models. While potentially complicated by variability and thermal instability in these energetic outflows, in this simplistic model we have calculated 2D kinematic field as well as density and ionization structure of the wind with density profile of 1/r corresponding to a constant column distribution per decade of ionization parameter. In particular we show semi-analytically that the inner layer of the disk-wind manifests itself as the strongly-ionized fast outflows while the outer layer is identified as the moderately-ionized absorbers. The computed characteristics of these two apparently distinct absorbers are consistent with X-ray data (i.e. a factor of ~100 difference in column and ionization parameters as well as low wind velocity vs. near-relativistic flow). With the predicted contour curves for these wind parameters one can constrain allowed regions for the presence of WAs and UFOs.The model further implies that the UFO's gas pressure is comparable to that of the observed radio jet in 3C111 suggesting that the magnetized disk-wind with density profile of 1/r is a viable agent to help sustain such a self-collimated jet at small radii.

  20. Basic concepts about application of dual vibration absorbers to seismic design of nuclear piping systems

    International Nuclear Information System (INIS)

    Hara, F.; Seto, K.


    The design value of damping for nuclear piping systems is a vital parameter in ensuring safety in nuclear plants during large earthquakes. Many experiments and on-site tests have been undertaken in nuclear-industry developed countries to determine rational design values. However damping value in nuclear piping systems is so strongly influenced by many piping parameters that it shows a tremendous dispersion in its experimental values. A new trend has recently appeared in designing nuclear pipings, where they attempt to use a device to absorb vibration energy induced by seismic excitation. A typical device is an energy absorbing device, made of a special material having a high capacity of plasticity, which is installed between the piping and the support. This paper deals with the basic study of application of dual vibration absorbers to nuclear piping systems to accomplish high damping value and reduce consequently seismic response at resonance frequencies of a piping system, showing their effectiveness from not only numerical calculation but also experimental evaluation of the vibration responses in a 3D model piping system equipped with dual two vibration absorbers