WorldWideScience

Sample records for c-si bond formations

  1. Sequential C-Si Bond Formations from Diphenylsilane: Application to Silanediol Peptide Isostere Precursors

    DEFF Research Database (Denmark)

    Nielsen, Lone; Skrydstrup, Troels

    2008-01-01

    and the first new carbon-silicon bond. The next step is the reduction of this hydridosilane with lithium metal providing a silyl lithium reagent, which undergoes a highly diastereoselective addition to an optically active tert-butanesulfinimine, thus generating the second C-Si bond. This method allows...

  2. Bonding analysis of telluroketones H₂A = Te (A = C, Si, Ge).

    Science.gov (United States)

    Jaufeerally, Naziah B; Ramasami, Ponnadurai; Jerabek, Paul; Frenking, Gernot

    2014-10-01

    Quantum chemical calculations using density functional theory BP86/def2-TZVPP and ab initio methods at CCSD(T)/def2-TZVPP have been carried for the telluroketones H2A=Te (A = C, Si, Ge). DFT calculations have also been carried out for the ketones H2C=E (E = O, S, Se, Te) and for the complexes NHC → [H2A=Te] → B(C6F5)3. The nature of the bonding has been investigated with charge- and energy decomposition analyses. The calculated bond dissociation energies for the double bonds of the H2C = E and H2A = Te molecules show the expected trends O > S > Se > Te for atom E and C > Si > Ge for atom A. Complexation of the telluroketones in NHC → [H2A = Te] → B(C6F5)3 leads to longer and weaker A-Te bonds which exhibit the surprising trend for the bond dissociation energy Si > Ge > C. The contribution of the π bonding in H2A = Te increases for the heavier atoms with the sequence C < Si < Ge.

  3. Glycerol-bonded 3C-SiC nanocrystal solid films exhibiting broad and stable violet to blue-green emission.

    Science.gov (United States)

    Wang, J; Xiong, S J; Wu, X L; Li, T H; Chu, Paul K

    2010-04-14

    We have produced glycerol-bonded 3C-SiC nanocrystal (NC) films, which when excited by photons of different wavelengths, produce strong and tunable violet to blue-green (360-540 nm) emission as a result of the quantum confinement effects rendered by the 3C-SiC NCs. The emission is so intense that the emission spots are visible to the naked eyes. The light emission is very stable and even after storing in air for more than six months, no intensity degradation can be observed. X-ray photoelectron spectroscopy and absorption fine structure measurements indicate that the Si-terminated NC surfaces are completely bonded to glycerol molecules. Calculations of geometry optimization and electron structures based on the density functional theory for 3C-SiC NCs with attached glycerol molecules show that these molecules are bonded on the NCs causing strong surface structural change, while the isolated levels in the conduction band of the bare 3C-SiC NCs are replaced with quasi-continuous bands that provide continuous tunability of the emitted light by changing the frequencies of exciting laser. As an application, we demonstrate the potential of using 3C-SiC NCs to fabricate full-color emitting solid films by incorporating porous silicon.

  4. Back contact formation for p-type based a-Si:H/c-Si heterojunction solar cells

    Energy Technology Data Exchange (ETDEWEB)

    Tucci, Mario; Serenelli, Luca; De Iuliis, Simona; Izzi, Massimo [ENEA Research Center Casaccia, Via Anguillarese 301, 00123 Rome (Italy); De Cesare, Giampiero; Caputo, Domenico [Department of Electronic Engineering, University ' ' Sapienza' ' , Via Eudossiana 18, 00184 Rome (Italy)

    2011-03-15

    Even if p-type silicon is a more common PV material, heterojunction solar cells on p-type c-Si are less popular than on n-type. In turn, it has been difficult to achieve high efficiency with double-sided heterojunction with intrinsic thin layer structure on p-type c-Si. The double-sided silicon heterojunction solar cell is more appropriate for n-type crystalline silicon wafers than for p-type c-Si ones because of larger band offset at the valence band edge between the amorphous and crystalline semiconductors with respect to the conduction band edge. Indeed, it represents a large barrier for majority carrier holes flowing through to the back contact. In turn at the backside, the small conduction band offset provides a much less effective mirror for the minority carrier electrons. We have found an alternative way to obtain a quasi-ohmic contact promoting the formation of a CrSi film on top of p-a-Si:H layer. This reduces the problem of low p-a-Si:H doping value and the high activation energy, leading to a better carrier collection. In this work we present a detailed investigation of the p-c-Si/i-a-Si:H/p-a-Si:H contact, comparing the experimental transport measurements with numerical model of the stacked structure. We verify the effectiveness of p-c-Si/i-a-Si:H/p-a-Si:H as back side contact on the heterojunction solar cell performances. (copyright 2011 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  5. Formation of permeation barriers on ceramic SiC/SiC composites

    Energy Technology Data Exchange (ETDEWEB)

    Racault, C. [Commission of the European Communities, Ispra (Italy). Joint Research Centre; Serra, E. [Safety Technology Institute, Ispra Establishment, I-21020 Ispra (Vatican City State, Holy See) (Italy); Fenici, P. [Commission of the European Communities, Ispra (Italy). Joint Research Centre

    1996-10-01

    The effectiveness as permeation barriers of the following CVD and PVD (sputtering) coatings has been investigated: TiC+Al{sub 2}O{sub 3}(CVD), SiC(CVD), SiO{sub 2}(CVD), TiN(CVD), TiN(CVD)+TiN(PVD) and SiC(CVD)+Al{sub 2}O{sub 3}(PVD). The substrate material was a SiC/SiC composite, proposed as low activation structural material for fusion applications. Permeation measurements were performed in the temperature range 300-750 K using deuterium at pressures in the range 0.5-150 kPa. A linear dependence of permeation rate on pressure was measured. The efficiency of the coatings as deuterium permeation barriers is discussed in terms of coating microstructure. The best result was obtained with a bilayer of TiN(CVD) (15 {mu}m) +TiN(PVD) (8 {mu}m). (orig.).

  6. Synergistic effect of displacement damage, helium and hydrogen on microstructural change of SiC/SiC composites fabricated by reaction bonding process

    Energy Technology Data Exchange (ETDEWEB)

    Taguchi, T.; Igawa, N.; Wakai, E.; Jitsukawa, S. [Japan Atomic Energy Agency, Naga-gun, Ibaraki-ken (Japan); Hasegawa, A. [Tohoku Univ., Dept. of Quantum Science and Energy Engr., Sendai (Japan)

    2007-07-01

    Full text of publication follows: Continuous silicon carbide (SiC) fiber reinforced SiC matrix (SiC/SiC) composites are known to be attractive candidate materials for first wall and blanket components in fusion reactors. In the fusion environment, helium and hydrogen are produced and helium bubbles can be formed in the SiC by irradiation of 14-MeV neutrons. Authors reported the synergistic effect of helium and hydrogen as transmutation products on swelling behavior and microstructural change of the SiC/SiC composites fabricated by chemical vapor infiltration (CVI) process. Authors also reported about the fabrication of high thermal conductive SiC/SiC composites by reaction bonding (RB) process. The matrix fabricated by RB process has different microstructures such as bigger grain size of SiC and including Si phase as second phase from that by CVI process. It is, therefore, investigated the synergistic effect of displacement damage, helium and hydrogen as transmutation products on the microstructure of SiC/SiC composite by RB process in this study. The SiC/SiC composites by RB process were irradiated by the simultaneous triple ion irradiation (Si{sup 2+}, He{sup +} and H{sup +}) at 800 and 1000 deg. C. The displacement damage was induced by 6.0 MeV Si{sup 2+} ion irradiation up to 10 dpa. The microstructures of irradiated SiC/SiC composites by RB process were observed by TEM. The double layer of carbon and SiC as interphase between fiber and matrix by a chemical vapor deposition (CVD) was coated on SiC fibers in the SiC/SiC composites by RB process. The TEM observation revealed that He bubbles were formed both in the matrix by RB and SiC interphase by CVD process. Almost all He bubbles were formed at the grain boundary in SiC interphase by CVD process. On the other hand, He bubbles were formed both at the grain boundary and in Si grain of the matrix by RB process. The average size of He bubbles in the matrix by RB was smaller than that in SiC interphase by CVD

  7. Vacancy effects on the formation of He and Kr cavities in 3C-SiC irradiated and annealed at elevated temperatures

    Energy Technology Data Exchange (ETDEWEB)

    Zang, Hang, E-mail: zanghang@xjtu.edu.cn [Department of Nuclear Science and Technology, Xi’an Jiaotong University, Xi’an 710049 (China); Jiang, Weilin, E-mail: weilin.jiang@pnnl.gov [Pacific Northwest National Laboratory, Richland, WA 99352 (United States); Liu, Wenbo [Department of Nuclear Science and Technology, Xi’an Jiaotong University, Xi’an 710049 (China); Devaraj, Arun; Edwards, Danny J.; Henager, Charles H.; Kurtz, Richard J. [Pacific Northwest National Laboratory, Richland, WA 99352 (United States); Li, Tao; He, Chaohui; Yun, Di [Department of Nuclear Science and Technology, Xi’an Jiaotong University, Xi’an 710049 (China); Wang, Zhiguang [Institute of Modern Physics, Chinese Academy of Sciences, Lanzhou 730000 (China)

    2016-12-15

    Highlights: • He and Kr cavities are formed in ion-implanted and 1600 °C annealed 3C-SiC. • A higher vacancy concentration leads to formation of cavities with a smaller size and higher density. • Presence of He in irradiated 3C-SiC can significantly promote cavity growth. • Small voids are formed in Kr ion penetrated 3C-SiC during thermal annealing at 1600 °C. • Local Kr migration and trapping at cavities in SiC are observed, but long-range Kr diffusion does not occur at 1600 °C. - Abstract: Polycrystalline 3C-SiC was sequentially irradiated at 400 and 750 °C with 120 keV He{sup 2+} and 4 MeV Kr{sup 15+} ions to 10{sup 17} and 4 × 10{sup 16} cm{sup −2}, respectively. The Kr{sup 15+} ions penetrated the entire depth region of the He{sup 2+} ion implantation. Three areas of He{sup 2+}, Kr{sup 15+} and He{sup 2+} + Kr{sup 15+} ion implanted SiC were created through masked overlapping irradiation. The sample was subsequently annealed at 1600 °C in vacuum and characterized using cross-sectional transmission electron microscopy and energy-dispersive X-ray spectroscopy. Compared to the He{sup 2+} ion only implanted SiC, He cavities show a smaller size and higher density in the co-implanted SiC. At 25 dpa, presence of He in the co-implanted 3C-SiC significantly promotes cavity growth; much smaller voids are formed in the Kr{sup 15+} ion only irradiated SiC at the same dose. In addition, local Kr migration and trapping at cavities occurs, but long-range Kr diffusion in SiC is not observed up to 1600 °C.

  8. Development and Property Evaluation of Selected HfO2-Silicon and Rare Earth-Silicon Based Bond Coats and Environmental Barrier Coating Systems for SiC/SiC Ceramic Matrix Composites

    Science.gov (United States)

    Zhu, Dongming

    2016-01-01

    Ceramic environmental barrier coatings (EBC) and SiC/SiC ceramic matrix composites (CMCs) will play a crucial role in future aircraft propulsion systems because of their ability to significantly increase engine operating temperatures, improve component durability, reduce engine weight and cooling requirements. Advanced EBC systems for SiC/SiC CMC turbine and combustor hot section components are currently being developed to meet future turbine engine emission and performance goals. One of the significant material development challenges for the high temperature CMC components is to develop prime-reliant, high strength and high temperature capable environmental barrier coating bond coat systems, since the current silicon bond coat cannot meet the advanced EBC-CMC temperature and stability requirements. In this paper, advanced NASA HfO2-Si and rare earth Si based EBC bond coat EBC systems for SiC/SiC CMC combustor and turbine airfoil applications are investigated. High temperature properties of the advanced EBC systems, including the strength, fracture toughness, creep and oxidation resistance have been studied and summarized. The advanced NASA EBC systems showed some promise to achieve 1500C temperature capability, helping enable next generation turbine engines with significantly improved engine component temperature capability and durability.

  9. Glass formation and magnetic properties of Fe-C-Si-B-P-(Cr-Al-Co) bulk metallic glasses fabricated using industrial raw materials

    Science.gov (United States)

    Li, H. X.; Wang, S. L.; Yi, S.; Jiao, Z. B.; Wu, Y.; Lu, Z. P.

    2009-09-01

    Formation of Fe-C-Si-B-P-(Cr-Al-Co) bulk metallic glasses with enhanced glass-forming ability (GFA) and magnetic properties fabricated using industrial pig-iron and Fe-P alloys as raw materials has been studied. It was found that GFA of the pig-iron (Fe 79.5C 18.0Si 2.3P 0.2, at%) could be improved by proper additions of only metalloids C, Si, P and B, and fully glassy structure was obtained in the Fe 75.5C 7.0Si 3.3B 5.5P 8.7 alloy with a critical diameter of 1 mm. With suitable additions of metallic elements Cr, Co and Al, the GFA is further increased and fully amorphous rods in 4 mm diameter can be prepared for the Fe 68.2C 7.0Si 3.3B 5.5P 8.7Cr 2.3Al 2.0Co 3.0 alloy that shows a unique combination of good soft-magnetic properties ( Ms=1.03 T, Hc=9.39 A/m), high GFA and high fracture strength. These low-cost Fe-based bulk metallic glasses fabricated using industrial raw materials have a potential to be utilized as engineering materials.

  10. Vacancy effects on the formation of helium and krypton cavities in 3-C-SiC irradiated and annealed at elevated temperatures

    Energy Technology Data Exchange (ETDEWEB)

    Zang, Hang; Liu, Wenbo; Li, Tao; He, Chaohui; Yun, Di; Jiang, Weilin; Devaraj, Arun; Edwards, Danny J.; Henager, Charles H.; Kurtz, Richard J.; Wang, Zhiguang

    2017-02-27

    Polycrystalline 3C-SiC was sequentially irradiated at 400 and 750°C with 120 keV He2+ and 4 MeV Kr15+ ions to 1017 and 41016 cm-2, respectively. The Kr15+ ions penetrated the entire depth of the He2+ ion implantation region. Three areas of He2+, Kr15+ and He2+ + Kr15+ ion implanted 3C-SiC were created through masked overlapping irradiations. The sample was subsequently annealed at 1600°C in vacuum and characterized using cross-sectional transmission electron microscopy and energy-dispersive x-ray spectroscopy. Compared to the He2+ ion only implanted 3C-SiC, helium cavities in the He2+ and Kr15+ co-implanted 3C-SiC had a smaller size but higher density. At 25 dpa, presence of He in the co-implanted 3C-SiC significantly promoted cavity growth; much smaller voids were formed in the Kr15+ ion only irradiated 3C-SiC at the same dose. In addition, local Kr migration and trapping at cavities occurred, but long-range Kr diffusion in 3C-SiC was not observed up to 1600°C.

  11. The unexpected formation of Au δ+ -Si δ- by the resonance neutralization of Ar + during the low energy bombardment of Au nanoparticles on c-Si

    Science.gov (United States)

    Yang, De-Quan; Sacher, Edward

    2009-05-01

    Nanoscale Au layers, with irregular porosities, have been formed by the low energy Ar + bombardment of Au nanoparticles that were sputter-deposited onto native oxide-covered Si surfaces. High-resolution field emission scanning electron microcopy (FE-SEM) and X-ray photoelectron spectroscopy (XPS) have been used to characterize the formation and evolution of the nanoporous layer. Under Ar + bombardment, the Au nanoparticles that were initially deposited were observed to flatten and spread across the native oxide surface, without diffusing, finally coalescing at their edges to form a nanoporous film having irregular pore dimensions. XPS showed that this evolution was accompanied by the loss of Au as a result of sputtering. The formation of such porous films necessitates strong interfacial bonding to avoid the lateral diffusion of the Au nanoparticles, and their ultimate coalescence into larger nanoparticles. We demonstrated that Ar + beam bombardment invariably caused the formation of Au δ+ -Si δ- bonding, rather than the expected Au δ- -Si δ+ bonding, and we explain this to be due to the resonance neutralization of the Ar + beam on impacting the Au layer. We also reveal that the presumed formation of AuSi x is not quantifiable by XPS, due to the superposition of the chemical shift of the Au nanoparticles with that of the quantum size effect, during Au loss on sputtering.

  12. Shedding light on disulfide bond formation

    DEFF Research Database (Denmark)

    Ostergaard, H; Henriksen, A; Hansen, F G

    2001-01-01

    To visualize the formation of disulfide bonds in living cells, a pair of redox-active cysteines was introduced into the yellow fluorescent variant of green fluorescent protein. Formation of a disulfide bond between the two cysteines was fully reversible and resulted in a >2-fold decrease in the i......To visualize the formation of disulfide bonds in living cells, a pair of redox-active cysteines was introduced into the yellow fluorescent variant of green fluorescent protein. Formation of a disulfide bond between the two cysteines was fully reversible and resulted in a >2-fold decrease...... reorganization of residues in the immediate chromophore environment. By combining this information with spectroscopic data, we propose a detailed mechanism accounting for the observed redox state-dependent fluorescence. The redox potential of the cysteine couple was found to be within the physiological range...

  13. Halogen-bonding-triggered supramolecular gel formation

    Science.gov (United States)

    Meazza, Lorenzo; Foster, Jonathan A.; Fucke, Katharina; Metrangolo, Pierangelo; Resnati, Giuseppe; Steed, Jonathan W.

    2013-01-01

    Supramolecular gels are topical soft materials involving the reversible formation of fibrous aggregates using non-covalent interactions. There is significant interest in controlling the properties of such materials by the formation of multicomponent systems, which exhibit non-additive properties emerging from interaction of the components. The use of hydrogen bonding to assemble supramolecular gels in organic solvents is well established. In contrast, the use of halogen bonding to trigger supramolecular gel formation in a two-component gel (‘co-gel’) is essentially unexplored, and forms the basis for this study. Here, we show that halogen bonding between a pyridyl substituent in a bis(pyridyl urea) and 1,4-diiodotetrafluorobenzene brings about gelation, even in polar media such as aqueous methanol and aqueous dimethylsulfoxide. This demonstrates that halogen bonding is sufficiently strong to interfere with competing gel-inhibitory interactions and create a ‘tipping point’ in gel assembly. Using this concept, we have prepared a halogen bond donor bis(urea) gelator that forms co-gels with halogen bond acceptors.

  14. A thermochemical approach to enhance hydrophobicity of SiC/SiO{sub 2} powder using γ-methacryloxypropyl trimethoxy silane and octylphenol polyoxyethylene ether (7)

    Energy Technology Data Exchange (ETDEWEB)

    Li, Chunxue; Feng, Dandan; Wang, Xiangke; Li, Zhihong; Zhu, Yumei, E-mail: zhuyumei@tju.edu.cn

    2016-01-01

    Graphical abstract: Through the exploration of modification mechanism, the hydrophilic properties of SiC/SiO{sub 2}-KH570-OP-7 were far superior to SiC/SiO{sub 2}-KH570. - Highlights: • A novel universal method is performed to enhance hydrophobicity of SiC/SiO{sub 2} powder. • Through pyrolysis of KH570 and OP-7, hydrophilic groups is grafted. • The hydrophobicity of SiC/SiO{sub 2}-KH570-OP-7 was far superior to SiC/SiO{sub 2}-KH570. • A possible formation mechanism of hydrophilic surface was proposed. • Surface changes on SiC/SiO{sub 2}-KH570-OP-7 powder were analyzed via SEM, FTIR, XPS. - Abstract: A thermochemical synthetic methodology for silicon carbide/silica (SiC/SiO{sub 2}) powder modified by integrating γ-methacryloxypropyl trimethoxy silane (KH570) and octylphenol polyoxyethylene ether (7) (OP-7) with hydrophilic SiC/SiO{sub 2} particles is described. On account of weak hydrophobicity of SiC/SiO{sub 2} powder modified by KH570 (SiC/SiO{sub 2}-KH570), the study focuses on the improvement of hydrophobicity utilizing alkylation reaction between OP-7 and KH570 at high temperature. Compared with using KH570 alone, SiC/SiO{sub 2} powder modified by KH570 and OP-7 (SiC/SiO{sub 2}-KH570-OP-7) shows better water resistance, and also an increased contact angle from 73.8° to 136.4°, resulting thus an improved hydrophobicity. Fourier transform infrared spectroscopy (FTIR), as well as X-ray photoelectron spectroscopy (XPS), was utilized to characterize these surfaces, and the results indicated that KH570 and OP-7 can be covalently bonded on the surface of SiC/SiO{sub 2} powder. Furthermore, it has been deeply investigated in the paper not only the possible modes of non-oxidative thermal degradation of OP-7 and KH570, but also the formation mechanism of more hydrophobic SiC/SiO{sub 2}-KH570-OP-7 powder, which probably will have a potential utility for other inorganic materials.

  15. Effect of VEGF-C siRNA and endostatin on ring formation and proliferation of esophageal squamous cell carcinoma lymphatic endothelial cells

    Directory of Open Access Journals (Sweden)

    Zheng YP

    2016-10-01

    Full Text Available Yuping Zheng,1–3,* Miaomiao Sun,4,* Jinyan Chen,1,2 Lulu He,1,2 Na Zhao,1,2 Kuisheng Chen1,2 1Pathology Department, The First Affiliated Hospital of Zhengzhou University, 2Henan Key Laboratory of Tumor Pathology, 3Pathology Department, The Second Hospital of Shandong University, Jinan, 4Pathology Department, Henan Tumor Hospital, Zhengzhou, People’s Republic of China *These authors contributed equally to this work Objective: To study the effects of vascular endothelial growth factor C small interfering RNA and endostatin on esophageal squamous cell carcinoma-related ring formation in vitro and proliferation of lymphatic endothelial cells.Materials and methods: KYSE150 cells were subjected to analysis of cell transfection and endostatin operation. The groups were as follows: negative group, blank group, negative plus endostatin group, endostatin group, SG1 group, SG2 group, SG1 plus endostatin group, and SG2 plus endostatin group. The esophageal cancer-related microlymphatic endothelial cells were three-dimensionally cultured. Cell Counting Kit-8 (CCK-8 assay was employed to detect cell proliferation.Results: The negative group’s three-dimensional culture result was the highest, followed by the blank group, negative plus endostatin group, endostatin group, SG2 group, SG1 group, SG1 plus endostatin group, and SG2 plus endostatin group. The quantity of living cells in the blank group was the highest, followed by the negative control, endostatin, SG2, SG1, negative plus endostatin, SG1 plus endostatin, and SG2 plus endostatin groups. Conclusion: Both vascular endothelial growth factor C small interfering RNA and endostatin could inhibit ring formation in esophageal squamous cell carcinoma and proliferation of lymphatic endothelial cells. Keywords: esophageal squamous carcinoma cells, esophageal cancer-associated lymphatic endothelial cells, VEGF-C, ring formation, proliferation

  16. Recent advances in C-S bond formation via C-H bond functionalization and decarboxylation.

    Science.gov (United States)

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

    2015-01-07

    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.

  17. The unexpected formation of Au{sup {delta}+}-Si{sup {delta}-} by the resonance neutralization of Ar{sup +} during the low energy bombardment of Au nanoparticles on c-Si

    Energy Technology Data Exchange (ETDEWEB)

    Yang Dequan [Regroupement Quebecois de Materiaux de Pointe, Departement de Genie Physique, Ecole Polytechnique, C.P. 6079, succursale Centre-Ville, Montreal, Quebec H3C 3A7 (Canada); Sacher, Edward, E-mail: edward.sacher@polymtl.ca [Regroupement Quebecois de Materiaux de Pointe, Departement de Genie Physique, Ecole Polytechnique, C.P. 6079, succursale Centre-Ville, Montreal, Quebec H3C 3A7 (Canada)

    2009-05-15

    Nanoscale Au layers, with irregular porosities, have been formed by the low energy Ar{sup +} bombardment of Au nanoparticles that were sputter-deposited onto native oxide-covered Si surfaces. High-resolution field emission scanning electron microcopy (FE-SEM) and X-ray photoelectron spectroscopy (XPS) have been used to characterize the formation and evolution of the nanoporous layer. Under Ar{sup +} bombardment, the Au nanoparticles that were initially deposited were observed to flatten and spread across the native oxide surface, without diffusing, finally coalescing at their edges to form a nanoporous film having irregular pore dimensions. XPS showed that this evolution was accompanied by the loss of Au as a result of sputtering. The formation of such porous films necessitates strong interfacial bonding to avoid the lateral diffusion of the Au nanoparticles, and their ultimate coalescence into larger nanoparticles. We demonstrated that Ar{sup +} beam bombardment invariably caused the formation of Au{sup {delta}+}-Si{sup {delta}-} bonding, rather than the expected Au{sup {delta}-}-Si{sup {delta}+} bonding, and we explain this to be due to the resonance neutralization of the Ar{sup +} beam on impacting the Au layer. We also reveal that the presumed formation of AuSi{sub x} is not quantifiable by XPS, due to the superposition of the chemical shift of the Au nanoparticles with that of the quantum size effect, during Au loss on sputtering.

  18. Low-molecular-weight oxidants involved in disulfide bond formation.

    Science.gov (United States)

    Ruddock, Lloyd W

    2012-05-15

    The biogenesis of most secreted and outer membrane proteins involves the formation of structure stabilizing disulfide bonds. Hence knowledge of the mechanisms for their formation is critical for understanding a myriad of cellular processes and associated disease states. Until recently it was thought that members of the Ero1 sulfhydryl oxidase family were responsible for catalyzing the majority of disulfide bond formation in the endoplasmic reticulum. However, multiple eukaryotic organisms are now known to show no or minor phenotypes when these enzymatic pathways are disrupted, suggesting that other pathways can catalyze disulfide bond formation to an extent sufficient to maintain normal physiology. This lack of a strong phenotype raises multiple questions regarding what pathways are acting and whether they themselves constitute the major route for disulfide bond formation. This review critically examines the potential low molecular oxidants that maybe involved in the catalyzed or noncatalyzed formation of disulfide bonds, with an emphasis on the mammalian endoplasmic reticulum, via an examination of their thermodynamics, kinetics, and availability and gives pointers to help guide future experimental work.

  19. Formation of Irreversible H-bonds in Cellulose Materials

    Science.gov (United States)

    Umesh P. Agarwal; Sally A. Ralph; Rick S. Reiner; Nicole M. Stark

    2015-01-01

    Understanding of formation of irreversible Hbonds in cellulose is important in a number of fields. For example, fields as diverse as pulp and paper and enzymatic saccharification of cellulose are affected. In the present investigation, the phenomenon of formation of irreversible H-bonds is studied in a variety of celluloses and under two different drying conditions....

  20. Brazing SiC/SiC Composites to Metals

    Science.gov (United States)

    Steffier, Wayne S.

    2004-01-01

    Experiments have shown that active brazing alloys (ABAs) can be used to join SiC/SiC composite materials to metals, with bond strengths sufficient for some structural applications. The SiC/SiC composite coupons used in the experiments were made from polymerbased SiC fiber preforms that were chemical-vapor-infiltrated with SiC to form SiC matrices. Some of the metal coupons used in the experiments were made from 304 stainless steel; others were made from oxygen-free, high-conductivity copper. Three ABAs were chosen for the experiments: two were chosen randomly from among a number of ABAs that were on hand at the time; the third ABA was chosen because its titanium content (1.25 percent) is less than those of the other two ABAs (1.75 and 4.5 percent, respectively) and it was desired to evaluate the effect of reducing the titanium content, as described below. The characteristics of ABAs that are considered to be beneficial for the purpose of joining SiC/SiC to metal include wettability, reactivity, and adhesion to SiC-based ceramics. Prior to further development, it was verified that the three chosen ABAs have these characteristics. For each ABA, suitable vacuum brazing process conditions were established empirically by producing a series of (SiC/SiC)/ABA wetting samples. These samples were then sectioned and subjected to scanning electron microscopy (SEM) and energy-dispersive x-ray spectrometry (EDS) for analysis of their microstructures and compositions. Specimens for destructive mechanical tests were fabricated by brazing of lap joints between SiC/SiC coupons 1/8-in. (.3.2- mm) thick and, variously, stainless steel or copper tabs. The results of destructive mechanical tests and the SEM/EDS analysis were used to guide the development of a viable method of brazing the affected materials.

  1. Cooperative Hydrogen Bonding in Amyloid Formation.

    Energy Technology Data Exchange (ETDEWEB)

    Tsemekhman, Kiril L.; Goldschmidt, Lukasz; Eisenberg, Dvaid; Baker, David

    2007-04-01

    The research described in this product was performed in part in the Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by the Department of Energy's Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory. Amyloid diseases, including Alzheimer's and prion diseases, are each associated with unbranched protein fibrils. Each fibril is made of a particular protein, yet they share common properties. One such property is nucleation-dependent fibril growth. Monomers of amyloid-forming proteins can remain in dissolved form for long periods, before rapidly assembly into fibrils. The lag before growth has been attributed to slow kinetics of formation of a nucleus, on which other molecules can deposit to form the fibril. We have explored the energetics of fibril formation, based on the known molecular structure of a fibril-forming peptide from the yeast prion, Sup35, using both classical and quantum (density functional theory) methods. We find that the energetics of fibril formation for the first three layers are cooperative using both methods. This cooperativity is consistent with the observation that formation of amyloid fibrils involves slow nucleation and faster growth.

  2. Creating σ-holes through the formation of beryllium bonds.

    Science.gov (United States)

    Brea, Oriana; Mó, Otilia; Yáñez, Manuel; Alkorta, Ibon; Elguero, José

    2015-09-01

    Through the use of ab initio theoretical models based on MP2/aug-cc-pVDZ-optimized geometries and CCSD(T)/aug-cc-pVTZ and CCSD(T)/aug-c-pVDZ total energies, it has been shown that the significant electron density rearrangements that follow the formation of a beryllium bond may lead to the appearance of a σ-hole in systems that previously do not exhibit this feature, such as CH3 OF, NO2 F, NO3 F, and other fluorine-containing systems. The creation of the σ-hole is another manifestation of the bond activation-reinforcement (BAR) rule. The appearance of a σ-hole on the F atoms of CH3 OF is due to the enhancement of the electronegativity of the O atom that participates in the beryllium bond. This atom recovers part of the charge transferred to Be by polarizing the valence density of the F into the bonding region. An analysis of the electron density shows that indeed this bond becomes reinforced, but the F atom becomes more electron deficient with the appearance of the σ-hole. Importantly, similar effects are also observed even when the atom participating in the beryllium bond is not directly attached to the F atom, as in NO2 F, NO3 F, or NCF. Hence, whereas the isolated CH3 OF, NO2 F, and NO3 F are unable to yield F⋅⋅⋅Base halogen bonds, their complexes with BeX2 derivatives are able to yield such bonds. Significant cooperative effects between the new halogen bond and the beryllium bond reinforce the strength of both noncovalent interactions. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Development and Performance Evaluations of HfO2-Si and Rare Earth-Si Based Environmental Barrier Bond Coat Systems for SiC/SiC Ceramic Matrix Composites

    Science.gov (United States)

    Zhu, Dongming

    2014-01-01

    Ceramic environmental barrier coatings (EBC) and SiCSiC ceramic matrix composites (CMCs) will play a crucial role in future aircraft propulsion systems because of their ability to significantly increase engine operating temperatures, improve component durability, reduce engine weight and cooling requirements. Advanced EBC systems for SiCSiC CMC turbine and combustor hot section components are currently being developed to meet future turbine engine emission and performance goals. One of the significant material development challenges for the high temperature CMC components is to develop prime-reliant, high strength and high temperature capable environmental barrier coating bond coat systems, since the current silicon bond coat cannot meet the advanced EBC-CMC temperature and stability requirements. In this paper, advanced NASA HfO2-Si based EBC bond coat systems for SiCSiC CMC combustor and turbine airfoil applications are investigated. The coating design approach and stability requirements are specifically emphasized, with the development and implementation focusing on Plasma Sprayed (PS) and Electron Beam-Physic Vapor Deposited (EB-PVD) coating systems and the composition optimizations. High temperature properties of the HfO2-Si based bond coat systems, including the strength, fracture toughness, creep resistance, and oxidation resistance were evaluated in the temperature range of 1200 to 1500 C. Thermal gradient heat flux low cycle fatigue and furnace cyclic oxidation durability tests were also performed at temperatures up to 1500 C. The coating strength improvements, degradation and failure modes of the environmental barrier coating bond coat systems on SiCSiC CMCs tested in simulated stress-environment interactions are briefly discussed and supported by modeling. The performance enhancements of the HfO2-Si bond coat systems with rare earth element dopants and rare earth-silicon based bond coats are also highlighted. The advanced bond coat systems, when

  4. Heats of Formation and Bond Energies in Group III Compounds

    Science.gov (United States)

    Bauschlicher, Charles W., Jr.; Allendorf, Mark D.; Melius, Carl F.; Arnold, James O. (Technical Monitor)

    1999-01-01

    We present heats of formation and bond energies for Group-III compounds obtained from calculations of molecular ground-state I electronic energies. Data for compounds of the form MXn are presented, where M = B, Al, Ga, and In, X = He H, Cl, and CH3, and n = 1-3. Energies for the B, Al, and Ga compounds are obtained from G2 predictions, while those for the In compounds are obtained from CCSD(T)/CBS calculations; these are the most accurate calculations for indium-containing compounds published to date. In most cases, the calculated thermochemistry is in good agreement with published values derived from experiments for those species that have well-established heats of formation. Bond energies obtained from the heats of formation follow the expected trend (Cl much greater than CH3 approx. H). However, the CH3M-(CH3)2 bond energies obtained for trimethylgallium and trimethylindium are considerably stronger (greater than 15 kcal/mol) than currently accepted values.

  5. SiC-SiC and C-SiC Honeycomb for Advanced Flight Structures Project

    Data.gov (United States)

    National Aeronautics and Space Administration — The proposed project builds upon the work done in Phase I with the development of a C-SiC CMC honeycomb material that was successfully tested for mechanical...

  6. A model of hydrogen bond formation in phosphatidylethanolamine bilayers.

    Science.gov (United States)

    Pink, D A; McNeil, S; Quinn, B; Zuckermann, M J

    1998-01-19

    We have modelled hydrogen bond formation in phospholipid bilayers formed, in excess water, from lipids with phosphatidylethanolamine (PE) headgroups. The hydrogen bonds are formed between the NH3+ group and either of the PO2- or the (sn2 chain) C=O groups. We used a model that represented the conformational states accessible to a PE headgroup by 17 states and modelled lipid dipole-dipole interactions using a non-local electrostatics theory to include the effects of hydrogen bonding in the aqueous medium. We used Monte-Carlo simulation to calculate equilibrium thermodynamic properties of bilayers in the fluid (T = 340 K) or gel (T = 300 K) phases of the bilayer. We defined Eh to be the difference in free energy between a hydrogen bond formed between a pair of lipid groups, and the energy of hydrogen bonds formed between water and those two groups, and we required its average value, [Eh], to be approximately -0.3kcal/mol (approximately -0.2 X 10(-13) erg) as reported by T.-B. Shin, R. Leventis, J.R. Silvius, Biochemistry 30 (1991) 7491. We found: (i) Eh = -0.9 X 10(-13) erg gave [Eh] = -0.21 X 10(-13) erg (gel phase) and [Eh] = -0.19 X 10(-13) erg (fluid phase). (ii) The relative number of C=O groups on the sn2 chain calculated to take part in interlipid hydrogen bonding in the fluid phase compared to the gel is 1.06 which compares well with the experimental ratio of approximately 1.25 (R.N.A.H. Lewis, R.N. McElhaney, Biophys. J. 64 (1993) 1081). The ratio of such groups taking part in interlipid hydrogen bonding compared to water hydrogen bonding in each phase was calculated to lie between 0.16 and 0.17. (iii) We calculated the distribution of positions of the headgroup moieties, P, O, CH2(alpha), CH2(beta) and N, and found that, in both phases, the O lay furthest from the hydrocarbon chain layer (average approximately 5.3A) with the PO2 and NH3 groups lying at approximately 5A. This results in the P-N dipole lying nearly parallel to the bilayer plane in both phases

  7. Detection of bond formations by DNA-programmed chemical reactions and PCR amplification.

    Science.gov (United States)

    Li, Yizhou; Zhang, Mingda; Zhang, Chi; Li, Xiaoyu

    2012-10-04

    A system capable of performing both DNA-templated chemical reactions and detection of bond formations is reported. Photocleavable DNA templates direct reactions. Products from bond-forming events re-ligate original templates, amplifiable by PCR, therefore distinguishing bond formation from background. This system provides a novel approach for discovering potential new chemical reactions.

  8. Simultaneous bond degradation and bond formation during phenol-formaldehyde curing with wood

    Science.gov (United States)

    Daniel J. Yelle; John Ralph

    2016-01-01

    Bonding of wood using phenol–formaldehyde adhesive develops highly durable bonds. Phenol– formaldehyde is believed to form primary bonds with wood cell wall polymers (e.g., lignin). However, it is unclear how this adhesive interacts and bonds to lignin. Through wood solubilisation methodologies, earlywood and latewood bonded assemblies were characterized using two-...

  9. Liquid phase diffusion bonding of A1070 by using metal formate coated Zn sheet

    Science.gov (United States)

    Ozawa, K.; Koyama, S.; shohji, I.

    2017-05-01

    Aluminium alloy have high strength and easily recycle due to its low melting point. Therefore, aluminium is widely used in the manufacturing of cars and electronic devices. In recent years, the most common way for bonding aluminium alloy is brazing and friction stir welding. However, brazing requires positional accuracy and results in the formation of voids by the flax residue. Moreover, aluminium is an excellent heat radiating and electricity conducting material; therefore, it is difficult to bond together using other bonding methods. Because of these limitations, liquid phase diffusion bonding is considered to the suitable method for bonding aluminium at low temperature and low bonding pressure. In this study, the effect of metal formate coating processing of zinc surface on the bond strength of the liquid phase diffusion bonded interface of A1070 has been investigated by SEM observation of the interfacial microstructures and fractured surfaces after tensile test. Liquid phase diffusion bonding was carried out under a nitrogen gas atmosphere at a bonding temperature of 673 K and 713 K and a bonding load of 6 MPa (bonding time: 15 min). As a result of the metal formate coating processing, a joint having the ultimate tensile strength of the base aluminium was provided. It is hypothesized that this is because metallic zinc is generated as a result of thermal decomposition of formate in the bonded interface at lower bonding temperatures.

  10. Addition of Carbon-Fluorine Bonds to a Mg(I)-Mg(I) Bond: An Equivalent of Grignard Formation in Solution

    OpenAIRE

    Bakewell, C; White, AJ; Crimmin, MR

    2016-01-01

    Addition of the carbon?fluorine bond of a series of perfluorinated and polyfluorinated arenes across the Mg?Mg bond of a simple coordination complex proceeds rapidly in solution. The reaction results in the formation of a new carbon?magnesium bond and a new fluorine?magnesium bond and is analogous to Grignard formation in homogeneous solution.

  11. Behaviors of hydrogen in C-SiC films with IR and SIMS analyses

    CERN Document Server

    Huang, N K; Xiong, Q; Liu, Y G; Wang, D Z; Lei, J R

    2002-01-01

    C-SiC films with different content of SiC were prepared with magnetron sputtering deposition followed by Ar sup + ion bombardment. Secondary ion mass spectroscopy depth profiles of hydrogen for the samples of C-SiC coated stainless steel and stainless steel substrate after H sup + ion implantation and thermal annealing show different hydrogen concentrations in C-SiC coatings and stainless steel. Infrared (IR) transmission measurement was selected to study the mechanism of hydrogen retention by C-SiC films. The vibrational spectra in the range between 400 and 3200 cm sup - sup 1 in IR transmission spectra show the Si-CH sub 3 , Si-CH sub 2 , Si-H, CH sub 2 , CH sub 3 etc. bonds, which are responsible for retaining hydrogen. Apart from the mode above, there also exist bonds related to carbon and silicon such as Si-C, C=C. The contamination of oxygen entered the film to form C=O and SiO sub 2 configurations and hydrogen contamination also formed Si-CH sub 2 mode in the films.

  12. Catalytic asymmetric carbon-carbon bond formation via allylic alkylations with organolithium compounds

    NARCIS (Netherlands)

    Perez, Manuel; Fananas Mastral, Martin; Bos, Pieter H.; Rudolph, Alena; Harutyunyan, Syuzanna R.; Feringa, Ben L.

    Carbon-carbon bond formation is the basis for the biogenesis of nature's essential molecules. Consequently, it lies at the heart of the chemical sciences. Chiral catalysts have been developed for asymmetric C-C bond formation to yield single enantiomers from several organometallic reagents.

  13. Preventing Disulfide Bond Formation Weakens Non-Covalent Forces among Lysozyme Aggregates

    OpenAIRE

    Vijay Kumar Ravi; Mohit Goel; Hema Chandra Kotamarthi; Sri Rama Koti Ainavarapu; Rajaram Swaminathan

    2014-01-01

    Nonnative disulfide bonds have been observed among protein aggregates in several diseases like amyotrophic lateral sclerosis, cataract and so on. The molecular mechanism by which formation of such bonds promotes protein aggregation is poorly understood. Here in this work we employ previously well characterized aggregation of hen eggwhite lysozyme (HEWL) at alkaline pH to dissect the molecular role of nonnative disulfide bonds on growth of HEWL aggregates. We employed time-resolved fluorescenc...

  14. Shedding light on disulfide bond formation: engineering a redox switch in green fluorescent protein

    DEFF Research Database (Denmark)

    Østergaard, H.; Henriksen, A.; Hansen, Flemming G.

    2001-01-01

    To visualize the formation of disulfide bonds in living cells, a pair of redox-active cysteines was introduced into the yellow fluorescent variant of green fluorescent protein. Formation of a disulfide bond between the two cysteines was fully reversible and resulted in a >2-fold decrease in the i......To visualize the formation of disulfide bonds in living cells, a pair of redox-active cysteines was introduced into the yellow fluorescent variant of green fluorescent protein. Formation of a disulfide bond between the two cysteines was fully reversible and resulted in a >2-fold decrease...... as a structural reorganization of residues in the immediate chromophore environment. By combining this information with spectroscopic data, we propose a detailed mechanism accounting for the observed redox state-dependent fluorescence. The redox potential of the cysteine couple was found to be within...

  15. Mild Catalytic methods for Alkyl-Alkyl Bond Formation

    Energy Technology Data Exchange (ETDEWEB)

    Vicic, David A

    2009-08-10

    Overview of Research Goals and Accomplishments for the Period 07/01/06 – 06/30/07: Our overall research goal is to transform the rapidly emerging synthetic chemistry involving alkyl-alkyl cross-couplings into more of a mechanism-based field so that that new, rationally-designed catalysts can be performed under energy efficient conditions. Our specific objectives for the previous year were 1) to obtain a proper electronic description of an active catalyst for alkyl-alkyl cross-coupling reactions and 2) to determine the effect of ligand structure on the rate, scope, selectivity, and functional group compatibility of C(sp3)-C(sp3) cross-coupling catalysis. We have completed both of these initial objectives and established a firm base for further studies. The specific significant achievements of the current grant period include: 1) we have performed magnetic and computational studies on (terpyridine)NiMe, an active catalyst for alkyl-alkyl cross couplings, and have discovered that the unpaired electron resides heavily on the terpyridine ligand and that the proper electronic description of this nickel complex is a Ni(II)-methyl cation bound to a reduced terpyridine ligand; 2) we have for the first time shown that alkyl halide reduction by terpyridyl nickel catalysts is substantially ligand based; 3) we have shown by isotopic labeling studies that the active catalyst (terpyridine)NiMe is not produced via a mechanism that involves the formation of methyl radicals when (TMEDA)NiMe2 is used as the catalyst precursor; 4) we have performed an extensive ligand survey for the alkyl-alkyl cross-coupling reactions and have found that electronic factors only moderately influence reactivity in the terpyridine-based catalysis and that the most dramatic effects arise from steric and solubility factors; 5) we have found that the use of bis(dialkylphosphino)methanes as ligands for nickel does not produce active catalysts for cross-coupling but rather leads to bridging hydride

  16. Molecular and ionic hydrogen bond formation in fluorous solvents.

    Science.gov (United States)

    O'Neal, Kristi L; Weber, Stephen G

    2009-01-08

    There are only a few studies of noncovalent association in fluorous solvents and even fewer that are quantitative. A full understanding, particularly of stoichiometry and binding strength of noncovalent interactions in fluorous solvents could be very useful in improved molecular-receptor-based extractions, advancements in sensor technologies, crystal engineering, and supramolecular chemistry. This work investigates hydrogen bonding between heterocyclic bases and a perfluoropolyether with a terminal carboxylic acid group (Krytox 157FSH (1)), chiefly in FC-72 (a mixture of perfluorohexanes). In particular, we were interested in whether or not proton transfer occurs, and if so, under what conditions in H-bonded complexes. Continuous variations experiments show that in FC-72 weaker bases (pyrazine, pyrimidine, and quinazoline) form 1:1 complexes with 1, whereas stronger bases (quinoline, pyridine, and isoquinoline) form 1:3 complexes. Ultraviolet and infrared spectral signatures reveal that the 1:1 complexes are molecular (B.HA) whereas the 1:3 complexes are ionic (BH+.A-HAHA). Infrared spectra of 1:3 ionic complexes are discussed in detail. Literature and experimental data on complexes between N-heterocyclic bases and carboxylic acids in a range of solvents are compiled to compare solvent effects on proton transfer. Polar solvents support ionic hydrogen bonds at a 1:1 mol ratio. In nonpolar organic solvents, ionic hydrogen bonds are only observed in complexes with 1:2 (base/acid) stoichiometries. In fluorous solvents, a larger excess of acid, 1:3, is necessary to facilitate proton transfer in hydrogen bonds between carboxylic acids and the bases studied.

  17. Structure and chemistry of passivated SiC/SiO{sub 2} interfaces

    Energy Technology Data Exchange (ETDEWEB)

    Houston Dycus, J.; Xu, Weizong; LeBeau, James M. [Department of Materials Science and Engineering, North Carolina State University, Raleigh, North Carolina 27695-7907 (United States); Lichtenwalner, Daniel J.; Hull, Brett; Palmour, John W. [Power Devices R& D, Wolfspeed, A Cree Company, Research Triangle Park, North Carolina 27709 (United States)

    2016-05-16

    Here, we report on the chemistry and structure of 4H-SiC/SiO{sub 2} interfaces passivated either by nitric oxide annealing or Ba deposition. Using aberration corrected scanning transmission electron microscopy and spectroscopy, we find that Ba and N remain localized at SiC/SiO{sub 2} interface after processing. Further, we find that the passivating species can introduce significant changes to the near-interface atomic structure of SiC. Specifically, we quantify significant strain for nitric oxide annealed sample where Si dangling bonds are capped by N. In contrast, strain is not observed at the interface of the Ba treated samples. Finally, we place these results in the context of field effect mobility.

  18. Csbnd N bond formation in alicyclic and heterocyclic compounds by amine-modified nanoclay

    Science.gov (United States)

    Zarnegar, Zohre; Alizadeh, Roghayeh; Ahmadzadeh, Majid; Safari, Javad

    2017-09-01

    In the current protocol, amine functionalized montmorillonite K10 nanoclay (NH2-MMT) was applied to catalyze the formation of Csbnd N bonds in the synthesis of azines and 2-aminothiazoles at room temperature. In comparison with the current methods of Csbnd N bond formation, this approach displays specific advantages include atom economy, clean conversion, design for energy efficiency, the use of nontoxic and heterogeneous catalyst, higher purity and yields, safer solvent and reagents for this organic transformation.

  19. Insights into the spontaneity of hydrogen bond formation between formic acid and phthalimide derivatives.

    Science.gov (United States)

    Júnior, Rogério V A; Moura, Gustavo L C; Lima, Nathalia B D

    2016-11-01

    We evaluated a group of phthalimide derivatives, which comprise a convenient test set for the study of the multiple factors involved in the energetics of hydrogen bond formation. Accordingly, we carried out quantum chemical calculations on the hydrogen bonded complexes formed between a sample of phthalimide derivatives with formic acid with the intent of identifying the most important electronic and structural factors related to how their strength and spontaneity vary across the series. The geometries of all species considered were fully optimized at DFT B3LYP/6-31++G(d,p), RM1, RM1-DH2, and RM1-D3H4 level, followed by frequency calculations to determine their Gibbs free energies of hydrogen bond formation using Gaussian 2009 and MOPAC 2012. Our results indicate that the phthalimide derivatives that form hydrogen bond complexes most favorably, have in their structures only one C=O group and at least one NH group. On the other hand, the phthalimide derivatives predicted to form hydrogen bonds least favorably, possess in their structures two carbonyl groups, C=O, and no NH group. The ability to donate electrons and simultaneously receive one acidic hydrogen is the most important property related to the spontaneity of hydrogen bond formation. We further chose two cyclic compounds, phthalimide and isoindolin-1-one, in which to study the main changes in molecular, structural and spectroscopic properties as related to the formation of hydrogen bonds. Thus, the greatest ability of the isoindolin-1-one compound in forming hydrogen bonds is evidenced by the larger effect on the structural, vibrational, and chemical shifts properties associated with the O-H group. In summary, the electron-donating ability of the hydrogen bond acceptor emerged as the most important property differentiating the spontaneity of hydrogen bond formation in this group of complexes.

  20. C-SiC Honeycomb for Advanced Flight Structures Project

    Data.gov (United States)

    National Aeronautics and Space Administration — The proposed project is to manufacture a C-SiC honeycomb structure to use as a high temperature material in advanced aircraft, spacecraft and industrial...

  1. Mechanisms of hydrogen bond formation between ionic liquids and cellulose and the influence of water content.

    Science.gov (United States)

    Rabideau, Brooks D; Ismail, Ahmed E

    2015-02-28

    We study the dynamics of the formation of multiple hydrogen bonds between ionic liquid anions and cellulose using molecular dynamics simulations. We examine fifteen different ionic liquids composed of 1-alkyl-3-methylimidazolium cations ([Cnmim], n = 1, 2, 3, 4, 5) paired with either chloride, acetate or dimethylphosphate. We map the transitions of anions hydrogen bonded to cellulose into different bonding states. We find that increased tail length in the ionic liquids has only a very minor effect on these transitions, tending to slow the dynamics of the transitions and increasing the hydrogen bond lifetimes. Each anion can form up to four hydrogen bonds with cellulose. We find that this hydrogen bond "redundancy" leads to multiply bonded anions having lifetimes three to four times that of singly bound anions. Such redundant hydrogen bonds account for roughly half of all anion-cellulose hydrogen bonds. Additional simulations for [C2mim]Cl, [C2mim]Ac and [C2mim]DMP were performed at different water concentrations between 70 mol% and 90 mol%. It was found that water crowds the hydrogen bond-accepting sites of the anions, preventing interactions with cellulose. The more water that is present in the system, the more crowded these sites become. Thus, if a hydrogen bond between an anion and cellulose breaks, the likelihood that it will be replaced by a nearby water molecule increases as well. We show that the formation of these "redundant" hydrogen bonding states is greatly affected by the presence of water, leading to steep drops in hydrogen bonding between the anions and cellulose.

  2. Carbon–heteroatom bond formation catalysed by organometallic complexes

    Science.gov (United States)

    Hartwig, John F.

    2010-01-01

    At one time the synthetic chemist’s last resort, reactions catalysed by transition metals are now the preferred method for synthesizing many types of organic molecule. A recent success in this type of catalysis is the discovery of reactions that form bonds between carbon and heteroatoms (such as nitrogen, oxygen, sulphur, silicon and boron) via complexes of transition metals with amides, alkoxides, thiolates, silyl groups or boryl groups. The development of these catalytic processes has been supported by the discovery of new elementary reactions that occur at metal–heteroatom bonds and by the identification of factors that control these reactions. Together, these findings have led to new synthetic processes that are in daily use and have formed a foundation for the development of processes that are likely to be central to synthetic chemistry in the future. PMID:18800130

  3. Admittance of a-Si:H/c-Si Schottky diodes

    Energy Technology Data Exchange (ETDEWEB)

    Gall, S.; Hirschauer, R.; Braeunig, D. [Hahn-Meitner-Inst., Berlin (Germany). Dept. AT; Kolter, M. [Forschungszentrum Juelich (Germany)

    1996-12-31

    Heterojunction devices, based on hydrogenated amorphous silicon (a-Si:H) and single crystalline silicon (c-Si), are likely candidates for high efficiency solar cells. The authors have measured the admittance (conductance and capacitance) of a-Si:H/c-Si heterostructure Schottky diodes as a function of frequency, temperature and voltage in the dark and under spectral illumination (in the wavelength range between {lambda} = 500nm and {lambda} = 1,200nm). Thus, it is possible to observe the activation/deactivation of trapping-detrapping effects within the a-Si:H layer (near the a-SiH/c-Si interface). They have determined the conduction band offset of the a-Si:H/c-Si heterostructure. The spectral behavior of the admittance is dominated by the absorption of light in the c-Si and the valence band offset of the heterojunction. The authors have also developed an equivalent circuit of the a-Si:H/c-Si heterostructure Schottky diode in the dark, which is capable of describing the measured behavior.

  4. "Pnicogen bonds" or "chalcogen bonds": exploiting the effect of substitution on the formation of PSe noncovalent bonds.

    Science.gov (United States)

    Shukla, Rahul; Chopra, Deepak

    2016-05-18

    In this article, we have analyzed the nature and characteristics of PSe noncovalent interactions by studying the effect of substitution on XH2PSeH2, H3PSeHX and XH2PSeHX (X= -H, -F, -CH3, -CF3, -Cl, -OH, -OCH3, -NH2, -NHCH3, and -CN) as our systems of interest at MP2/aug-cc-pVDZ level of theory. Binding energy calculations depict that binding energy increases in the order XH2PSeH2 bonds. NBO analysis helped in categorizing these interactions into pnicogen and chalcogen bonds, depending on the strength of P(lp) to σ*(Se-X) orbitals or Se(lp) to σ*(P-X) orbitals.

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

    Energy Technology Data Exchange (ETDEWEB)

    Colby, Denise; Bergman, Robert; Ellman, Jonathan

    2010-05-13

    that has seen widespread success involves the use of a proximal heteroatom that serves as a directing group for the selective functionalization of a specific C-H bond. In a survey of examples of heteroatom-directed Rh catalysis, two mechanistically distinct reaction pathways are revealed. In one case, the heteroatom acts as a chelator to bind the Rh catalyst, facilitating reactivity at a proximal site. In this case, the formation of a five-membered metallacycle provides a favorable driving force in inducing reactivity at the desired location. In the other case, the heteroatom initially coordinates the Rh catalyst and then acts to stabilize the formation of a metal-carbon bond at a proximal site. A true test of the utility of a synthetic method is in its application to the synthesis of natural products or complex molecules. Several groups have demonstrated the applicability of C-H bond functionalization reactions towards complex molecule synthesis. Target-oriented synthesis provides a platform to test the effectiveness of a method in unique chemical and steric environments. In this respect, Rh-catalyzed methods for C-H bond functionalization stand out, with several syntheses being described in the literature that utilize C-H bond functionalization in a key step. These syntheses are highlighted following the discussion of the method they employ.

  6. Catalytic asymmetric carbon-carbon bond formation via allylic alkylations with organolithium compounds.

    Science.gov (United States)

    Pérez, Manuel; Fañanás-Mastral, Martín; Bos, Pieter H; Rudolph, Alena; Harutyunyan, Syuzanna R; Feringa, Ben L

    2011-05-01

    Carbon-carbon bond formation is the basis for the biogenesis of nature's essential molecules. Consequently, it lies at the heart of the chemical sciences. Chiral catalysts have been developed for asymmetric C-C bond formation to yield single enantiomers from several organometallic reagents. Remarkably, for extremely reactive organolithium compounds, which are among the most broadly used reagents in chemical synthesis, a general catalytic methodology for enantioselective C-C formation has proven elusive, until now. Here, we report a copper-based chiral catalytic system that allows carbon-carbon bond formation via allylic alkylation with alkyllithium reagents, with extremely high enantioselectivities and able to tolerate several functional groups. We have found that both the solvent used and the structure of the active chiral catalyst are the most critical factors in achieving successful asymmetric catalysis with alkyllithium reagents. The active form of the chiral catalyst has been identified through spectroscopic studies as a diphosphine copper monoalkyl species.

  7. Aeropyrum pernix membrane topology of protein VKOR promotes protein disulfide bond formation in two subcellular compartments.

    Science.gov (United States)

    Hibender, Stijntje; Landeta, Cristina; Berkmen, Mehmet; Beckwith, Jon; Boyd, Dana

    2017-11-15

    Disulfide bonds confer stability and activity to proteins. Bioinformatic approaches allow predictions of which organisms make protein disulfide bonds and in which subcellular compartments disulfide bond formation takes place. Such an analysis, along with biochemical and protein structural data, suggests that many of the extremophile Crenarachaea make protein disulfide bonds in both the cytoplasm and the cell envelope. We have sought to determine the oxidative folding pathways in the sequenced genomes of the Crenarchaea, by seeking homologues of the enzymes known to be involved in disulfide bond formation in bacteria. Some Crenarchaea have two homologues of the cytoplasmic membrane protein VKOR, a protein required in many bacteria for the oxidation of bacterial DsbAs. We show that the two VKORs of Aeropyrum pernix assume opposite orientations in the cytoplasmic membrane, when expressed in E. coli. One has its active cysteines oriented toward the E. coli periplasm (ApVKORo) and the other toward the cytoplasm (ApVKORi). Furthermore, the ApVKORo promotes disulfide bond formation in the E. coli cell envelope, while the ApVKORi promotes disulfide bond formation in the E. coli cytoplasm via a co-expressed archaeal protein ApPDO. Amongst the VKORs from different archaeal species, the pairs of VKORs in each species are much more closely related to each other than to the VKORs of the other species. The results suggest two independent occurrences of the evolution of the two topologically inverted VKORs in archaea. Our results suggest a mechanistic basis for the formation of disulfide bonds in the cytoplasm of Crenarchaea.

  8. Relationship between chemical structure and supramolecular effective molarity for formation of intramolecular H-bonds.

    Science.gov (United States)

    Sun, Hongmei; Hunter, Christopher A; Navarro, Cristina; Turega, Simon

    2013-09-04

    Effective molarity (EM) is a key parameter that determines the efficiency of a range of supramolecular phenomena from the folding of macromolecules to multivalent ligand binding. Coordination complexes formed between zinc porphyrins equipped H-bond donor sites and pyridine ligands equipped with H-bond acceptor sites have allowed systematic quantification of EM values for the formation of intramolecular H-bonds in 240 different systems. The results provide insights into the relationship of EM to supramolecular architecture, H-bond strength, and solvent. Previous studies on ligands equipped with phosphonate diester and ether H-bond acceptors were inconclusive, but the experiments described here on ligands equipped with phosphine oxide, amide, and ester H-bond acceptors resolve these ambiguities. Chemical double-mutant cycles were used to dissect the thermodynamic contributions of individual H-bond interactions to the overall stabilities of the complexes and hence determine the values of EM, which fall in the range 1-1000 mM. Solvent has little effect on EM, and the values measured in toluene and 1,1,2,2-tetrachloroethane are similar. For H-bond acceptors that have similar geometries but different H-bond strengths (amide and ester), the values of EM are very similar. For H-bond acceptors that have different geometries but similar H-bond strengths (amide and phosphonate diester), there is little correlation between the values of EM. These results imply that supramolecular EMs are independent of solvent and intrinsic H-bond strength but depend on supramolecular architecture and geometric complementarity.

  9. Drinking alcohol has sex-dependent effects on pair bond formation in prairie voles.

    Science.gov (United States)

    Anacker, Allison M J; Ahern, Todd H; Hostetler, Caroline M; Dufour, Brett D; Smith, Monique L; Cocking, Davelle L; Li, Ju; Young, Larry J; Loftis, Jennifer M; Ryabinin, Andrey E

    2014-04-22

    Alcohol use and abuse profoundly influences a variety of behaviors, including social interactions. In some cases, it erodes social relationships; in others, it facilitates sociality. Here, we show that voluntary alcohol consumption can inhibit male partner preference (PP) formation (a laboratory proxy for pair bonding) in socially monogamous prairie voles (Microtus ochrogaster). Conversely, female PP is not inhibited, and may be facilitated by alcohol. Behavior and neurochemical analysis suggests that the effects of alcohol on social bonding are mediated by neural mechanisms regulating pair bond formation and not alcohol's effects on mating, locomotor, or aggressive behaviors. Several neuropeptide systems involved in the regulation of social behavior (especially neuropeptide Y and corticotropin-releasing factor) are modulated by alcohol drinking during cohabitation. These findings provide the first evidence to our knowledge that alcohol has a direct impact on the neural systems involved in social bonding in a sex-specific manner, providing an opportunity to explore the mechanisms by which alcohol affects social relationships.

  10. Formation of RNA phosphodiester bond by histidine-containing dipeptides

    DEFF Research Database (Denmark)

    Wieczorek, Rafal; Dörr, Mark; Chotera, Agata

    2013-01-01

    A new scenario for prebiotic formation of nucleic acid oligomers is presented. Peptide catalysis is applied to achieve condensation of activated RNA monomers into short RNA chains. As catalysts, L-dipeptides containing a histidine residue, primarily Ser-His, were used. Reactions were carried out ...

  11. Preventing disulfide bond formation weakens non-covalent forces among lysozyme aggregates.

    Directory of Open Access Journals (Sweden)

    Vijay Kumar Ravi

    Full Text Available Nonnative disulfide bonds have been observed among protein aggregates in several diseases like amyotrophic lateral sclerosis, cataract and so on. The molecular mechanism by which formation of such bonds promotes protein aggregation is poorly understood. Here in this work we employ previously well characterized aggregation of hen eggwhite lysozyme (HEWL at alkaline pH to dissect the molecular role of nonnative disulfide bonds on growth of HEWL aggregates. We employed time-resolved fluorescence anisotropy, atomic force microscopy and single-molecule force spectroscopy to quantify the size, morphology and non-covalent interaction forces among the aggregates, respectively. These measurements were performed under conditions when disulfide bond formation was allowed (control and alternatively when it was prevented by alkylation of free thiols using iodoacetamide. Blocking disulfide bond formation affected growth but not growth kinetics of aggregates which were ∼50% reduced in volume, flatter in vertical dimension and non-fibrillar in comparison to control. Interestingly, single-molecule force spectroscopy data revealed that preventing disulfide bond formation weakened the non-covalent interaction forces among monomers in the aggregate by at least ten fold, thereby stalling their growth and yielding smaller aggregates in comparison to control. We conclude that while constrained protein chain dynamics in correctly disulfide bonded amyloidogenic proteins may protect them from venturing into partial folded conformations that can trigger entry into aggregation pathways, aberrant disulfide bonds in non-amyloidogenic proteins (like HEWL on the other hand, may strengthen non-covalent intermolecular forces among monomers and promote their aggregation.

  12. Argon plasma treatment of silicon nitride (SiN) for improved antireflection coating on c-Si solar cells

    Energy Technology Data Exchange (ETDEWEB)

    Ghosh, Hemanta; Mitra, Suchismita; Saha, Hiranmay; Datta, Swapan Kumar; Banerjee, Chandan, E-mail: chandanbanerjee74@gmail.com

    2017-01-15

    Highlights: • Antireflection properties of argon plasma treated silicon nitride layer and its effect on crystalline silicon solar cell. • The reduction in reflection due to the formation of a silicon oxynitride/silicon nitride double layer. • EQE reveals a relative increase of 2.72% in J{sub sc} and 4.46% in conversion efficiency. - Abstract: Antireflection properties of argon plasma treated silicon nitride layer and its effect on crystalline silicon solar cell is presented here. Hydrogenated silicon nitride (a-SiN:H) layer has been deposited on a silicon substrate by Plasma Enhanced Chemical Vapour Deposition (PECVD) using a mixture of silane (SiH{sub 4}), ammonia (NH{sub 3}) and hydrogen (H{sub 2}) gases followed by a argon plasma treatment. Optical analysis reveals a significant reduction in reflectance after argon plasma treatment of silicon nitride layer. While FESEM shows nanostructures on the surface of the silicon nitride film, FTIR reveals a change in Si−N, Si−O and N−H bonds. On the other hand, ellipsometry shows the variation of refractive index and formation of double layer. Finally, a c-Si solar cell has been fabricated with the said anti-reflection coating. External quantum efficiency reveals a relative increase of 2.72% in the short circuit current density and 4.46% in conversion efficiency over a baseline efficiency of 16.58%.

  13. Spectroscopic phonon and extended x-ray absorption fine structure measurements on 3C-SiC/Si (001) epifilms

    Science.gov (United States)

    Talwar, Devki N.; Wan, Linyu; Tin, Chin-Che; Lin, Hao-Hsiung; Feng, Zhe Chuan

    2018-01-01

    Comprehensive experimental and theoretical studies are reported to assess the vibrational and structural properties of 3C-SiC/Si (001) epilayers grown by chemical vapor deposition in a vertical reactor configuration. While the phonon features are evaluated using high resolution infrared reflectance (IRR) and Raman scattering spectroscopy (RSS) - the local inter-atomic structure is appraised by synchrotron radiation extended x-ray absorption fine structure (SR-EXAFS) method. Unlike others, our RSS results in the near backscattering geometry revealed markedly indistinctive longitudinal- and transverse-optical phonons in 3C-SiC epifilms of thickness d theory is utilized to explain the observed atypical IRR spectra in 3C-SiC/Si (001) epifilms. High density intrinsic defects present in films and/or epilayer/substrate interface are likely to be responsible for (a) releasing misfit stress/strains, (b) triggering atypical features in IRR spectra, and (c) affecting observed local structural traits in SR-EXAFS.

  14. Radicals and ions controlling by adjusting the antenna-substrate distance in a-Si:H deposition using a planar ICP for c-Si surface passivation

    Energy Technology Data Exchange (ETDEWEB)

    Zhou, H.P., E-mail: haipzhou@uestc.edu.cn [School of Energy Science and Engineering, University of Electronic Science and Technology of China, 2006 Xiyuan Ave., West High-Tech Zone, Chengdu, Sichuan, 611731 (China); Plasma Sources and Application Center, NIE, and Institute of Advanced Studies, Nanyang Technological University, 637616 (Singapore); Xu, S., E-mail: shuyan.xu@nie.edu.sg [Plasma Sources and Application Center, NIE, and Institute of Advanced Studies, Nanyang Technological University, 637616 (Singapore); Xu, M. [Key Laboratory of Information Materials of Sichuan Province & School of Electrical and Information Engineering, Southwest University for Nationalities, Chengdu, 610041 (China); Xu, L.X.; Wei, D.Y. [Plasma Sources and Application Center, NIE, and Institute of Advanced Studies, Nanyang Technological University, 637616 (Singapore); Xiang, Y. [School of Energy Science and Engineering, University of Electronic Science and Technology of China, 2006 Xiyuan Ave., West High-Tech Zone, Chengdu, Sichuan, 611731 (China); Xiao, S.Q. [Key Laboratory of Advanced Process Control for Light Industry (Ministry of Education), Department of Electronic Engineering, Jiangnan University, Wuxi, 214122 (China)

    2017-02-28

    Highlights: • A planar ICP was used to grow a-Si:H films for c-Si surface passivation. • The direct- and remote-plasma was compared for high-quality c-Si surface passivation. • The remote ICP with controlled plasma species and ion bombardments is preferable for the surface passivation of c-Si. - Abstract: Being a key issue in the research and fabrication of silicon heterojunction (SHJ) solar cells, crystalline silicon (c-Si) surface passivation is theoretically and technologically intricate due to its complicate dependence on plasma characteristics, material properties, and plasma-material interactions. Here amorphous silicon (a-Si:H) grown by a planar inductively coupled plasma (ICP) reactor working under different antenna-substrate distances of d was used for the surface passivation of low-resistivity p-type c-Si. It is found that the microstructures (i.e., the crystallinity, Si-H bonding configuration etc.) and passivation function on c-Si of the deposited a-Si:H were profoundly influenced by the parameter of d, which primarily determines the types of growing precursors of SiH{sub n}/H contributing to the film growth and the interaction between the plasma and growing surface. c-Si surface passivation is analyzed in terms of the d-dependent a-Si:H properties and plasma characteristics. The controlling of radical types and ion bombardment on the growing surface through adjusting parameter d is emphasized.

  15. Lightweight C/SiC mirrors for space application

    Science.gov (United States)

    Zhou, Hao; Zhang, Chang-rui; Cao, Ying-bin; Zhou, Xin-gui

    2006-02-01

    Challenges in high resolution space telescopes have led to the desire to create large primary mirror apertures. Ceramic mirrors and complex structures are becoming more important for high precision lightweight optical applications in adverse environments. Carbon-fiber reinforced silicon carbide (C/SiC) has shown great potential to be used as mirror substrate. This material has a high stiffness to weight ratio, dimensional stability from ambient to cryo temperatures, and thermal conductivity, low thermal expansion as well. These properties make C/SiC very attractive for a variety of applications in precision optical structures, especially when considering space-borne application. In this paper, lightweight C/SiC mirror prepared for a scan mirror of a high resolution camera is presented. The manufacturing of C/SiC mirror starts with a porous rigid felt made of short chopped carbon fibers. The fibers are molded with phenolic resin under pressure to form a carbon fiber reinforced plastic blank, followed by a pyrolization process by which the phenolic resin reacts to a carbon matrix. The C/C-felt can be machined by standard computer controlled milling techniques to any virtual shape. This is one of the most significant advantages of this material, as it drastically reduces the making costs and enables the manufacture of truly ultra-lightweight mirrors, reflectors and structures. Upon completion of milling, the C/C-felt preform is mounted in a high-temperature furnace together with silicon and heated under vacuum condition to 1500°C at which the silicon changes into liquid phase. Subsequently, the molten silicon is infiltrated into the porous preform under capillary forces to react with carbon matrix and the surfaces of the carbon fibers to form a density C/SiC substrate. The C/SiC material retains the preform shape to within a tight tolerance after sintering means the ceramization process is a nearly net shaping process. Reactive melt infiltrated C/SiC, followed by

  16. Organocatalytic aryl-aryl bond formation: an atroposelective [3,3]-rearrangement approach to BINAM derivatives.

    Science.gov (United States)

    Li, Gong-Qiang; Gao, Hongyin; Keene, Craig; Devonas, Michael; Ess, Daniel H; Kürti, László

    2013-05-22

    Herein we disclose an organocatalytic aryl-aryl bond-forming process for the regio- and atroposelective synthesis of 2,2'-diamino-1,1'-binaphthalenes (BINAMs). In the presence of catalytic amounts of axially chiral phosphoric acids, achiral N,N'-binaphthyl hydrazines undergo a facile [3,3]-sigmatropic rearrangement to afford enantiomerically enriched BINAM derivatives in good to excellent yield. This transformation represents the first example of a metal-free, catalytic C(sp(2))-C(sp(2)) bond formation between two aromatic rings with concomitant de novo atroposelective installation of an axis of chirality. Density functional calculations reveal that, in the transition state for C-C bond formation, the phosphoric acid proton of the catalyst is fully transferred to one of the N-atoms of the substrate, and the resulting phosphate acts as a chiral counterion.

  17. Phase Stability and Thermal Conductivity of Composite Environmental Barrier Coatings on SiC/SiC Ceramic Matrix Composites

    Science.gov (United States)

    Benkel, Samantha; Zhu, Dongming

    2011-01-01

    Advanced environmental barrier coatings are being developed to protect SiC/SiC ceramic matrix composites in harsh combustion environments. The current coating development emphasis has been placed on the significantly improved cyclic durability and combustion environment stability in high-heat-flux and high velocity gas turbine engine environments. Environmental barrier coating systems based on hafnia (HfO2) and ytterbium silicate, HfO2-Si nano-composite bond coat systems have been processed and their stability and thermal conductivity behavior have been evaluated in simulated turbine environments. The incorporation of Silicon Carbide Nanotubes (SiCNT) into high stability (HfO2) and/or HfO2-silicon composite bond coats, along with ZrO2, HfO2 and rare earth silicate composite top coat systems, showed promise as excellent environmental barriers to protect the SiC/SiC ceramic matrix composites.

  18. Disulfide bond formation and ToxR activity in Vibrio cholerae.

    Directory of Open Access Journals (Sweden)

    Vera H I Fengler

    Full Text Available Virulence factor production in Vibrio cholerae is complex, with ToxRS being an important part of the regulatory cascade. Additionally, ToxR is the transcriptional regulator for the genes encoding the major outer membrane porins OmpU and OmpT. ToxR is a transmembrane protein and contains two cysteine residues in the periplasmic domain. This study addresses the influence of the thiol-disulfide oxidoreductase system DsbAB, ToxR cysteine residues and ToxR/ToxS interaction on ToxR activity. The results show that porin production correlates with ToxR intrachain disulfide bond formation, which depends on DsbAB. In contrast, formation of ToxR intrachain or interchain disulfide bonds is dispensable for virulence factor production and in vivo colonization. This study further reveals that in the absence of ToxS, ToxR interchain disulfide bond formation is facilitated, whereat cysteinyl dependent homo- and oligomerization of ToxR is suppressed if ToxS is coexpressed. In summary, new insights into gene regulation by ToxR are presented, demonstrating a mechanism by which ToxR activity is linked to a DsbAB dependent intrachain disulfide bond formation.

  19. Cyclodiphosphazanes as synthetic probes: P-C/P-N bond formation ...

    Indian Academy of Sciences (India)

    Cyclodiphosphazanes as synthetic probes: P-C/P-N bond formation from the reaction with functionalized propargyl ... compounds wonderful precursors to probe organic reac- tions (chart 1). In this study, although reaction ..... 528.43, Monoclinic, Space group C2/c,a = 21.035(4), b = 10.233(2), c = 15.523(3)Å, β = 128.87(3),.

  20. Mechanism of Amide Bond Formation from Carboxylic Acids and Amines Promoted by 9-Silafluorenyl Dichloride Derivatives.

    Science.gov (United States)

    Jiang, Yuan-Ye; Zhu, Ling; Liang, Yujie; Man, Xiaoping; Bi, Siwei

    2017-09-01

    The couplings of carboxylic acids and amines promoted by dichlorosilane derivatives provide a promising tool for amide synthesis and peptide coupling, in which an unprecedented mechanism was proposed for the amide bond formation process. To investigate this mechanistic proposal and enrich the understanding of this novel reaction, a theoretical study was conducted herein. The formation and interconversion of silylamine and silyl ester intermediates were calculated to be kinetically feasible under the experiment conditions. However, the subsequent amidation via direct elimination on the AcO-Si(L)(L')-NHMe intermediate was found to involve a high energy barrier due to the formation of an unstable silanone. By contrast, the in situ generated salts can promote the amidation process by generating a silanol as the temporary product. Similarly, the anhydride formation mechanism can proceed via direct elimination or salt-assisted elimination on the AcO-Si(L)(L')-OAc intermediate but is less favorable. Finally, we found that the intermolecular nucleophilic addition on the AcO-Si(L)(L')-Cl intermediate is the most favorable mechanism among all the candidates considered. In this mechanism, carboxylic acids or bases can act as self-catalysts to promote the amide bond formation via hydrogen bonding, and the formation of the unstable silanone or anhydride is avoided.

  1. The compatibility of SiC/SiC composites with ceramic breeder materials

    Energy Technology Data Exchange (ETDEWEB)

    Sample, T. (Institute for Advanced Materials, Commission of the European Communities, Joint Research Centre, I-21020, Ispra (Vatican City State, Holy See) (Italy)); Fenici, P. (Institute for Advanced Materials, Commission of the European Communities, Joint Research Centre, I-21020, Ispra (Vatican City State, Holy See) (Italy)); Kolbe, H. (Institute for Advanced Materials, Commission of the European Communities, Joint Research Centre, I-21020, Ispra (Vatican City State, Holy See) (Italy)); Orecchia, L. (Institute for Advanced Materials, Commission of the European Communities, Joint Research Centre, I-21020, Ispra (Vatican City State, Holy See) (Italy))

    1994-09-01

    The compatibility of three lithium-containing ceramic breeder materials Li[sub 4]SiO[sub 4], Li[sub 2]ZrO[sub 3] and LiAlO[sub 2] with two industrially available SiC/SiC composites was determined. Simple capsule tests were carried out at 600 and 800 C in closed capsules, dynamic vacuum and flowing helium. All three breeder materials were reactive towards the SiO[sub 2] content of the SiC/SiC composites forming a surface layer of Li[sub 2]SiO[sub 3]. The as-received' Li[sub 4]SiO[sub 4] was found to be much more reactive than Li[sub 2]ZrO[sub 3] or LiAlO[sub 2]. However, the greater reactivity was found to be governed by the Li[sub 2]CO[sub 3] impurity content of the Li[sub 4]SiO[sub 4] granules. Removal of the Li[sub 2]CO[sub 3], through thermal decomposition under vacuum, reduced the extend of Li[sub 2]SiO[sub 3] formation. The reaction of the breeder materials to form Li[sub 2]SiO[sub 3] is briefly discussed in relation to the probable operating conditions for a SiC/SiC composite structural material in a blanket. ((orig.))

  2. In situ synthesis of ZrC/SiC nanocomposite via carbothermic reduction of binary xerogel

    Energy Technology Data Exchange (ETDEWEB)

    El-Sheikh, S.M. [Nano-structured Materials Division, Central Metallurgical Research and Development Institute, CMRDI, P.O. Box: 87 Helwan, 11421 Helwan (Egypt); Zaki, Z.I. [Ceramic and Refractory Materials Division, Central Metallurgical Research and Development Institute, CMRDI, P.O. Box: 87 Helwan, 11421 Helwan (Egypt); Ahmed, Y.M.Z., E-mail: yayoyasser@yahoo.com [Ceramic and Refractory Materials Division, Central Metallurgical Research and Development Institute, CMRDI, P.O. Box: 87 Helwan, 11421 Helwan (Egypt)

    2014-11-15

    Highlights: • ZrC/SiC Nanocomposite was prepared via carbothermic reduction. • The percentage of carbon added was higher than stoichiometric. • The silicon carbide was formed in size of about 50 nm and in a rod like structure. • The zirconium carbide was formed in a spherical like structure. • The composite was synthesized at much lower than mentioned in literature. - Abstract: Nano-sized powder composite of zirconium carbide/silicon carbide (ZrC/SiC) was successfully synthesized via a combined sol gel/carbothermic reduction techniques. A sol containing zirconium from zirconium n-propoxide (ZTP) as well as a sol containing silicon from tetraethoxy orthosilicate (TEOS) was separately prepared. The two sols were mixed together for preparing a binary gel containing both. The produced binary xerogel was subjected to a carbothermic reduction reaction at temperature of 1500 °C for 3 h. The synthesized powder was characterized from compositional as well as morphological point of views using XRD, FT-IR, XPS, SEM and TEM analysis. The XRD data revealed that the powder composite consisted of pure ZrC/SiC was produced. This data was confirmed by presence of main planes (0 1 0) and (0 1 1) for ZrC and (1 1 1) plane for SiC, respectively. Moreover, XPS with help of FT-IR data show obviously that the ZrC/SiC composite was formed with traces of zirconium oxycarbide. Furthermore, SEM and TEM images confirmed that cubic nano-sized ZrC particles of size ∼40 nm and hexagonal β-SiC nano-rods of size ∼50 nm were obtained. In addition, the thermogravimetric analysis of the produced nanocomposite revealed the high homogeneity in the particle size distribution. Based on the obtained data, a mechanism of nanocomposite formation was postulated.

  3. Direct Mechanism of the First Carbon-Carbon Bond Formation in the Methanol-to-Hydrocarbons Process.

    Science.gov (United States)

    Wu, Xinqiang; Xu, Shutao; Zhang, Wenna; Huang, Jindou; Li, Jinzhe; Yu, Bowen; Wei, Yingxu; Liu, Zhongmin

    2017-07-24

    In the past two decades, the reaction mechanism of C-C bond formation from either methanol or dimethyl ether (DME) in the methanol-to-hydrocarbons (MTH) process has been a highly controversial issue. Described here is the first observation of a surface methyleneoxy analogue, originating from the surface-activated DME, by in situ solid-state NMR spectroscopy, a species crucial to the first C-C bond formation in the MTH process. New insights into the first C-C bond formation were provided, thus suggesting DME/methanol activation and direct C-C bond formation by an interesting synergetic mechanism, involving C-H bond breakage and C-C bond coupling during the initial methanol reaction within the chemical environment of the zeolite catalyst. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Metastability of a-SiO{sub x}:H thin films for c-Si surface passivation

    Energy Technology Data Exchange (ETDEWEB)

    Serenelli, L., E-mail: luca.serenelli@enea.it [ENEA Research centre “Casaccia”, via Anguillarese 301, 00123 Rome (Italy); DIET University of Rome “Sapienza”, via Eudossiana 18, 00184 Rome (Italy); Martini, L. [DIET University of Rome “Sapienza”, via Eudossiana 18, 00184 Rome (Italy); Imbimbo, L. [ENEA Research centre “Casaccia”, via Anguillarese 301, 00123 Rome (Italy); DIET University of Rome “Sapienza”, via Eudossiana 18, 00184 Rome (Italy); Asquini, R. [DIET University of Rome “Sapienza”, via Eudossiana 18, 00184 Rome (Italy); Menchini, F.; Izzi, M.; Tucci, M. [ENEA Research centre “Casaccia”, via Anguillarese 301, 00123 Rome (Italy)

    2017-01-15

    Highlights: • a-SiO{sub x}:H film deposition by RF-PECVD is optimized from SiH{sub 4}, CO{sub 2} and H{sub 2} gas mixture. • Metastability of a-SiO{sub x}:H/c-Si passivation is investigated under thermal annealing and UV exposure. • A correlation between passivation metastability and Si−H bonds is found by FTIR spectra. • A metastability model is proposed. - Abstract: The adoption of a-SiO{sub x}:H films obtained by PECVD in heterojunction solar cells is a key to further increase their efficiency, because of its transparency in the UV with respect to the commonly used a-Si:H. At the same time this layer must guarantee high surface passivation of the c-Si to be suitable in high efficiency solar cell manufacturing. On the other hand the application of amorphous materials like a-Si:H and SiN{sub x} on the cell frontside expose them to the mostly energetic part of the sun spectrum, leading to a metastability of their passivation properties. Moreover as for amorphous silicon, thermal annealing procedures are considered as valuable steps to enhance and stabilize thin film properties, when performed at opportune temperature. In this work we explored the reliability of a-SiO{sub x}:H thin film layers surface passivation on c-Si substrates under UV exposition, in combination with thermal annealing steps. Both p- and n-type doped c-Si substrates were considered. To understand the effect of UV light soaking we monitored the minority carriers lifetime and Si−H and Si−O bonding, by FTIR spectra, after different exposure times to light coming from a deuterium lamp, filtered to UV-A region, and focused on the sample to obtain a power density of 50 μW/cm{sup 2}. We found a certain lifetime decrease after UV light soaking in both p- and n-type c-Si passivated wafers according to a a-SiO{sub x}:H/c-Si/a-SiO{sub x}:H structure. The role of a thermal annealing, which usually enhances the as-deposited SiO{sub x} passivation properties, was furthermore considered. In

  5. Recent progress in the catalytic carbene insertion reactions into the silicon-hydrogen bond.

    Science.gov (United States)

    Keipour, Hoda; Carreras, Virginie; Ollevier, Thierry

    2017-07-05

    The following review will explore the historical development of Si-H bond insertion reactions, giving an up-to-date account on the metal catalysts often employed, in addition to an assessment of their strengths and weaknesses. Diazo compounds have great synthetic potential as versatile reagents for the formation of metal carbenes, allowing the selective formation of C-C and C-heteroatom bonds and thus the introduction of functional groups into organic molecules. C-Si bond-forming methods, that introduce silicon motifs into organic molecules, rely on catalysts derived from metals such as rhodium, copper, iridium, silver, ruthenium, and iron to achieve the desired activities and selectivities.

  6. Structural basis for Diels-Alder ribozyme-catalyzed carbon-carbon bond formation

    Science.gov (United States)

    Serganov, Alexander; Keiper, Sonja; Malinina, Lucy; Tereshko, Valentina; Skripkin, Eugene; Höbartner, Claudia; Polonskaia, Anna; Phan, Anh Tuân; Wombacher, Richard; Micura, Ronald; Dauter, Zbigniew; Jäschke, Andres; Patel, Dinshaw J

    2015-01-01

    The majority of structural efforts addressing RNA’s catalytic function have focused on natural ribozymes, which catalyze phosphodiester transfer reactions. By contrast, little is known about how RNA catalyzes other types of chemical reactions. We report here the crystal structures of a ribozyme that catalyzes enantioselective carbon-carbon bond formation by the Diels-Alder reaction in the unbound state and in complex with a reaction product. The RNA adopts a λ-shaped nested pseudoknot architecture whose preformed hydrophobic pocket is precisely complementary in shape to the reaction product. RNA folding and product binding are dictated by extensive stacking and hydrogen bonding, whereas stereoselection is governed by the shape of the catalytic pocket. Catalysis is apparently achieved by a combination of proximity, complementarity and electronic effects. We observe structural parallels in the independently evolved catalytic pocket architectures for ribozyme- and antibody-catalyzed Diels-Alder carbon-carbon bond-forming reactions. PMID:15723077

  7. Bragg reflector and laser fired back contact in a-Si:H/c-Si heterostructure solar cell

    Energy Technology Data Exchange (ETDEWEB)

    Tucci, M. [ENEA, Research Center Casaccia, via Anguillarese 301, S. Maria di Galeria 00123, Rome (Italy)], E-mail: mario.tucci@casaccia.enea.it; Serenelli, L.; Salza, E.; Pirozzi, L. [ENEA, Research Center Casaccia, via Anguillarese 301, S. Maria di Galeria 00123, Rome (Italy); De Cesare, G.; Caputo, D.; Ceccarelli, M. [Department of Electronic Engineering, University ' Sapienza' , via Eudossiana 18 00184, Rome (Italy)

    2009-03-15

    The amorphous/crystalline silicon (a-Si/c-Si) heterostructure has recently attracted new interest due to higher open circuit voltage V{sub oc} and low temperature fabrication processes. By reducing the wafer thickness all these characteristics become a necessity, together with the requirement of a back reflecting mirror, to obtain an effective optical confinement. To this aim dielectric mirrors can be adopted in the rear side of the solar cells, together with a local process of laser fired back Al contact. Taking advantage of a-Si/SiN{sub x} passivation properties of c-Si surface a Bragg reflector configuration can be formed on the rear side of the c-Si wafer by Plasma Enhanced Chemical Vapor Deposition (PECVD) alternating several couples of a-Si/SiN{sub x} and choosing their thicknesses to maximize the reflectance inward the c-Si wafer in the NIR spectrum. In this work we have adopted this mirror on the rear side of an n-a-Si/i-a-Si/p-c-Si heterostructure solar cell to obtain a full low temperature process. The cell back contact has been ensured by an Al diffusion into the c-Si wafer promoted by Nd-YAG pulsed laser. The front cell contact has been enhanced by chromium silicide CrSi formation on top of the n-a-Si layer and ITO deposition followed by an Ag grid. A V{sub oc} of 681 mV and 94% of IQE at 1000 nm have been reached.

  8. Structural investigation of the amorphous/crystalline interface by means of quantitative high-resolution transmission electron microscopy on the systems a-Si/c-Si and a-Ge/c-Si; Strukturelle Untersuchung der amorph/kristallinen Grenzflaeche mittels quantitativer hochaufloesender Transmissionselektronenmikroskopie an den Systemen a-Si/c-Si und a-Ge/c-Si

    Energy Technology Data Exchange (ETDEWEB)

    Thiel, K.

    2006-11-02

    In this Thesis the interfaces between covalently bonded crystalline and amorphous materials were studied with regard to the induced ordering in the amorphous material in the interfacial region by means of high-resolution transmission electron microscopy (HREM). The interface between amorphous germanium and crystalline silicon and the interface between amorphous and crystalline silicon served as material system. In order to quantify the influence of the crystalline order on the amorphous material, the HREM images were periodically averaged along the interface. The intensity components, which are correlated with the period of the lattice image, could thus be separated from the statistical intensity fluctuations, which are characteristic for images of amorphous materials. Since amorphous materials can only be described meaningful by statistical distribution functions, for the induced order a three-dimensional distribution function {rho}{sub 3D}(r) was taken as a basis, which describes the probability to find an atom in the amorphous material, if r=0 is the position of an atom in the crystal. Its two-dimensional projection, {rho}, can be determined using iterative image matching techniques on averaged experimental and simulated interface images. For the analyzed material systems {rho} exhibits lateral ordering as well as a pronounced layering in the vicinity of the interface. In the case of the a-Si/c-Si sample the mean orientation of bonds was 70.5 , as is in the case of the undistorted diamond lattice, while for the a-Ge/c-Si sample 65 resulted. The standard deviation for the distribution of the deviations from the mean bond angle yields for the a-Ge/c-Si sample in the first atomic layer a value of 11.3 and for the a-Si/c-Si sample 1.9 . These results suggest the conclusion, that the differences in these values are to be interpreted as the reaction of the amorphous material to the volume misfit. Although for both material systems 1.4 nm was calculated for the width

  9. Corrosion Study and Intermetallics Formation in Gold and Copper Wire Bonding in Microelectronics Packaging

    Directory of Open Access Journals (Sweden)

    Christopher Breach

    2013-07-01

    Full Text Available A comparison study on the reliability of gold (Au and copper (Cu wire bonding is conducted to determine their corrosion and oxidation behavior in different environmental conditions. The corrosion and oxidation behaviors of Au and Cu wire bonding are determined through soaking in sodium chloride (NaCl solution and high temperature storage (HTS at 175 °C, 200 °C and 225 °C. Galvanic corrosion is more intense in Cu wire bonding as compared to Au wire bonding in NaCl solution due to the minimal formation of intermetallics in the former. At all three HTS annealing temperatures, the rate of Cu-Al intermetallic formation is found to be three to five times slower than Au-Al intermetallics. The faster intermetallic growth rate and lower activation energy found in this work for both Au/Al and Cu/Al as compared to literature could be due to the thicker Al pad metallization which removed the rate-determining step in previous studies due to deficit in Al material.

  10. Chemical methods and approaches to the regioselective formation of multiple disulfide bonds.

    Science.gov (United States)

    Shimamoto, Shigeru; Katayama, Hidekazu; Okumura, Masaki; Hidaka, Yuji

    2014-04-01

    Disulfide-bond formation plays an important role in the stabilization of the native conformation of peptides and proteins. In the case of multidisulfide-containing peptides and proteins, numerous folding intermediates are produced, including molecules that contain non-native and native disulfide bonds during in vitro folding. These intermediates can frequently be trapped covalently during folding and subsequently analyzed. The structural characterization of these kinetically trapped disulfide intermediates provides a clue to understanding the oxidative folding pathway. To investigate the folding of disulfide-containing peptides and proteins, in this unit, chemical methods are described for regulating regioselective disulfide formation (1) by using a combination of several types of thiol protecting groups, (2) by incorporating unique SeCys residues into a protein or peptide molecule, and (3) by combining with post-translational modification. Copyright © 2014 John Wiley & Sons, Inc.

  11. Renewable Formate from C-H Bond Formation with CO2: Using Iron Carbonyl Clusters as Electrocatalysts.

    Science.gov (United States)

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

    2017-09-19

    As a society, we are heavily dependent on nonrenewable petroleum-derived fuels and chemical feedstocks. Rapid depletion of these resources and the increasingly evident negative effects of excess atmospheric CO 2 drive our efforts to discover ways of converting excess CO 2 into energy dense chemical fuels through selective C-H bond formation and using renewable energy sources to supply electrons. In this way, a carbon-neutral fuel economy might be realized. To develop a molecular or heterogeneous catalyst for C-H bond formation with CO 2 requires a fundamental understanding of how to generate metal hydrides that selectively donate H - to CO 2 , rather than recombining with H + to liberate H 2 . Our work with a unique series of water-soluble and -stable, low-valent iron electrocatalysts offers mechanistic and thermochemical insights into formate production from CO 2 . Of particular interest are the nitride- and carbide-containing clusters: [Fe 4 N(CO) 12 ] - and its derivatives and [Fe 4 C(CO) 12 ] 2- . In both aqueous and mixed solvent conditions, [Fe 4 N(CO) 12 ] - forms a reduced hydride intermediate, [H-Fe 4 N(CO) 12 ] - , through stepwise electron and proton transfers. This hydride selectively reacts with CO 2 and generates formate with >95% efficiency. The mechanism for this transformation is supported by crystallographic, cyclic voltammetry, and spectroelectrochemical (SEC) evidence. Furthermore, installation of a proton shuttle onto [Fe 4 N(CO) 12 ] - facilitates proton transfer to the active site, successfully intercepting the hydride intermediate before it reacts with CO 2 ; only H 2 is observed in this case. In contrast, isoelectronic [Fe 4 C(CO) 12 ] 2- features a concerted proton-electron transfer mechanism to form [H-Fe 4 C(CO) 12 ] 2- , which is selective for H 2 production even in the presence of CO 2 , in both aqueous and mixed solvent systems. Higher nuclearity clusters were also studied, and all are proton reduction electrocatalysts, but none

  12. Fabrication of laminated ZrC-SiC composite by vacuum hot-pressing sintering

    Directory of Open Access Journals (Sweden)

    Yuanyuan Li

    2015-03-01

    Full Text Available Laminated ZrC-SiC ceramic was prepared through tape casting and hot pressing. The green tapes of ZrC and SiC were prepared at room temperature. In order to improve the density of composite, the binder of green tapes were removed at 550 °C for 1 h. The laminated structure and the cracks propagation path, which is not a straight line, are observed by optical metalloscope. The compact laminated ZrC-SiC composite sintered by vacuum hot-pressing at 1650 °C for 90 min under pressure of 20 MPa was researched by X-ray diffraction and scanning electron microscopy (SEM equipped with energy dispersive X-ray analysis. The results showed that interlayer bonding is tight, and no disordered phase has formed in the interlayers of ZrC or SiC, and the combination mode is physical mechanism.

  13. The Mechanical and Electrical Effects of MEMS Capacitive Pressure Sensor Based 3C-SiC for Extreme Temperature

    Directory of Open Access Journals (Sweden)

    N. Marsi

    2014-01-01

    Full Text Available This paper discusses the mechanical and electrical effects on 3C-SiC and Si thin film as a diaphragm for MEMS capacitive pressure sensor operating for extreme temperature which is 1000 K. This work compares the design of a diaphragm based MEMS capacitive pressure sensor employing 3C-SiC and Si thin films. A 3C-SiC diaphragm was bonded with a thickness of 380 μm Si substrate, and a cavity gap of 2.2 μm is formed between the wafers. The MEMS capacitive pressure sensor designs were simulated using COMSOL ver 4.3 software to compare the diaphragm deflection, capacitive performance analysis, von Mises stress, and total electrical energy performance. Both materials are designed with the same layout dimensional with different thicknesses of the diaphragm which are 1.0 μm, 1.6 μm, and 2.2 μm. It is observed that the 3C-SiC thin film is far superior materials to Si thin film mechanically in withstanding higher applied pressures and temperatures. For 3C-SiC and Si, the maximum von Mises stress achieved is 148.32 MPa and 125.48 MPa corresponding to capacitance value which is 1.93 pF and 1.22 pF, respectively. In terms of electrical performance, the maximum output capacitance of 1.93 pF is obtained with less total energy of 5.87 × 10−13 J, thus having a 50% saving as compared to Si.

  14. C-C bond formation and cleavage in radical enzymes, a theoretical perspective.

    Science.gov (United States)

    Himo, Fahmi

    2005-02-25

    Quantum chemical methods are today a viable tool in the study of enzyme catalysis. The development of new density functional techniques and the enormous advancement in computer power have made it possible to accurately describe active sites of enzymes. This review gives a brief account of the methods and models used in this field. Three specific enzymes are discussed: pyruvate-formate lyase (PFL), spore photoproduct lyase (SPL), and benzylsuccinate synthase (BSS). What these enzymes have in common is that they use radical chemistry to catalyze C-C bond formation or cleavage reactions.

  15. Palladium(II)-Catalyzed C-H Bond Activation/C-C and C-O Bond Formation Reaction Cascade: Direct Synthesis of Coumestans.

    Science.gov (United States)

    Neog, Kashmiri; Borah, Ashwini; Gogoi, Pranjal

    2016-12-02

    A palladium catalyzed cascade reaction of 4-hydroxycoumarins and in situ generated arynes has been developed for the direct synthesis of coumestans. This cascade strategy proceeds via C-H bond activation/C-O and C-C bond formations in a single reaction vessel. This methodology affords moderate to good yields of coumestans and is tolerant of a variety of functional groups including halide. The methodology was applied to the synthesis of natural product flemichapparin C.

  16. Nano-motion dynamics are determined by surface-tethered selectin mechanokinetics and bond formation.

    Directory of Open Access Journals (Sweden)

    Brian J Schmidt

    2009-12-01

    Full Text Available The interaction of proteins at cellular interfaces is critical for many biological processes, from intercellular signaling to cell adhesion. For example, the selectin family of adhesion receptors plays a critical role in trafficking during inflammation and immunosurveillance. Quantitative measurements of binding rates between surface-constrained proteins elicit insight into how molecular structural details and post-translational modifications contribute to function. However, nano-scale transport effects can obfuscate measurements in experimental assays. We constructed a biophysical simulation of the motion of a rigid microsphere coated with biomolecular adhesion receptors in shearing flow undergoing thermal motion. The simulation enabled in silico investigation of the effects of kinetic force dependence, molecular deformation, grouping adhesion receptors into clusters, surface-constrained bond formation, and nano-scale vertical transport on outputs that directly map to observable motions. Simulations recreated the jerky, discrete stop-and-go motions observed in P-selectin/PSGL-1 microbead assays with physiologic ligand densities. Motion statistics tied detailed simulated motion data to experimentally reported quantities. New deductions about biomolecular function for P-selectin/PSGL-1 interactions were made. Distributing adhesive forces among P-selectin/PSGL-1 molecules closely grouped in clusters was necessary to achieve bond lifetimes observed in microbead assays. Initial, capturing bond formation effectively occurred across the entire molecular contour length. However, subsequent rebinding events were enhanced by the reduced separation distance following the initial capture. The result demonstrates that vertical transport can contribute to an enhancement in the apparent bond formation rate. A detailed analysis of in silico motions prompted the proposition of wobble autocorrelation as an indicator of two-dimensional function. Insight into two

  17. {alpha}-Man monolayer formation via Si-C bond formation and protein recognition

    Energy Technology Data Exchange (ETDEWEB)

    Funato, Koji [School of Materials Science, Japan Advanced Institute of Science and Technology, 1-1 Asahidai, Nomi, Ishikawa 923-1292 (Japan); Shirahata, Naoto [National Institute for Materials Science (NIMS), 1-2-1 Sengen, Tsukuba, Ibaraki 305-0047 (Japan); Miura, Yoshiko, E-mail: miuray@jaist.ac.j [School of Materials Science, Japan Advanced Institute of Science and Technology, 1-1 Asahidai, Nomi, Ishikawa 923-1292 (Japan)

    2009-11-30

    An acetylenyl-terminated saccharide was synthesized and the thin layer formation on the hydrogen-terminated silicon was investigated. The acetylenyl-terminated saccharide was synthesized by the condensation reaction of hexynoic acid and p-aminophenyl saccharide. This was reacted with hydrogen-terminated silicon (Si-H) by a photochemical reaction. The resulting saccharide modified substrate was analyzed by ellipsometry and X-ray photoelectron spectroscopy, which showed the formation of a uniform monolayer. The surface's ability to recognize proteins was analyzed by fluorescent microscopy, and showed specific interactions with sugar recognition proteins.

  18. Improved C/SiC Ceramic Composites Made Using PIP

    Science.gov (United States)

    Easler, Timothy

    2007-01-01

    Improved carbon-fiber-reinforced SiC ceramic-matrix composite (C/SiC CMC) materials, suitable for fabrication of thick-section structural components, are producible by use of a combination of raw materials and processing conditions different from such combinations used in the prior art. In comparison with prior C/SiC CMC materials, these materials have more nearly uniform density, less porosity, and greater strength. The majority of raw-material/processing-condition combinations used in the prior art involve the use of chemical vapor infiltration (CVI) for densifying the matrix. In contrast, in synthesizing a material of the present type, one uses a combination of infiltration with, and pyrolysis of, a preceramic polymer [polymer infiltration followed by pyrolysis (PIP)]. PIP processing is performed in repeated, tailored cycles of infiltration followed by pyrolysis. Densification by PIP processing takes less time and costs less than does densification by CVI. When one of these improved materials was tested by exposure to a high-temperature, inert-gas environment that caused prior C/SiC CMCs to lose strength, this material did not lose strength. (Information on the temperature and exposure time was not available at the time of writing this article.) A material of the present improved type consists, more specifically, of (1) carbon fibers coated with an engineered fiber/matrix interface material and (2) a ceramic matrix, containing SiC, derived from a pre-ceramic polymer with ceramic powder additions. The enhancements of properties of these materials relative to those of prior C/SiC CMC materials are attributable largely to engineering of the fiber/ matrix interfacial material and the densification process. The synthesis of a material of this type includes processing at an elevated temperature to a low level of open porosity. The approach followed in this processing allows one to fabricate not only simple plates but also more complexly shaped parts. The carbon fiber

  19. Joining of SiC ceramics and SiC/SiC composites

    Energy Technology Data Exchange (ETDEWEB)

    Rabin, B.H. [Idaho National Engineering Lab., Idaho Falls, ID (United States)

    1995-08-01

    This project has successfully developed a practical and reliable method for fabricating SiC ceramic-ceramic joints. This joining method has the potential to facilitate the use of SiC-based ceramics in a variety of elevated temperature fossil energy applications. The technique is based on a reaction bonding approach that provides joint interlayers compatible with SiC, and excellent joint mechanical properties at temperatures exceeding 1000{degrees}C. Recent efforts have focused on transferring the joining technology to industry. Several industrial partners have been identified and collaborative research projects are in progress. Investigations are focusing on applying the joining method to sintered a-SiC and fiber-reinforced SiC/SiC composites for use in applications such as heat exchangers, radiant burners and gas turbine components.

  20. Joining of SiC ceramics and SiC/SiC composites

    Energy Technology Data Exchange (ETDEWEB)

    Rabin, B.H. [Idaho National Engineering Lab., Idaho Falls, ID (United States)

    1996-08-01

    This project has successfully developed a practical and reliable method for fabricating SiC ceramic-ceramic joints. This joining method will permit the use of SiC-based ceramics in a variety of elevated temperature fossil energy applications. The technique is based on a reaction bonding approach that provides joint interlayers compatible with SiC, and excellent joint mechanical properties at temperatures exceeding 1000{degrees}C. Recent emphasis has been given to technology transfer activities, and several collaborative research efforts are in progress. Investigations are focusing on applying the joining method to sintered {alpha}-SiC and fiber-reinforced SiC/SiC composites for use in applications such as heat exchangers, radiant burners and gas turbine components.

  1. Formation of the market of high-bond (junk bonds in the United States in 1970–1980 years

    Directory of Open Access Journals (Sweden)

    Moshenskyi S.Z.

    2017-03-01

    Full Text Available Market of high-yield bonds (also known as «junk bonds» began to emerge in the US in the mid-1970s and was associated with the activities of «junk bond king» Michael Milken from Drexel investment company. Junk bonds emitents are small and newly established companies which cannot get a high credit rating. Emission of high-yield (8–10 % bond was their only chance to find its place in the financial market. Michael Milken realized the potential of these bonds, which, in fact, were often quite reliable securities, and started organizing their emissions by selling junk bonds to Savings and Loan Associations and other investors. In the 1980 issue of such bonds used for aggressive corporate takeovers, which supplied the capital from junk bonds market. Some of takeovers carried out in violation of laws that led to the arrest of Michael Milken, Drexel bankruptcy and the collapse of the entire junk bonds market.

  2. Tribological properties of C/C-SiC composites for brake discs

    Science.gov (United States)

    Jang, G. H.; Cho, K. H.; Park, S. B.; Lee, W. G.; Hong, U. S.; Jang, H.

    2010-02-01

    This study examines the friction and wear of ceramic matrix composites designed for use in automotive brake discs. The composites are produced by reinforcing a SiC matrix with carbon fibers using a liquid silicon infiltration method. C/C-SiC composites with two different compositions are fabricated to examine the compositional effect on the tribological properties. The tribological properties are evaluated using a scale dynamometer with a low-steel type friction material. The results show that the coefficient of friction is determined by the composition of the composite, which affects the propensity of friction film formation on the disc surface. A stable friction film on the disc surface also improves the wear resistance by diminishing the abrasive action of the disc. On the other hand, the friction film formation on the disc is affected by the applied pressure, and stable films are obtained at high pressures. This trend is prominent with discs with high Si content. However, both C/C/-SiC composites show superior performance in terms of the friction force oscillation, which is closely related to brake-induced vibration.

  3. SiC/SiC Cladding Materials Properties Handbook

    Energy Technology Data Exchange (ETDEWEB)

    Snead, Mary A. [Brookhaven National Lab. (BNL), Upton, NY (United States); Katoh, Yutai [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Koyanagi, Takaaki [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Singh, Gyanender P. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

    2017-08-01

    When a new class of material is considered for a nuclear core structure, the in-pile performance is usually assessed based on multi-physics modeling in coordination with experiments. This report aims to provide data for the mechanical and physical properties and environmental resistance of silicon carbide (SiC) fiber–reinforced SiC matrix (SiC/SiC) composites for use in modeling for their application as accidenttolerant fuel cladding for light water reactors (LWRs). The properties are specific for tube geometry, although many properties can be predicted from planar specimen data. This report presents various properties, including mechanical properties, thermal properties, chemical stability under normal and offnormal operation conditions, hermeticity, and irradiation resistance. Table S.1 summarizes those properties mainly for nuclear-grade SiC/SiC composites fabricated via chemical vapor infiltration (CVI). While most of the important properties are available, this work found that data for the in-pile hydrothermal corrosion resistance of SiC materials and for thermal properties of tube materials are lacking for evaluation of SiC-based cladding for LWR applications.

  4. Spectral characteristics of a-Si:H/c-Si heterostructures

    Energy Technology Data Exchange (ETDEWEB)

    Gall, S.; Hirschauer, R.; Braeunig, D. [Hahn-Meitner-Institut Berlin, Department AT, Berlin (Germany); Kolter, M. [Forschungszentrum Juelich, Department ISI-PV, Juelich (Germany)

    1997-10-21

    We have examined the current-voltage characteristic of i-a-Si:H/n-c-Si heterojunction Schottky solar cells in the dark and under different illumination (spectrum AM1.5) intensities as well as the voltage- and temperature-dependent spectral response of these devices. The photocurrent from the crystalline silicon depends on both voltage and temperature due to their influence on the impact of the band offsets. From our measurements of the spectral response we conclude that there is a small conduction band offset {Delta}E{sub c} and a large valence band offset {Delta}E{sub v} at the i-a-Si:H/n-c-Si heterojunction. The large valence band offset inhibits the collection of photogenerated holes from the crystalline silicon under normal photovoltaic conditions. Thus, the current-voltage characteristic under illumination between V=0 V and V=V{sub oc} is caused only by the photocurrent from the a-Si:H layer

  5. C–C Bond formation catalyzed by natural gelatin and collagen proteins

    Directory of Open Access Journals (Sweden)

    Dennis Kühbeck

    2013-06-01

    Full Text Available The activity of gelatin and collagen proteins towards C–C bond formation via Henry (nitroaldol reaction between aldehydes and nitroalkanes is demonstrated for the first time. Among other variables, protein source, physical state and chemical modification influence product yield and kinetics, affording the nitroaldol products in both aqueous and organic media under mild conditions. Significantly, the scale-up of the process between 4-nitrobenzaldehyde and nitromethane is successfully achieved at 1 g scale and in good yield. A comparative kinetic study with other biocatalysts shows an increase of the first-order rate constant in the order chitosan < gelatin < bovine serum albumin (BSA < collagen. The results of this study indicate that simple edible gelatin can promote C–C bond forming reactions under physiological conditions, which may have important implications from a metabolic perspective.

  6. Dissecting the role of disulfide bonds on the amyloid formation of insulin.

    Science.gov (United States)

    Li, Yang; Gong, Hao; Sun, Yue; Yan, Juan; Cheng, Biao; Zhang, Xin; Huang, Jing; Yu, Mengying; Guo, Yu; Zheng, Ling; Huang, Kun

    2012-06-29

    Disulfide bonds play a critical role in the stability and folding of proteins. Here, we used insulin as a model system, to investigate the role of its individual disulfide bond during the amyloid formation of insulin. Tris(2-carboxyethyl)phosphine (TCEP) was applied to reduce two of the three disulfide bonds in porcine insulin and the reduced disulfide bonds were then alkylated by iodoacetamide. Three disulfide bond-modified insulin analogs, INS-2 (lack of A6-A11), INS-3 (lack of A7-B7) and INS-6 (lack of both A6-A11 and A7-B7), were obtained. Far-UV circular dichroism (CD) spectroscopy results indicated that the secondary structure of INS-2 was the closest to insulin under neutral conditions, followed by INS-3 and INS-6, whereas in an acidic solution all analogs were essentially unfolded. To test how these modifications affect the amyloidogenicity of insulin, thioflavin-T (ThT) fluorescence and transmission electronic microscopy (TEM) were performed. Our results showed that all analogs were more prone to aggregation than insulin, with the order of aggregation rates being INS-6>INS-3>INS-2. Cross-linking of unmodified proteins (PICUP) assay results showed that analogs without A6-A11 (INS-2 and INS-6) have a higher potential for oligomerization than insulin and INS-3, which is accompanied with a higher cytotoxicity as the hemolytic assays of human erythrocytes suggested. The results indicated that breakage of A7-B7 induced more unfolding of the insulin structure and a higher amyloidogenicity than breakage of A6-A11, but breakage of A6-A11 caused a significant cytotoxicity increase and a higher potency to form high order toxic oligomers. Copyright © 2012 Elsevier Inc. All rights reserved.

  7. Porous nC-Si/SiOx nanostructured layer on Si substrate with tunable photoluminescent properties fabricated by direct, precursor-free microplasma irradiation in air

    Science.gov (United States)

    Wang, Tao; Hu, Mingshan; Yang, Bin; Wang, Xiaolin; Liu, Jingquan

    2018-03-01

    Porous nC-Si/SiOx photoluminescent nanostructured layer is fabricated by direct, precursor-free microplasma irradiation on Si substrate in air. It is confirmed that the deposited layer has porous and cluster-like structures by scanning electron microscopy (SEM) and profile scanning. Fourier transform infrared transmission (FTIR), X-ray diffraction (XRD) and X-ray photoelectron spectrum (XPS) results indicate the produced layer is actually composed of nanocrystalline silicon (nC-Si) embedded in SiOx matrix. Transmission electron microscopy (TEM) and Raman results show the mean particle size of nC-Si is mainly between 2 and 4 nm and the highest crystalline volume fraction reaches 86.9%. The photoluminescence (PL) measurement of nC-Si/SiOx layer exhibited a broad band centered at 1.7-1.9 eV, ranging from 1.2-2.4 eV, and could be tuned by varying the applied voltage. The synthetical mechanisms are discussed to explain the PL properties of the layers. We propose that the energetic ions bombing induced by high compressed electric field near the Si surface is the main reason for porous nC-Si/SiOx formation. Maskless deposition of the line pattern of nC-Si/SiOx layer was also successfully fabricated. This simple, maskless, vacuum-free and precursor-free technique could be used in various potential optoelectronics and biological applications in the future.

  8. Madumycin II inhibits peptide bond formation by forcing the peptidyl transferase center into an inactive state

    Energy Technology Data Exchange (ETDEWEB)

    Osterman, Ilya A.; Khabibullina, Nelli F.; Komarova, Ekaterina S.; Kasatsky, Pavel; Kartsev, Victor G.; Bogdanov, Alexey A.; Dontsova, Olga A.; Konevega, Andrey L.; Sergiev, Petr V.; Polikanov, Yury S. (InterBioScreen); (UIC); (MSU-Russia); (Kurchatov)

    2017-05-13

    The emergence of multi-drug resistant bacteria is limiting the effectiveness of commonly used antibiotics, which spurs a renewed interest in revisiting older and poorly studied drugs. Streptogramins A is a class of protein synthesis inhibitors that target the peptidyl transferase center (PTC) on the large subunit of the ribosome. In this work, we have revealed the mode of action of the PTC inhibitor madumycin II, an alanine-containing streptogramin A antibiotic, in the context of a functional 70S ribosome containing tRNA substrates. Madumycin II inhibits the ribosome prior to the first cycle of peptide bond formation. It allows binding of the tRNAs to the ribosomal A and P sites, but prevents correct positioning of their CCA-ends into the PTC thus making peptide bond formation impossible. We also revealed a previously unseen drug-induced rearrangement of nucleotides U2506 and U2585 of the 23S rRNA resulting in the formation of the U2506•G2583 wobble pair that was attributed to a catalytically inactive state of the PTC. The structural and biochemical data reported here expand our knowledge on the fundamental mechanisms by which peptidyl transferase inhibitors modulate the catalytic activity of the ribosome.

  9. Bridging and bonding interactions in higher education: social capital and students' academic and professional identity formation.

    Science.gov (United States)

    Jensen, Dorthe H; Jetten, Jolanda

    2015-01-01

    It is increasingly recognized that graduates' achievements depend in important ways on their opportunities to develop an academic and a professional identity during their studies. Previous research has shown that students' socio-economic status (SES) and social capital prior to entering university affects their ability to obtain these identities in higher education. However, what is less well understood is whether social capital that is built during university studies shapes identity development, and if so, whether the social capital gained during university years impacts on academic and professional identity differently. In a qualitative study, we interviewed 26 Danish and 11 Australian university students about their social interaction experiences, their opportunities to develop bonding capital as well as bridging capital, and their academic and professional identity. Findings show that while bonding social capital with co-students facilitated academic identity formation, such social capital does not lead to professional identity development. We also found that the development of bridging social capital with educators facilitated students' professional identity formation. However, bonding social capital among students stood in the way of participating in bridging interaction with educators, thereby further hindering professional identity formation. Finally, while students' parental background did not affect the perceived difficulty of forming professional identity, there was a tendency for students from lower SES backgrounds to be more likely to make internal attributions while those from higher SES backgrounds were more likely to make external attributions for the failure to develop professional identity. Results point to the importance of creating opportunities for social interaction with educators at university because this facilitates the generation of bridging social capital, which, in turn, is essential for students' professional identity development.

  10. Bridging and bonding interactions in higher education: social capital and students’ academic and professional identity formation

    Science.gov (United States)

    Jensen, Dorthe H.; Jetten, Jolanda

    2015-01-01

    It is increasingly recognized that graduates’ achievements depend in important ways on their opportunities to develop an academic and a professional identity during their studies. Previous research has shown that students’ socio-economic status (SES) and social capital prior to entering university affects their ability to obtain these identities in higher education. However, what is less well understood is whether social capital that is built during university studies shapes identity development, and if so, whether the social capital gained during university years impacts on academic and professional identity differently. In a qualitative study, we interviewed 26 Danish and 11 Australian university students about their social interaction experiences, their opportunities to develop bonding capital as well as bridging capital, and their academic and professional identity. Findings show that while bonding social capital with co-students facilitated academic identity formation, such social capital does not lead to professional identity development. We also found that the development of bridging social capital with educators facilitated students’ professional identity formation. However, bonding social capital among students stood in the way of participating in bridging interaction with educators, thereby further hindering professional identity formation. Finally, while students’ parental background did not affect the perceived difficulty of forming professional identity, there was a tendency for students from lower SES backgrounds to be more likely to make internal attributions while those from higher SES backgrounds were more likely to make external attributions for the failure to develop professional identity. Results point to the importance of creating opportunities for social interaction with educators at university because this facilitates the generation of bridging social capital, which, in turn, is essential for students’ professional identity

  11. An Erbium-Based Bifuctional Heterogeneous Catalyst: A Cooperative Route Towards C-C Bond Formation

    Directory of Open Access Journals (Sweden)

    Manuela Oliverio

    2014-07-01

    Full Text Available Heterogeneous bifuctional catalysts are multifunctional synthetic catalysts enabling efficient organic transformations by exploiting two opposite functionalities without mutual destruction. In this paper we report the first Er(III-based metallorganic heterogeneous catalyst, synthesized by post-calcination MW-assisted grafting and modification of the natural aminoacid L-cysteine. The natural acid–base distance between sites was maintained to assure the cooperation. The applicability of this new bifunctional heterogeneous catalyst to C-C bond formation and the supposed mechanisms of action are discussed as well.

  12. Ring-opening of cyclic ethers with carbon–carbon bond formation by Grignard reagents

    DEFF Research Database (Denmark)

    Christensen, Stig Holden; Holm, Torkil; Madsen, Robert

    2014-01-01

    The ring-opening of cyclic ethers with concomitant C–C bond formation was studied with a number of Grignard reagents. The transformation was performed in a sealed vial by heating to ∼160 °C in an aluminum block or at 180 °C in a microwave oven. Good yields of the product alcohols were obtained...... with allyl- and benzylmagnesium halides when the ether was tetrahydrofuran or 3,3-dimethyloxetane. Lower yields were obtained with substituted tetrahydrofurans while no ring-opening was observed with tetrahydropyran. Only highly reactive allyl and benzyl Grignard reagents participated in the transformation...

  13. Dissecting the role of disulfide bonds on the amyloid formation of insulin

    Energy Technology Data Exchange (ETDEWEB)

    Li, Yang; Gong, Hao [Tongji School of Pharmacy, Huazhong University of Science and Technology, Wuhan 430030 (China); Sun, Yue [College of Life Sciences, Wuhan University, Wuhan 430072 (China); Yan, Juan; Cheng, Biao; Zhang, Xin [Tongji School of Pharmacy, Huazhong University of Science and Technology, Wuhan 430030 (China); Huang, Jing [College of Life Sciences, Wuhan University, Wuhan 430072 (China); Yu, Mengying; Guo, Yu [Tongji School of Pharmacy, Huazhong University of Science and Technology, Wuhan 430030 (China); Zheng, Ling, E-mail: lzheng217@hotmail.com [College of Life Sciences, Wuhan University, Wuhan 430072 (China); Huang, Kun, E-mail: kunhuang2008@hotmail.com [Tongji School of Pharmacy, Huazhong University of Science and Technology, Wuhan 430030 (China); Centre for Biomedicine Research, Wuhan Institutes of Biotechnology, Wuhan 430070 (China)

    2012-06-29

    Highlights: Black-Right-Pointing-Pointer We dissect how individual disulfide bond affects the amyloidogenicity of insulin. Black-Right-Pointing-Pointer A controlled reduction system for insulin is established in this study. Black-Right-Pointing-Pointer Disulfide breakage is associated with unfolding and increased amyloidogenicity. Black-Right-Pointing-Pointer Breakage of A6-A11 is associated with significantly increased cytotoxicity. Black-Right-Pointing-Pointer Analogs without A6-A11 have a higher potency to form high order toxic oligomers. -- Abstract: Disulfide bonds play a critical role in the stability and folding of proteins. Here, we used insulin as a model system, to investigate the role of its individual disulfide bond during the amyloid formation of insulin. Tris(2-carboxyethyl)phosphine (TCEP) was applied to reduce two of the three disulfide bonds in porcine insulin and the reduced disulfide bonds were then alkylated by iodoacetamide. Three disulfide bond-modified insulin analogs, INS-2 (lack of A6-A11), INS-3 (lack of A7-B7) and INS-6 (lack of both A6-A11 and A7-B7), were obtained. Far-UV circular dichroism (CD) spectroscopy results indicated that the secondary structure of INS-2 was the closest to insulin under neutral conditions, followed by INS-3 and INS-6, whereas in an acidic solution all analogs were essentially unfolded. To test how these modifications affect the amyloidogenicity of insulin, thioflavin-T (ThT) fluorescence and transmission electronic microscopy (TEM) were performed. Our results showed that all analogs were more prone to aggregation than insulin, with the order of aggregation rates being INS-6 > INS-3 > INS-2. Cross-linking of unmodified proteins (PICUP) assay results showed that analogs without A6-A11 (INS-2 and INS-6) have a higher potential for oligomerization than insulin and INS-3, which is accompanied with a higher cytotoxicity as the hemolytic assays of human erythrocytes suggested. The results indicated that breakage of A7

  14. Acetic Acid Can Catalyze Succinimide Formation from Aspartic Acid Residues by a Concerted Bond Reorganization Mechanism: A Computational Study

    Directory of Open Access Journals (Sweden)

    Ohgi Takahashi

    2015-01-01

    Full Text Available Succinimide formation from aspartic acid (Asp residues is a concern in the formulation of protein drugs. Based on density functional theory calculations using Ace-Asp-Nme (Ace = acetyl, Nme = NHMe as a model compound, we propose the possibility that acetic acid (AA, which is often used in protein drug formulation for mildly acidic buffer solutions, catalyzes the succinimide formation from Asp residues by acting as a proton-transfer mediator. The proposed mechanism comprises two steps: cyclization (intramolecular addition to form a gem-diol tetrahedral intermediate and dehydration of the intermediate. Both steps are catalyzed by an AA molecule, and the first step was predicted to be rate-determining. The cyclization results from a bond formation between the amide nitrogen on the C-terminal side and the side-chain carboxyl carbon, which is part of an extensive bond reorganization (formation and breaking of single bonds and the interchange of single and double bonds occurring concertedly in a cyclic structure formed by the amide NH bond, the AA molecule and the side-chain C=O group and involving a double proton transfer. The second step also involves an AA-mediated bond reorganization. Carboxylic acids other than AA are also expected to catalyze the succinimide formation by a similar mechanism.

  15. Environmental Barrier Coating Development for SiC/SiC Ceramic Matrix Composites: Recent Advances and Future Directions

    Science.gov (United States)

    Zhu, Dongming

    2016-01-01

    This presentation briefly reviews the SiC/SiC major environmental and environment-fatigue degradations encountered in simulated turbine combustion environments, and thus NASA environmental barrier coating system evolution for protecting the SiC/SiC Ceramic Matrix Composites for meeting the engine performance requirements. The presentation will review several generations of NASA EBC materials systems, EBC-CMC component system technologies for SiC/SiC ceramic matrix composite combustors and turbine airfoils, highlighting the temperature capability and durability improvements in simulated engine high heat flux, high pressure, high velocity, and with mechanical creep and fatigue loading conditions. This paper will also focus on the performance requirements and design considerations of environmental barrier coatings for next generation turbine engine applications. The current development emphasis is placed on advanced NASA candidate environmental barrier coating systems for SiC/SiC CMCs, their performance benefits and design limitations in long-term operation and combustion environments. The efforts have been also directed to developing prime-reliant, self-healing 2700F EBC bond coat; and high stability, lower thermal conductivity, and durable EBC top coats. Major technical barriers in developing environmental barrier coating systems, the coating integrations with next generation CMCs having the improved environmental stability, erosion-impact resistance, and long-term fatigue-environment system durability performance will be described. The research and development opportunities for turbine engine environmental barrier coating systems by utilizing improved compositions, state-of-the-art processing methods, and simulated environment testing and durability modeling will be briefly discussed.

  16. Structural analysis of SgvP involved in carbon-sulfur bond formation during griseoviridin biosynthesis.

    Science.gov (United States)

    Li, Qin; Chen, Yan; Zhang, Guiqin; Zhang, Huaidong

    2017-05-01

    Griseoviridin (GV) is a broad-spectrum antibiotic with antibacterial and antifungal activity. In the GV biosynthetic pathway, SgvP catalyzes formation of the carbon-sulfur bond in GV. Herein, we report the recombinant expression and characterization of SgvP from Streptomyces griseoviridis NRRL2427. We also present the 2.6 Å crystal structure of SgvP, which is the first structure of a cytochrome P450 involved in carbon-sulfur bond formation in GV. Structural analysis indicates that Pro237 in the I-helix of SgvP may play a critical role in dioxygen binding and proton transfer during the catalytic cycle. Of the three channels we observed in SgvP, channel 3 may be essential for substrate ingress and egress from the active site, while channels 1 and 2 may be the solvent and water pathway, respectively. Coordinate and structure factor were deposited in the Protein Data Bank database under the accession number 4MM0. © 2017 Federation of European Biochemical Societies.

  17. Efficient surface patterning of oligonucleotides inside a glass capillary through oxime bond formation.

    Science.gov (United States)

    Dendane, Nabil; Hoang, Antoine; Guillard, Ludovic; Defrancq, Eric; Vinet, Françoise; Dumy, Pascal

    2007-01-01

    The efficient surface patterning of oligonucleotides was accomplished onto the inner wall of fused-silica capillary tubes as well as on the surface of glass slides through oxime bond formation. The robustness of the method was demonstrated by achieving the surface immobilization of up to three different oligonucleotide sequences inside the same capillary tube. The method involves the preparation of surfaces grafted with reactive aminooxy functionalities masked with the photocleavable protecting group, 2-(2-nitrophenyl) propyloxycarbonyl group (NPPOC). Briefly, NPPOC-aminooxy silane 1 was prepared and used to silanize the glass surfaces. The NPPOC group was cleaved under brief irradiation to unmask the reactive aminooxy group on surfaces. These reactive aminooxy groups were allowed to react with aldehyde-containing oligonucleotides to achieve an efficient surface immobilization. The advantage associated with the present approach is that it combines the high-coupling efficiency of oxime bond formation with the convenience associated with the use of photolabile groups. The present strategy thus offers an alternative approach for the immobilization of biomolecules in the microchannels of "labs on a chip" devices.

  18. In vivo biofilm formation on stainless steel bonded retainers during different oral health-care regimens.

    Science.gov (United States)

    Jongsma, Marije A; van der Mei, Henny C; Atema-Smit, Jelly; Busscher, Henk J; Ren, Yijin

    2015-03-23

    Retention wires permanently bonded to the anterior teeth are used after orthodontic treatment to prevent the teeth from relapsing to pre-treatment positions. A disadvantage of bonded retainers is biofilm accumulation on the wires, which produces a higher incidence of gingival recession, increased pocket depth and bleeding on probing. This study compares in vivo biofilm formation on single-strand and multi-strand retention wires with different oral health-care regimens. Two-centimetre wires were placed in brackets that were bonded to the buccal side of the first molars and second premolars in the upper arches of 22 volunteers. Volunteers used a selected toothpaste with or without the additional use of a mouthrinse containing essential oils. Brushing was performed manually. Regimens were maintained for 1 week, after which the wires were removed and the oral biofilm was collected to quantify the number of organisms and their viability, determine the microbial composition and visualize the bacteria by electron microscopy. A 6-week washout period was employed between regimens. Biofilm formation was reduced on single-strand wires compared with multi-strand wires; bacteria were observed to adhere between the strands. The use of antibacterial toothpastes marginally reduced the amount of biofilm on both wire types, but significantly reduced the viability of the biofilm organisms. Additional use of the mouthrinse did not result in significant changes in biofilm amount or viability. However, major shifts in biofilm composition were induced by combining a stannous fluoride- or triclosan-containing toothpaste with the mouthrinse. These shifts can be tentatively attributed to small changes in bacterial cell surface hydrophobicity after the adsorption of the toothpaste components, which stimulate bacterial adhesion to the hydrophobic oil, as illustrated for a Streptococcus mutans strain.

  19. Lewis acid mediated tandem reaction of propargylic alcohols to tetrazoles involving C-O- and C-C-bond cleavage reactions and a C-N-bond formation.

    Science.gov (United States)

    Song, Xian-Rong; Han, Ya-Ping; Qiu, Yi-Feng; Qiu, Zi-Hang; Liu, Xue-Yuan; Xu, Peng-Fei; Liang, Yong-Min

    2014-09-15

    A novel and direct synthesis of 1-aryl-5-arylvinyl-tetrazoles from easily prepared propargylic alcohols and TMSN3 is developed in the presence of TMSCl under mild conditions (TMS = trimethylsilyl). The process involves an allenylazide intermediate, followed by a C-C-bond cleavage and C-N-bond formation to afford the desired products. Moreover, this method offers a good functional-group applicability and can be scaled-up to grams (yield up to 85 %). © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. AlGaN/GaN high electron mobility transistors grown on 3C-SiC/Si(1 1 1)

    Science.gov (United States)

    Cordier, Yvon; Portail, Marc; Chenot, Sébastien; Tottereau, Olivier; Zielinski, Marcin; Chassagne, Thierry

    2008-10-01

    The elaboration of Gallium nitride (GaN)-based high electron mobility transistors (HEMTs) structures is comparatively investigated on cubic SiC/Si(1 1 1) templates and on silicon substrates. As compared with silicon, 3C-SiC/Si(1 1 1) template is less sensitive to the detrimental nitridation effect of ammonia, and it allows a reduction of the stress in GaN films due to both lower lattice and thermal expansion coefficient mismatch. Crack-free GaN layers and AlGaN/GaN HEMTs with total thicknesses exceeding 2 μm were successfully grown by molecular beam epitaxy on optimized 0.8-μm-thick 3C-SiC/Si templates elaborated by chemical vapor deposition. A threading dislocation density below 5×10 9 cm -2 and a two-dimensional electron gas with a sheet carrier concentration of 1.1×10 13 cm -2 and an electron mobility of 2050 cm 2/V s at room temperature have been obtained. The feasibility of the 3C-SiC/Si(1 1 1) approach is demonstrated by the structural and electrical quality of these structures, as well as the characteristics of transistors that are at least equivalent to reference transistors realized on bulk silicon substrates.

  1. Intra- and inter-subunit disulfide bond formation is nonessential in adeno-associated viral capsids.

    Directory of Open Access Journals (Sweden)

    Nagesh Pulicherla

    Full Text Available The capsid proteins of adeno-associated viruses (AAV have five conserved cysteine residues. Structural analysis of AAV serotype 2 reveals that Cys289 and Cys361 are located adjacent to each other within each monomer, while Cys230 and Cys394 are located on opposite edges of each subunit and juxtaposed at the pentamer interface. The Cys482 residue is located at the base of a surface loop within the trimer region. Although plausible based on molecular dynamics simulations, intra- or inter-subunit disulfides have not been observed in structural studies. In the current study, we generated a panel of Cys-to-Ser mutants to interrogate the potential for disulfide bond formation in AAV capsids. The C289S, C361S and C482S mutants were similar to wild type AAV with regard to titer and transduction efficiency. However, AAV capsid protein subunits with C230S or C394S mutations were prone to proteasomal degradation within the host cells. Proteasomal inhibition partially blocked degradation of mutant capsid proteins, but failed to rescue infectious virions. While these results suggest that the Cys230/394 pair is critical, a C394V mutant was found viable, but not the corresponding C230V mutant. Although the exact nature of the structural contribution(s of Cys230 and Cys394 residues to AAV capsid formation remains to be determined, these results support the notion that disulfide bond formation within the Cys289/361 or Cys230/394 pair appears to be nonessential. These studies represent an important step towards understanding the role of inter-subunit interactions that drive AAV capsid assembly.

  2. Spectroscopic Investigation of the Formation and Disruption of Hydrogen Bonds in Pharmaceutical Semicrystalline Dispersions.

    Science.gov (United States)

    Van Duong, Tu; Reekmans, Gunter; Venkatesham, Akkaladevi; Van Aerschot, Arthur; Adriaensens, Peter; Van Humbeeck, Jan; Van den Mooter, Guy

    2017-05-01

    . Screening of crystallization inhibitors of semicrystalline polymers discovers numerous candidates that exhibit the same behavior as IMC, demonstrating a general pattern of polymer crystallization inhibition rather than a particular case. Furthermore, the crystallization inhibition effect of drugs on PEG is independent of the carrier molecular weight. These mechanistic findings on the formation and disruption of hydrogen bonds in semicrystalline dispersions can be extended to amorphous dispersions and are of significant importance for preparation of solid dispersions with consistent and reproducible physicochemical properties.

  3. Fracture behavior of C/SiC composites at elevated temperature

    Energy Technology Data Exchange (ETDEWEB)

    Yoon, Dong Hyun; Lee, Jeong Won; Kim, Jae Hoon; Shin, Ihn Cheol; Lim, Byung Joo [Chungnam National University, Daejeon (Korea, Republic of)

    2017-08-15

    The fracture behavior of carbon fiber-reinforced silicon carbide (C/SiC) composites used in rocket nozzles has been investigated under tension, compression, and fracture conditions at room temperature, 773 K and 1173 K. The C/SiC composites used in this study were manufactured by liquid silicon infiltration process at ~1723 K. All experiments were conducted using two types of specimens, considering fiber direction and oxidation condition. Experimental results show that temperature, fiber direction, and oxidation condition affect the behavior of C/SiC composites. Oxidation was found to be the main factor that changes the strength of C/SiC composites. By applying an anti-oxidation coating, the tensile and compressive strengths of the C/SiC composites increased with temperature. The fracture toughness of the C/SiC composites also increased with increase temperature. A fractography analysis of the fractured specimens was conducted using a scanning electron microscope.

  4. Low-oxidation state indium-catalyzed C-C bond formation.

    Science.gov (United States)

    Schneider, Uwe; Kobayashi, Shu

    2012-08-21

    The development of innovative metal catalysis for selective bond formation is an important task in organic chemistry. The group 13 metal indium is appealing for catalysis because indium-based reagents are minimally toxic, selective, and tolerant toward various functional groups. Among elements in this group, the most stable oxidation state is typically +3, but in molecules with larger group 13 atoms, the chemistry of the +1 oxidation state is also important. The use of indium(III) compounds in organic synthesis has been well-established as Lewis acid catalysts including asymmetric versions thereof. In contrast, only sporadic examples of the use of indium(I) as a stoichiometric reagent have been reported: to the best of our knowledge, our investigations represent the first synthetic method that uses a catalytic amount of indium(I). Depending on the nature of the ligand or the counteranion to which it is coordinated, indium(I) can act as both a Lewis acid and a Lewis base because it has both vacant p orbitals and a lone pair of electrons. This potential ambiphilicity may offer unique reactivity and unusual selectivity in synthesis and may have significant implications for catalysis, particularly for dual catalytic processes. We envisioned that indium(I) could be employed as a metallic Lewis base catalyst to activate Lewis acidic boron-based pronucleophiles for selective bond formation with suitable electrophiles. Alternatively, indium(I) could serve as an ambiphilic catalyst that activates both reagents at a single center. In this Account, we describe the development of low-oxidation state indium catalysts for carbon-carbon bond formation between boron-based pronucleophiles and various electrophiles. We discovered that indium(I) iodide was an excellent catalyst for α-selective allylations of C(sp(2)) electrophiles such as ketones and hydrazones. Using a combination of this low-oxidation state indium compound and a chiral semicorrin ligand, we developed catalytic

  5. Disruption of reducing pathways is not essential for efficient disulfide bond formation in the cytoplasm of E. coli

    Directory of Open Access Journals (Sweden)

    Hatahet Feras

    2010-09-01

    Full Text Available Abstract Background The formation of native disulfide bonds is a complex and essential post-translational modification for many proteins. The large scale production of these proteins can be difficult and depends on targeting the protein to a compartment in which disulfide bond formation naturally occurs, usually the endoplasmic reticulum of eukaryotes or the periplasm of prokaryotes. It is currently thought to be impossible to produce large amounts of disulfide bond containing protein in the cytoplasm of wild-type bacteria such as E. coli due to the presence of multiple pathways for their reduction. Results Here we show that the introduction of Erv1p, a sulfhydryl oxidase and FAD-dependent catalyst of disulfide bond formation found in the inter membrane space of mitochondria, allows the efficient formation of native disulfide bonds in heterologously expressed proteins in the cytoplasm of E. coli even without the disruption of genes involved in disulfide bond reduction, for example trxB and/or gor. Indeed yields of active disulfide bonded proteins were higher in BL21 (DE3 pLysSRARE, an E. coli strain with the reducing pathways intact, than in the commercial Δgor ΔtrxB strain rosetta-gami upon co-expression of Erv1p. Conclusions Our results refute the current paradigm in the field that disruption of at least one of the reducing pathways is essential for the efficient production of disulfide bond containing proteins in the cytoplasm of E. coli and open up new possibilities for the use of E. coli as a microbial cell factory.

  6. Impact Resistance of Uncoated SiC/SiC Composites

    Science.gov (United States)

    Bhatt, Ramakrishna T.; Choi, Sung R.; Cosgriff, Laura M.; Fox, Dennis S.; Lee, Kang N.

    2008-01-01

    Two-dimensional woven SiC/SiC composites fabricated by melt infiltration method were impact tested at room temperature and at 1316 C in air using 1.59-mm diameter steel-ball projectiles at velocities ranging from 115 to 400 m/s. The extent of substrate damage with increasing projectile velocity was imaged and analyzed using optical and scanning electron microscopy, and non-destructive evaluation (NDE) methods such as pulsed thermography, and computed tomography. The impacted specimens were tensile tested at room temperature to determine their residual mechanical properties. Results indicate that at 115 m/s projectile velocity, the composite showed no noticeable surface or internal damage and retained its as-fabricated mechanical properties. As the projectile velocity increased above this value, the internal damage increased and mechanical properties degraded: At velocities >300 m/s, the projectile penetrated through the composite, but the composite retained approx.50% of the ultimate tensile strength of the as-fabricated composite and exhibited non-brittle failure. Predominant internal damages are delamination of fiber plies, fiber fracture and matrix shearing.

  7. Carbon-Heteroatom Bond Formation by an Ultrasonic Chemical Reaction for Energy Storage Systems.

    Science.gov (United States)

    Kim, Hyun-Tak; Shin, HyeonOh; Jeon, In-Yup; Yousaf, Masood; Baik, Jaeyoon; Cheong, Hae-Won; Park, Noejung; Baek, Jong-Beom; Kwon, Tae-Hyuk

    2017-12-01

    The direct formation of CN and CO bonds from inert gases is essential for chemical/biological processes and energy storage systems. However, its application to carbon nanomaterials for improved energy storage remains technologically challenging. A simple and very fast method to form CN and CO bonds in reduced graphene oxide (RGO) and carbon nanotubes (CNTs) by an ultrasonic chemical reaction is described. Electrodes of nitrogen- or oxygen-doped RGO (N-RGO or O-RGO, respectively) are fabricated via the fixation between N2 or O2 carrier gas molecules and ultrasonically activated RGO. The materials exhibit much higher capacitance after doping (133, 284, and 74 F g-1 for O-RGO, N-RGO, and RGO, respectively). Furthermore, the doped 2D RGO and 1D CNT materials are prepared by layer-by-layer deposition using ultrasonic spray to form 3D porous electrodes. These electrodes demonstrate very high specific capacitances (62.8 mF cm-2 and 621 F g-1 at 10 mV s-1 for N-RGO/N-CNT at 1:1, v/v), high cycling stability, and structural flexibility. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. 3C-SiC/ZnS heterostructured nanospheres with high photocatalytic activity and enhancement mechanism

    Directory of Open Access Journals (Sweden)

    J. Zhang

    2015-03-01

    Full Text Available 3C-SiC/n-type ZnS heterostructured nanospheres synthesized hydrothermally deliver enhanced photocatalytic performance under visible light excitation. The heterostructured catalysts consisting of 3C-SiC and ZnS nanocrystals with a mean size being less than 5 nm exhibit extended light absorption to the visible range. The proper band structure of the 3C-SiC and ZnS nanocrystals and intrinsic electric field induced by the heterojunction promote separation of photoexcited electrons and holes in the ZnS and 3C-SiC nanocrystals resulting in the increased photocatalytic efficiency. The associated mechanism is studied and proposed.

  9. Isotopic Studies of O-O Bond Formation During Water Oxidation (SISGR)

    Energy Technology Data Exchange (ETDEWEB)

    Roth, Justine P. [Johns Hopkins Univ., Baltimore, MD (United States)

    2015-03-03

    Isotopic Studies of O-O Bond Formation During Water Oxidation (SISGR) Research during the project period focused primarily on mechanisms of water oxidation by structurally defined transition metal complexes. Competitive oxygen isotope fractionation of water, mediated by oxidized precursors or reduced catalysts together with ceric, Ce(IV), ammonium nitrate in aqueous media, afforded oxygen-18 kinetic isotope effects (O-18 KIEs). Measurement, calculation, and interpretation of O-18 KIEs, described in the accompanying report has important ramifications for the production of electricity and solar hydrogen (as fuel). The catalysis division of BES has acknowledged that understanding mechanisms of transition metal catalyzed water oxidation has major ramifications, potentially leading to transformation of the global economy and natural environment in years to come. Yet, because of program restructuring and decreased availability of funds, it was recommended that the Solar Photochemistry sub-division of BES would be a more appropriate parent program for support of continued research.

  10. Enhanced TiC/SiC Ohmic contacts by ECR hydrogen plasma pretreatment and low-temperature post-annealing

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Bingbing [School of Electronic Science and Technology, Faculty of Electronic Information and Electrical Engineering, Dalian University of Technology, Dalian 116024 (China); Qin, Fuwen [State Key Laboratory of Material Modification by Laser, Ion and Electron Beam (Ministry of Education), Dalian University of Technology, Dalian 116024 (China); Wang, Dejun, E-mail: dwang121@dlut.edu.cn [School of Electronic Science and Technology, Faculty of Electronic Information and Electrical Engineering, Dalian University of Technology, Dalian 116024 (China)

    2015-11-15

    Highlights: • Low-temperature ECR microwave hydrogen plasma were pretreated for moderately doped (1 × 10{sup 18} cm{sup −3}) SiC surfaces. • The relationship among Ohmic properties, the SiC surface properties and TiC/SiC interface properties were established. • Interface band structures were analyzed to elucidate the mechanism by which the Ohmic contacts were formed. - Abstract: We proposed an electronic cyclotron resonance (ECR) microwave hydrogen plasma pretreatment (HPT) for moderately doped (1 × 10{sup 18} cm{sup −3}) SiC surfaces and formed ideal TiC/SiC Ohmic contacts with significantly low contact resistivity (1.5 × 10{sup −5} Ω cm{sup 2}) after low-temperature annealing (600 °C). This is achieved by reducing barrier height at TiC/SiC interface because of the release of pinned Fermi level by surface flattening and SiC surface states reduction after HPT, as well as the generation of donor-type carbon vacancies, which reduced the depletion-layer width for electron tunneling after annealing. Interface band structures were analyzed to elucidate the mechanism of Ohmic contact formations.

  11. Ablation behavior and mechanism of 3D Cf/ZrC-SiC composites in a plasma wind tunnel environment

    Directory of Open Access Journals (Sweden)

    Qinggang Li

    2015-12-01

    Full Text Available Three-dimensional needle-like Cf/ZrC-SiC composites were successfully fabricated by polymer infiltration and pyrolysis combined with ZrC precursor impregnation. The ablation properties of the composites were tested in a plasma wind tunnel environment at different temperatures and different times. The microstructure and morphology of the composites were examined after ablation by scanning electron microscopy, and their composition was confirmed by energy dispersive spectroscopy. The composites exhibited good configurational stability with a surface temperature of greater than 2273 K over a 300–1000 s period. The formation of ZrSiO4 and SiO2 melts on the surface of the 3D Cf/ZrC-SiC composites contributed significantly to improvement in their ablation properties. However, these composites exhibited serious ablation when the temperature was increased to 2800 K. The 3D Cf/ZrC-SiC composites obtained after ablation showed three different layers attributed to the temperature and pressure gradients: the ablation central region, the ablation transition region, and the unablation region.

  12. Bane of Hydrogen-Bond Formation on the Photoinduced Charge-Transfer Process in Donor–Acceptor Systems

    KAUST Repository

    Alsam, Amani Abdu

    2017-03-14

    Controlling the ultrafast dynamical process of photoinduced charge transfer at donor acceptor interfaces remains a major challenge for physical chemistry and solar cell communities. The process is complicated by the involvement of other complex dynamical processes, including hydrogen bond formation, energy transfer, and solvation dynamics occurring on similar time scales. In this study, we explore the remarkable impact of hydrogen-bond formation on the interfacial charge transfer between a negatively charged electron donating anionic porphyrin and a positively charged electron accepting pi-conjugated polymer, as a model system in solvents with different polarities and capabilities for hydiogen bonding using femtosecond transient absorption spectroscopy. Unlike the conventional understanding of the key role of hydrogen bonding in promoting the charge-transfer process, our steadystate and time-resolved results reveal that the intervening hydrogen-bonding environment and, consequently, the probable longer spacing between the donor and acceptor molecules significantly hinders the charge-transfer process between them. These results show that site-specific hydrogen bonding and geometric considerations between donor and acceptor can be exploited to control both the charge-transfer dynamics and its efficiency not only at donor acceptor interfaces but also in complex biological systems.

  13. Doping and stability of 3C-SiC: from thinfilm to bulk growth

    DEFF Research Database (Denmark)

    Jokubavicius, V.; Sun, J.; Linnarsson, M. K.

    Cubic silicon carbide (3C-SiC) could pave the way for development of advanced electronic and optoelectronic devices. It could be an excellent substrate for growth of nitride and epitaxial graphene layers. Boron doped 3C-SiC films could reach up to 60% efficiency and pave the way for a new solar c...

  14. Paleobotany and palynology of the Bristol Hill Coal Member (Bond Formation) and Friendsville Coal Member (Mattoon Formation) of the Illinois Basin (Upper Pennsylvania)

    Energy Technology Data Exchange (ETDEWEB)

    Willard, D.A.; Phillips, T.L. [US Geological Survey, Reston, VA (United States)

    1993-12-01

    Late Pennsylvanian coal swamps of the Illinois Basin were dominated by Psaronius tree ferns with a spatially heterogeneous distribution of medullosan pteridosperms (subdominant), calamites, sigillarian lycopsids, and cordaites. Miospore and coal-ball plant assemblages from the Missourian-age Bristol Hill Coal Member (Bond Formation) and Friendsville Coal Member (Mattoon Formation) of southeastern Illinois were quantified to analyze vegetational patterns in Late Pennsylvanian peat swamps and to compare vegetational composition of the coals.

  15. Hydroxyl radical formation by O-O bond homolysis in peroxynitrous acid.

    Science.gov (United States)

    Lymar, Sergei V; Khairutdinov, Rafail F; Hurst, James K

    2003-08-25

    Peroxynitrite decay in weakly alkaline media occurs by two concurrent sets of pathways which are distinguished by their reaction products. One set leads to net isomerization to NO(3)(-) and the other set to net decomposition to O(2) plus NO(2)(-). At sufficiently high peroxynitrite concentrations, the decay half-time becomes concentration-independent and approaches a limiting value predicted by a mechanism in which reaction is initiated by unimolecular homolysis of the peroxo O-O bond, i.e., the following reaction: ONOOH --> (*)OH + (*)NO(2). This dynamical behavior excludes alternative postulated mechanisms that ascribe decomposition to bond rearrangement within bimolecular adducts. Nitrate and nitrite product distributions measured at very low peroxynitrite concentrations also correspond to predictions of the homolysis model, contrary to a recent report from another laboratory. Additionally, (1) the rate constant for the reaction ONOO(-) --> (*)NO + (*)O(2)(-), which is critical to the kinetic model, has been confirmed, (2) the apparent volume of activation for ONOOH decay (DeltaV() = 9.7 +/- 1.4 cm(3)/mol) has been shown to be independent of the concentration of added nitrite and identical to most other reported values, and (3) complex patterns of inhibition of O(2) formation by radical scavengers, which are impossible to rationalize by alternative proposed reaction schemes, are shown to be quantitatively in accord with the homolysis model. These observations resolve major disputes over experimental data existing in the literature; despite extensive investigation of these reactions, no verifiable experimental evidence has been advanced that contradicts the homolysis model.

  16. Misfit dislocation locking and rotation during gallium nitride growth on SiC/Si substrates

    Science.gov (United States)

    Kukushkin, S. A.; Osipov, A. V.; Bessolov, V. N.; Konenkova, E. V.; Panteleev, V. N.

    2017-04-01

    The effect of changing the misfit dislocation propagation direction during GaN layer growth on the AlN/SiC/Si(111) structure surface is detected. The effect is as follows. As the GaN layer growing on AlN/SiC/Si(111) reaches a certain thickness of 300 nm, misfit dislocations initially along the layer growth axis stop and begin to move in the direction perpendicular to the growth axis. A theoretical model of AlN and GaN nucleation on the (111) SiC/Si face, explaining the effect of changing the misfit dislocation motion direction, is constructed. The effect of changing the nucleation mechanism from the island one for AlN on SiC/Si(111) to the layer one for the GaN layer on AlN/SiC/Si is experimentally detected and theoretically explained.

  17. Radicals and ions controlling by adjusting the antenna-substrate distance in a-Si:H deposition using a planar ICP for c-Si surface passivation

    Science.gov (United States)

    Zhou, H. P.; Xu, S.; Xu, M.; Xu, L. X.; Wei, D. Y.; Xiang, Y.; Xiao, S. Q.

    2017-02-01

    Being a key issue in the research and fabrication of silicon heterojunction (SHJ) solar cells, crystalline silicon (c-Si) surface passivation is theoretically and technologically intricate due to its complicate dependence on plasma characteristics, material properties, and plasma-material interactions. Here amorphous silicon (a-Si:H) grown by a planar inductively coupled plasma (ICP) reactor working under different antenna-substrate distances of d was used for the surface passivation of low-resistivity p-type c-Si. It is found that the microstructures (i.e., the crystallinity, Si-H bonding configuration etc.) and passivation function on c-Si of the deposited a-Si:H were profoundly influenced by the parameter of d, which primarily determines the types of growing precursors of SiHn/H contributing to the film growth and the interaction between the plasma and growing surface. c-Si surface passivation is analyzed in terms of the d-dependent a-Si:H properties and plasma characteristics. The controlling of radical types and ion bombardment on the growing surface through adjusting parameter d is emphasized.

  18. MICROWAVE-ASSISTED CHEMISTRY: SYNTHESIS OF AMINES AND HETEROCYCLES VIA CARBON-NITROGEN BOND FORMATION IN AQUEOUS MEDIA

    Science.gov (United States)

    Improved C-N bond formation under MW influence is demonstrated by a) solventless three-component coupling reaction to generate propargyl amines that uses only Cu (I); b) aqueous N-alkylation of amines by alkyl halides that proceeds expeditiously in the presence of NaOH to deliver...

  19. Intermolecular Formation of Two C−C Bonds across Olefins Enabled by Boron-Based Relay Strategies

    Czech Academy of Sciences Publication Activity Database

    Hidasová, Denisa; Jahn, Ullrich

    2017-01-01

    Roč. 56, č. 33 (2017), s. 9656-9658 ISSN 1433-7851 Institutional support: RVO:61388963 Keywords : 1,2-metalate rearrangement * C−C bond formation * radical reactions * transition metal catalysis * vinyl boronates Subject RIV: CC - Organic Chemistry Impact factor: 11.994, year: 2016

  20. Neutral copper-phosphido-borane complexes: synthesis, characterization, and use as precatalysts in C(sp)-P bond formation.

    Science.gov (United States)

    Abdellah, Ibrahim; Bernoud, Elise; Lohier, Jean-François; Alayrac, Carole; Toupet, Loïc; Lepetit, Christine; Gaumont, Annie-Claude

    2012-04-28

    Copper-phosphido-borane complexes were synthesized and isolated for the first time. Their structures were experimentally and computationally investigated. They were shown to display catalytic activity in C(sp)-P bond formation. This journal is © The Royal Society of Chemistry 2012

  1. Early biofilm formation and the effects of antimicrobial agents on orthodontic bonding materials in a parallel plate flow chamber

    NARCIS (Netherlands)

    Chin, Yeen; Busscher, HJ; Evans, R; Noar, J; Pratten, J

    Decalcification is a commonly recognized complication of orthodontic treatment with fixed appliances. A technology, based on a parallel plate flow chamber, was developed to investigate early biofilm formation of a strain of Streptococcus sanguis on the surface of four orthodontic bonding materials:

  2. Role of Hydrogen Bonding in the Formation of Adenine Chains on Cu(110 Surfaces

    Directory of Open Access Journals (Sweden)

    Lanxia Cheng

    2016-12-01

    Full Text Available Understanding the adsorption properties of DNA bases on metal surfaces is fundamental for the rational control of surface functionalization leading to the realisation of biocompatible devices for biosensing applications, such as monitoring of particular parameters within bio-organic environments and drug delivery. In this study, the effects of deposition rate and substrate temperature on the adsorption behavior of adenine on Cu(110 surfaces have been investigated using scanning tunneling microscopy (STM and density functional theory (DFT modeling, with a focus on the characterization of the morphology of the adsorbed layers. STM results revealed the formation of one-dimensional linear chains and ladder-like chains parallel to the [110] direction, when dosing at a low deposition rate at room temperature, followed by annealing to 490 K. Two mirror related, well-ordered chiral domains oriented at ±55° with respect to the [110] direction are formed upon deposition on a substrate kept at 490 K. The molecular structures observed via STM are rationalized and qualitatively described on the basis of the DFT modeling. The observation of a variety of ad-layer structures influenced by deposition rate and substrate temperature indicates that dynamic processes and hydrogen bonding play an important role in the self-assembly of adenine on the Cu(110 surface.

  3. Carenium—Calkyl Bond Making and Breaking: Key Process in the Platinum-Mediated Caryl—Calkyl Bond Formation. Analogies to Organic Electrophilic Aromatic Substitution

    OpenAIRE

    van Koten, G.; Albrecht, M.A.; Spek, A.L.

    2001-01-01

    The reaction of cationic platinum aqua complexes 2 [Pt(C6H2{CH2NMe2}2-E-4)(OH2)](X') (X' = SO3CF3, BF4) with alkyl halides RX gave various air-stable arenium complexes 3-5 containing a new C-C bond (R = Me, 3; Et, 4; Bn, 5). Electron-releasing oxo-substituents on the aromatic ligand (E = e.g., OH, b; OMe, c) enhance the reactivity of the aqua complex 2 and were essential for arenium formation from alkyl halides different from MeX. This process is initiated by oxidative addition of alkyl halid...

  4. Microstructure Evolution and Durability of Advanced Environmental Barrier Coating Systems for SiC/SiC Ceramic Matrix Composites

    Science.gov (United States)

    Zhu, Dongming; Evans, Laura J.; McCue, Terry R.; Harder, Bryan

    2016-01-01

    Environmental barrier coated SiC-SiC ceramic matrix composites (CMCs) systems will play a crucial role in next generation turbine engines for hot-section component applications because of their ability to significantly increase engine operating temperatures with improved efficiency, reduce engine weight and cooling requirements. Advanced HfO2 and rare earth silicate environmental barrier coatings (EBCs), along with multicomponent hafnium and rare earth silicide EBC bond coats have been developed. The coating degradation mechanisms in the laboratory simulated engine thermal cycling, and fatigue-creep operating environments are also being investigated. This paper will focus on the microstructural and compositional evolutions of an advanced environmental barrier coating system on a SiC-SiC CMC substrate during the high temperature simulated durability tests, by using a Field Emission Gun Scanning Electron Microscopy, Energy Dispersive Spectroscopy (EDS) and Wavelength Dispersive Spectroscopy (WDS). The effects of Calcium-Magnesium-Alumino-Silicate (CMAS) from road sand or volcano-ash deposits on the degradation mechanisms of the environmental barrier coating systems will also be discussed. The detailed analysis results help understand the EBC-CMC system performance, aiming at the durability improvements to achieve more robust, prime-reliant environmental barrier coatings.

  5. Biofilm formation on stainless steel and gold wires for bonded retainers in vitro and in vivo and their susceptibility to oral antimicrobials

    NARCIS (Netherlands)

    Jongsma, Marije A.; Pelser, Floris D. H.; van der Mei, Henny C.; Atema-Smit, Jelly; van de Belt-Gritter, Betsy; Busscher, Henk J.; Ren, Yijin

    OBJECTIVE: Bonded retainers are used in orthodontics to maintain treatment result. Retention wires are prone to biofilm formation and cause gingival recession, bleeding on probing and increased pocket depths near bonded retainers. In this study, we compare in vitro and in vivo biofilm formation on

  6. Quantum chemical studies of a model for peptide bond formation. 3. Role of magnesium cation in formation of amide and water from ammonia and glycine

    Science.gov (United States)

    Oie, T.; Loew, G. H.; Burt, S. K.; MacElroy, R. D.

    1984-01-01

    The SN2 reaction between glycine and ammonia molecules with magnesium cation Mg2+ as a catalyst has been studied as a model reaction for Mg(2+)-catalyzed peptide bond formation using the ab initio Hartree-Fock molecular orbital method. As in previous studies of the uncatalyzed and amine-catalyzed reactions between glycine and ammonia, two reaction mechanisms have been examined, i.e., a two-step and a concerted reaction. The stationary points of each reaction including intermediate and transition states have been identified and free energies calculated for all geometry-optimized reaction species to determine the thermodynamics and kinetics of each reaction. Substantial decreases in free energies of activation were found for both reaction mechanisms in the Mg(2+)-catalyzed amide bond formation compared with those in the uncatalyzed and amine-catalyzed amide bond formation. The catalytic effect of the Mg2+ cation is to stabilize both the transition states and intermediate, and it is attributed to the neutralization of the developing negative charge on the electrophile and formation of a conformationally flexible nonplanar five-membered chelate ring structure.

  7. In vivo biofilm formation on stainless steel bonded retainers during different oral health-care regimens

    NARCIS (Netherlands)

    Jongsma, Marije A.; van der Mei, Henny C.; Atema-Smit, Jelly; Busscher, Henk I.; Ren, Yijin

    Retention wires permanently bonded to the anterior teeth are used after orthodontic treatment to prevent the teeth from relapsing to pre-treatment positions. A disadvantage of bonded retainers is biofilm accumulation on the wires, which produces a higher incidence of gingival recession, increased

  8. Structural and Morphological Investigation of Pendeo-Epitaxy 3C-SiC on Si Substrates

    Science.gov (United States)

    Kim, Byeung C.; Capano, Michael A.

    2008-05-01

    Successful pendeo-epitaxy growth of cubic silicon carbide (3C-SiC) on off-axis Si(001) substrates was achieved. The structural and morphological characteristics of pendeo-epitaxy 3C-SiC were strongly affected by underlying stripes and seed layer thickness. Stripes perpendicular to the Si substrate off-axis provide about three times faster lateral growth rate compared with parallel oriented stripes. Root-mean-square (RMS) measurements using atomic force microscope (AFM) indicate that the surface morphology of Pendeo-epitaxy 3C-SiC films remarkably improves with increasing seed layer thickness: from 9.8 nm for 3 μm thickness to 0.5 nm for 10 μm thickness. These effects on pendeo-epitaxy 3C-SiC are discussed with scanning electron microscopy (SEM) and AFM investigation.

  9. A computational study on the mechanism of ynamide-mediated amide bond formation from carboxylic acids and amines.

    Science.gov (United States)

    Zhang, Song-Lin; Wan, Hai-Xing; Deng, Zhu-Qin

    2017-08-02

    This paper reports a computational study elucidating the reaction mechanism for ynamide-mediated amide bond formation from carboxylic acids and amines. The mechanisms have been studied in detail for ynamide hydrocarboxylation and the subsequent aminolysis of the resulting adduct by an amine. Ynamide hydrocarboxylation is kinetically favorable and thermodynamically irreversible, resulting in the formation of a key low-lying intermediate CP1 featuring geminal vinylic acyloxy and sulfonamide groups. The aminolysis of CP1 by the amine is proposed to be catalyzed by the carboxylic acid itself that imparts favourable bifunctional effects. In the proposed key transition state TSaminolysis-acid-iso2, the amine undergoes direct nucleophilic substitution at the acyl of CP1 to replace the enolate group in a concerted way, which is promoted by secondary hydrogen bonding of carboxylic acid with both the amine and CP1. These secondary interactions are suggested to increase the nucleophilicity of the amine and to activate the Cacyl-O bond to be cleaved, thereby stabilizing the aminolysis transition state. The concerted aminolysis mechanism is competitive with the classic stepwise nucleophilic acyl substitution mechanism that features sequential amine addition to acyl/intramolecular proton transfer/C-O bond cleavage and a key tetrahedral intermediate. Based on the mechanistic model, the carboxylic acid substrate effect and studies of more acidic CF3SO3H as the catalyst are in good agreement with the experimental observations, lending further support for the mechanistic model. The bifunctional catalytic effect of the carboxylic acid substrate may widely play a role in related amide bond-forming reactions and peptide formation chemistry.

  10. Decreasing the Viscosity in CO2 Capture by Amino-Functionalized Ionic Liquids through the Formation of Intramolecular Hydrogen Bond.

    Science.gov (United States)

    Luo, Xiao Y; Fan, Xi; Shi, Gui L; Li, Hao R; Wang, Cong M

    2016-03-17

    A strategy for decreasing the viscosity variation in the process of CO2 capture by amino-functionalized ionic liquids (ILs) through the formation of intramolecular hydrogen bond was reported. Different with the dramatic increase in viscosity during CO2 uptake by traditional amino-functionalized ILs, slight increase or even decrease in viscosity was achieved through introducing a N or O atom as hydrogen acceptor into amino-functionalized anion, which could stabilize the active hydrogen of produced carbamic acid. Quantum chemical calculations and spectroscopic investigations demonstrated that the formation of intramolecular hydrogen bond between introduced hydrogen acceptor and carbamic acid was the key to avoid the dramatic increase in viscosity during the capture of CO2 by these amino-functionalized ILs.

  11. Activation of dinitrogen-derived hafnium nitrides for nucleophilic N-C bond formation with a terminal isocyanate.

    Science.gov (United States)

    Semproni, Scott P; Chirik, Paul J

    2013-12-02

    Better by Hf: Anion coordination to a bridging hafnocene nitride complex, prepared from CO-induced N2 cleavage, increases the nucleophilicity of the nitrogen atom, thus promoting additional NC bond formation with a typically inert terminal isocyanate ligand. This cascade sequence allows synthesis of otherwise challenging mono-substituted ureas using N2 , CO, and an appropriate electrophile. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Chiral BINOL-derived phosphoric acids: privileged Brønsted acid organocatalysts for C-C bond formation reactions.

    Science.gov (United States)

    Zamfir, Alexandru; Schenker, Sebastian; Freund, Matthias; Tsogoeva, Svetlana B

    2010-12-07

    BINOL-derived phosphoric acids have emerged during the last five years as powerful chiral Brønsted acid catalysts in many enantioselective processes. The most successful transformations carried out with chiral BINOL phosphates include C-C bond formation reactions. The recent advances have been reviewed in this article with a focus being placed on hydrocyanations, aldol-type, Mannich, Friedel-Crafts, aza-ene-type, Diels-Alder, as well as cascade and multi-component reactions.

  13. Effects of Preform Density on Structure and Property of C/C-SiC Composites Fabricated by Gaseous Silicon Infiltration

    Directory of Open Access Journals (Sweden)

    CAO Yu

    2016-07-01

    Full Text Available The 3-D needled C/C preforms with different densities deposited by chemical vapor infiltration (CVI method were used to fabricate C/C-SiC composites by gaseous silicon infiltration (GSI. The porosity and CVI C thickness of the preforms were studied, and the effects of preform density on the mechanical and thermal properties of C/C-SiC composites were analyzed. The results show that with the increase of preform density, the preform porosity decreases and the CVI C thickness increases from several hundred nanometers to several microns. For the C/C-SiC composites, as the preform density increases, the residual C content increases while the density and residual Si content decreases. The SiC content first keeps at a high level of about 40% (volume fraction, which then quickly reduces. Meanwhile, the mechanical properties increase to the highest values when the preform density is 1.085g/cm3, with the flexure strength up to 308.31MP and fracture toughness up to 11.36MPa·m1/2, which then decrease as the preform density further increases. The thermal conductivity and CTE of the composites, however, decrease with the increase of preform density. It is found that when the preform porosity is too high, sufficient infiltration channels lead to more residual Si, and thinner CVI C thickness results in the severe corrosion of the reinforcing fibers by Si and lower mechanical properties. When the preform porosity is relatively low, the contents of Si and SiC quickly reduce since the infiltration channels are rapidly blocked, resulting in the formation of large closed pores and not high mechanical properties.

  14. Exploring the Role of Substitution on the Formation of Se···O/N Noncovalent Bonds.

    Science.gov (United States)

    Shukla, Rahul; Chopra, Deepak

    2015-11-25

    In this article, we have examined the effect of substitution on the formation of neutral XHSe···O/N (X = -H, -F, -CH3, -CF3, -Cl, -OH, -OCH3, -NH2, -NHCH3, -CN) noncovalent bonds with the oxygen atom from H2O molecule and the nitrogen atom from NH3 being the electron donor atoms, respectively. In addition to this, analysis has also been performed on XMeSe···O/N complexes to study the effect of the role of hydrogen bonding with the hydrogen atoms of the methyl group on Se···O/N interactions. Binding energy calculations were performed to determine the strength of these contacts. The obtained results establish the fact that the presence of a methyl group influences the strength of the observed Se···O/N interactions. Also in some cases, the O-H···Se interaction was observed to be more preferable over the Se···O interaction. The major contribution for stabilization of such Se···O/N interactions is from an interplay among the electrostatics and the exchange energy. To obtain deeper insights and understanding of such Se···O/N contacts, a topological analysis, using the QTAIM approach were also performed. This analysis showed that although the presence of a Me group modifies the Se···O/N interaction, it does not necessitate the formation of hydrogen bonds. To obtain insights into the orbital contributions, a natural bond orbital (NBO) analysis were performed which depicts that the strength of such interactions were derived via charge transfer from the oxygen/nitrogen lone pair to the σ* orbital of the Se-X bond.

  15. Progress on Fabrication of Planar Diffusion Couples with Representative TRISO PyC/SiC Microstructure

    Energy Technology Data Exchange (ETDEWEB)

    Hunn, John D. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Jolly, Brian C. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Gerczak, Tyler J. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Campbell, Anne A. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Schumacher, Austin T. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

    2017-10-01

    Release of fission products from tristructural-isotropic (TRISO) coated particle fuel limits the fuel’s operational lifetime and creates potential safety and maintenance concerns. A need for diffusion analysis in representative TRISO layers exists to provide fuel performance models with high fidelity data to improve fuel performance and efficiency. An effort has been initiated to better understand fission product transport in, and release from, quality TRISO fuel by investigating diffusion couples with representative pyrocarbon (PyC) and silicon carbide (SiC). Here planar PyC/SiC diffusion couples are being developed with representative PyC/SiC layers using a fluidized bed chemical vapor deposition (FBCVD) system identical to those used to produce laboratory-scale TRISO fuel for the Advanced Gas Reactor Fuel Qualification and Development Program’s (AGR) first fuel irradiation. The diffusivity of silver, the silver and palladium system, europium, and strontium in the PyC/SiC will be studied at elevated temperatures and under high temperature neutron irradiation. The study also includes a comparative study of PyC/SiC diffusion couples with varying TRISO layer properties to understand the influence of SiC microstructure (grain size) and the PyC/SiC interface on fission product transport. The first step in accomplishing these goals is the development of the planar diffusion couples. The diffusion couple construction consists of multiple steps which includes fabrication of the primary PyC/SiC structures with targeted layer properties, introduction of fission product species and seal coating to create an isolated system. Coating development has shown planar PyC/SiC diffusion couples with similar properties to AGR TRISO fuel can be produced. A summary of the coating development process, characterization methods, and status are presented.

  16. CVD growth of (001) and (111)3C-SiC epilayers and their interface reactivity with pradeodymium oxide dielectric layers

    Energy Technology Data Exchange (ETDEWEB)

    Sohal, R.

    2006-07-24

    In this work, growth and characterisation of 3C-SiC thin films, investigation of oxidation of thus prepared layers and Pr-silicate and AlON based interface with SiC have been studied. Chemical vapor deposition of 3C-SiC thin films on Si(001) and Si(111) substrates has been investigated. Prior to the actual SiC growth, preparation of initial buffer layers of SiC was done. Using such a buffer layer, epitaxial growth of 3C-SiC has been achieved on Si(111) and Si(001) substrates. The temperature of 1100 C and 1150 C has been determined to be the optimal temperature for 3C-SiC growth on Si (111) and Si(001) substrates respectively. The oxidation studies on SiC revealed that a slow oxidation process at moderate temperatures in steps was useful in reducing and suppressing the g-C at the SiO{sub 2}/SiC interface. Clean, graphite-free SiO{sub 2} has been successfully grown on 3C-SiC by silicon evaporation and UHV anneal. For the application of high-k Pr{sub 2}O{sub 3} on silicon carbide, plausible interlayer, Pr-Silicate and AlON, have been investigated. Praseodymium silicate has been prepared successfully completely consuming the SiO2 and simultaneously suppressing the graphitic carbon formation. A comparatively more stable interlayer using AlON has been achieved. This interlayer mainly consists of stable phases of AlN along with some amount of Pr-aluminates and CN. Such layers act as a reaction barrier between Pr{sub 2}O{sub 3} and SiC, and simultaneously provide higher band offsets. (orig.)

  17. Shear-bond strength between a new format of intra-buccal acrylic bioadhesive drug delivery system and adhesive systems.

    Science.gov (United States)

    Pedrazzi, V; Del Ciampo, J O; Panzeri, H; Lara, E Helena Guimarães; Issa, J P Mardegan; Do Nascimento, C

    2009-04-01

    An intra-buccal acrylic bioadhesive device designated for drug programmed release that can stay adhered to dental enamel, and also on removable prosthetic restorations, with preventive and/or therapeutic purpose for a large clinical applications based on polymethyl methacrylate/methyl methacrylate/2 hydroxyethyl methacrylate (PMMA/MMA/HEMA) was developed, using the sodium fluoride as an active principle. This bioadhesive was evaluated for its shear bond strength when bonded with different adhesive systems. Two substrates (recently extracted human teeth and acrylic prosthesis basis) were used to obtain the 96 test-specimens. Four adhesive systems (Cyanoacrylate ester, 3M Concise Enamel Bond Resin with or without previous enamel etching, MMA/HEMA or PMMA/MMA/ HEMA) were chosen for the fixation of the bioadhesives to substrate. Artificial saliva or distilled water was used as medium for maintaining the specimens until test. Statistical analysis showed that the interaction bioadhesives/acrylic prosthesis basis/cyanoacrylate ester adhesive was the most resistant to the physical removal by shearing. The newly rounded semi-convex format of acrylic device developed in this study presented satisfactory shear bond strength and might contribute to the comfort of intra-buccal use.

  18. The effects of orthodontic bonding steps on biofilm formation of Streptococcus mutans in the presence of saliva.

    Science.gov (United States)

    Ahn, Sug-Joon; Cho, Eun-Jung; Oh, Sung-Suk; Lim, Bum-Soon

    2012-12-01

    To investigate the effects of various orthodontic bonding steps on biofilm formation of Streptococcus mutans in the presence of saliva. Hydroxyapatite (HA) and orthodontic adhesive (AD) disks were prepared to a uniform size. HA disks were etched with 37% phosphoric acid gel in the etched group (HE). In the primed group (HP), Transbond XT primer was applied to the etched HA surface and light-cured. For biofilm formation, Streptococcus mutans was grown on each specimen in a biofilm medium with either glucose or sucrose in the presence of fluid-phase UWS (F-UWS) or surface adsorbed saliva (S-UWS). The adherent bacteria were quantified by enumeration of the total viable counts of bacteria. Biofilms formed on each surface were examined by scanning electron microscopy. When glucose was used, both F-UWS and S-UWS suppressed biofilm formation of S. mutans. Compared to HA and HE, biofilm formation was significantly inhibited on HP and AD in the presence of glucose. Biofilm-forming patterns that were inhibited by saliva were restored in a sucrose-containing medium. F-UWS promoted biofilm formation on HA and HE, while S-UWS significantly promoted biofilm formation on HP. S. mutans developed biofilm better on HA and HE than on AD when sucrose was used as the sole carbohydrate source. This study suggests that the biofilm development by S. mutans is significantly influenced by the orthodontic bonding procedure. Biofilm formation of S. mutans was inhibited on AD more than other surfaces, irrespective of the presence of saliva or a carbohydrate source.

  19. Theoretical prediction of new C-Si alloys in {\\boldsymbol{C}}2/{\\boldsymbol{m}}-20 structure

    Science.gov (United States)

    Xu, Xiangyang; Chai, Changchun; Fan, Qingyang; Yang, Yintang

    2017-04-01

    We study structural, mechanical, and electronic properties of C20, Si20 and their alloys (C16Si4, C12Si8, C8Si12, and C4 {{Si}}16) in C2/m structure by using density functional theory (DFT) based on first-principles calculations. The obtained elastic constants and the phonon spectra reveal mechanical and dynamic stability. The calculated formation enthalpy shows that the C-Si alloys might exist at a specified high temperature scale. The ratio of B/G and Poisson’s ratio indicate that these C-Si alloys in C2/m-20 structure are all brittle. The elastic anisotropic properties derived by bulk modulus and shear modulus show slight anisotropy. In addition, the band structures and density of states are also depicted, which reveal that C20, C16Si4, and Si20 are indirect band gap semiconductors, while C8Si12 and C4Si16 are semi-metallic alloys. Notably, a direct band gap semiconductor (C12Si8) is obtained by doping two indirect band gap semiconductors (C20 and Si20). Project supported by the National Natural Science Foundation of China (Grant No. 61474089) and the Open Fund of Key Laboratory of Complex Electromagnetic Environment Science and Technology, China Academy of Engineering Physics (Grant No. 2015-0214.XY.K).

  20. Electrical Resistance of SiC/SiC Ceramic Matrix Composites for Damage Detection and Life-Prediction

    Science.gov (United States)

    Smith, Craig; Morscher, Gregory; Xia, Zhenhai

    2009-01-01

    Ceramic matrix composites (CMC) are suitable for high temperature structural applications such as turbine airfoils and hypersonic thermal protection systems due to their low density high thermal conductivity. The employment of these materials in such applications is limited by the ability to accurately monitor and predict damage evolution. Current nondestructive methods such as ultrasound, x-ray, and thermal imaging are limited in their ability to quantify small scale, transverse, in-plane, matrix cracks developed over long-time creep and fatigue conditions. CMC is a multifunctional material in which the damage is coupled with the material s electrical resistance, providing the possibility of real-time information about the damage state through monitoring of resistance. Here, resistance measurement of SiC/SiC composites under mechanical load at both room temperature monotonic and high temperature creep conditions, coupled with a modal acoustic emission technique, can relate the effects of temperature, strain, matrix cracks, fiber breaks, and oxidation to the change in electrical resistance. A multiscale model can in turn be developed for life prediction of in-service composites, based on electrical resistance methods. Results of tensile mechanical testing of SiC/SiC composites at room and high temperatures will be discussed. Data relating electrical resistivity to composite constituent content, fiber architecture, temperature, matrix crack formation, and oxidation will be explained, along with progress in modeling such properties.

  1. Growth and characterization of few unit-cell NbN superconducting films on 3C-SiC/Si substrate

    Science.gov (United States)

    Chang, H. W.; Wang, C. L.; Huang, Y. R.; Chen, T. J.; Wang, M. J.

    2017-11-01

    Superconducting δ-NbN ultrathin film has become a key element in extremely sensitive detector applications in recent decades because of its excellent electronic properties. We have realized the epitaxial growth of ultrathin δ-NbN films on (100)-oriented 3C-SiC/Si substrates by dc reactive magnetron sputtering at 760 °C with a deposition rate of 0.054 nm s-1. High-resolution transmission electron microscope images confirm the excellent epitaxy of these films. Even with a thickness of 1.3 nm (˜3 unit cells), the δ-NbN film shows a superconducting transition above 8 K. Furthermore, our ultrathin δ-NbN films demonstrate a long Ginzburg-Landau superconducting coherent length ({ξ }{{G}{{L}}}(0)> 5 {{nm}}) with a critical current density of about 2.2 MA cm-2, and good stability in an ambient environment.

  2. Reusable ionic liquid-catalyzed oxidative coupling of azoles and benzylic compounds via sp(3) C-N bond formation under metal-free conditions.

    Science.gov (United States)

    Liu, Wenbo; Liu, Chenjiang; Zhang, Yonghong; Sun, Yadong; Abdukadera, Ablimit; Wang, Bin; Li, He; Ma, Xuecheng; Zhang, Zengpeng

    2015-07-14

    The heterocyclic ionic liquid-catalyzed direct oxidative amination of benzylic sp(3) C-H bonds via intermolecular sp(3) C-N bond formation for the synthesis of N-alkylated azoles under metal-free conditions is reported for the first time. The catalyst 1-butylpyridinium iodide can be recycled and reused with similar efficacies for at least eight cycles.

  3. Advances in SiC/SiC Composites for Aero-Propulsion

    Science.gov (United States)

    DiCarlo, James A.

    2013-01-01

    In the last decade, considerable progress has been made in the development and application of ceramic matrix composites consisting of silicon carbide (SiC) based matrices reinforced by small-diameter continuous-length SiC-based fibers. For example, these SiC/SiC composites are now in the early stages of implementation into hot-section components of civil aero-propulsion gas turbine engines, where in comparison to current metallic components they offer multiple advantages due to their lighter weight and higher temperature structural capability. For current production-ready SiC/SiC, this temperature capability for long time structural applications is 1250 degC, which is better than 1100 degC for the best metallic superalloys. Foreseeing that even higher structural reliability and temperature capability would continue to increase the advantages of SiC/SiC composites, progress in recent years has also been made at NASA toward improving the properties of SiC/SiC composites by optimizing the various constituent materials and geometries within composite microstructures. The primary objective of this chapter is to detail this latter progress, both fundamentally and practically, with particular emphasis on recent advancements in the materials and processes for the fiber, fiber coating, fiber architecture, and matrix, and in the design methods for incorporating these constituents into SiC/SiC microstructures with improved thermo-structural performance.

  4. Tribological Property of C/C-SiC Composites Fabricated by Isothermal Chemical Vapor Infiltration

    Directory of Open Access Journals (Sweden)

    WANG Yueming

    2017-08-01

    Full Text Available Four kinds of C/C-SiC composites were fabricated by isothermal chemical vapor infiltration (ICVI, and the 2.5D needle-punching carbon felt was taken as the preform. The volume fraction of carbon fiber in felt is 30%. The density of C/C-SiC composites is similar (1.87-1.91 g/cm3, while the weight ratio of SiC is decreased from 56% to 15%. The microstructure and phase composition of C/C-SiC composites were observed by SEM and XRD respectively. Friction and wear behavior of the C/C-SiC composites were investigated with the MM-1000 friction machine. The results show that the average macro hardness of matrix is decreased from 98.2HRA to 65.1HRA with the decrease of SiC content from 56% to 15%, and uniformity of hardness distribution is significantly decreased. Finally, by the analysis of microtopography of friction surface and wear debris, it is found that the superficial hardness has an obvious influence on mechanism of wear during braking process. The wear mechanism of the C/C-SiC composites transforms from grain wear to the combination of grain wear and adherent wear with the decrease of surface hardness. At the same time, the average friction coefficient and mass wear rate is increased obviously during breaking process.

  5. The mechanism of hydrocarbon oxygenate reforming: C-C bond scission, carbon formation, and noble-metal-free oxide catalysts.

    Science.gov (United States)

    Lykhach, Yaroslava; Neitzel, Armin; Ševčíková, Klára; Johánek, Viktor; Tsud, Nataliya; Skála, Tomáš; Prince, Kevin C; Matolín, Vladimír; Libuda, Jörg

    2014-01-01

    Towards a molecular understanding of the mechanism behind catalytic reforming of bioderived hydrocarbon oxygenates, we explore the C-C bond scission of C2 model compounds (acetic acid, ethanol, ethylene glycol) on ceria model catalysts of different complexity, with and without platinum. Synchrotron photoelectron spectroscopy reveals that the reaction pathway depends very specifically on both the reactant molecule and the catalyst surface. Whereas C-C bond scission on Pt sites and on oxygen vacancies involves intermittent surface carbon species, the reaction occurs without any carbon formation and deposition for ethylene glycol on CeO2(111). Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Assessment of covalent bond formation between coupling agents and wood by FTIR spectroscopy and pull strength tests

    DEFF Research Database (Denmark)

    Rasmussen, Jonas Stensgaard; Barsberg, Søren Talbro; Venås, Thomas Mark

    2014-01-01

    of ether linkages between lignin and titanium coupling agent. In the present work, changes were found in the attenuated total reflectance-Fourier transform IR (ATR-FTIR) spectra of lignin and wood mixed with silane, and titanium coupling agents, and to a lesser extent for a zirconium coupling agent....... This was seen as evidence for covalent bonds between lignin phenolics and the coupling agents. No spectral changes were observed when the coupling agents were mixed with the wood constituents cellulose and hemicellulose. For verification of the results, a modified EN 311 wet adhesion pull strength test......In the focus was the question whether metal alkoxide coupling agents – titanium, silane, and zirconium – form covalent bonds to wood and how they improve coating adhesion. In a previous work, a downshift of the lignin infrared (IR) band ∼1600 cm-1 was shown to be consistent with the formation...

  7. Hexagonal wheel formation through the hydrogen-bonded assembly of cobalt Pacman complexes.

    Science.gov (United States)

    Leeland, James W; White, Fraser J; Love, Jason B

    2011-04-14

    A cobalt aquo-hydroxo complex of a ditopic Schiff-base pyrrole-crown ether macrocycle has been prepared and forms a rigid Pacman-clefted structure that assembles through hydrogen-bonding into a hexagonal wheel motif in the solid state.

  8. Nucleophilicity and P-C bond formation reactions of a terminal phosphanido iridium complex

    NARCIS (Netherlands)

    Serrano, Á.L.; Casado, M.A.; Ciriano, M.A.; de Bruin, B.; López, J.A.; Tejel, C.

    2016-01-01

    The diiridium complex [{Ir(ABPN(2))(CO)}(2)(μ-CO)] (1; [ABPN(2)]- = [(allyl)B(Pz)(2)(CH(2)PPh(2))]-) reacts with diphenylphosphane affording [Ir(ABPN(2))(CO)(H) (PPh(2))] (2), the product of the oxidative addition of the P-H bond to the metal. DFT studies revealed a large contribution of the

  9. Effects of the c-Si/a-SiO2 interfacial atomic structure on its band alignment: an ab initio study.

    Science.gov (United States)

    Zheng, Fan; Pham, Hieu H; Wang, Lin-Wang

    2017-12-13

    The crystalline-Si/amorphous-SiO2 (c-Si/a-SiO2) interface is an important system used in many applications, ranging from transistors to solar cells. The transition region of the c-Si/a-SiO2 interface plays a critical role in determining the band alignment between the two regions. However, the question of how this interface band offset is affected by the transition region thickness and its local atomic arrangement is yet to be fully investigated. Here, by controlling the parameters of the classical Monte Carlo bond switching algorithm, we have generated the atomic structures of the interfaces with various thicknesses, as well as containing Si at different oxidation states. A hybrid functional method, as shown by our calculations to reproduce the GW and experimental results for bulk Si and SiO2, was used to calculate the electronic structure of the heterojunction. This allowed us to study the correlation between the interface band characterization and its atomic structures. We found that although the systems with different thicknesses showed quite different atomic structures near the transition region, the calculated band offset tended to be the same, unaffected by the details of the interfacial structure. Our band offset calculation agrees well with the experimental measurements. This robustness of the interfacial electronic structure to its interfacial atomic details could be another reason for the success of the c-Si/a-SiO2 interface in Si-based electronic applications. Nevertheless, when a reactive force field is used to generate the a-SiO2 and c-Si/a-SiO2 interfaces, the band offset significantly deviates from the experimental values by about 1 eV.

  10. High-temperature protective coatings for C/SiC composites

    Directory of Open Access Journals (Sweden)

    Xiang Yang

    2014-12-01

    Full Text Available Carbon fiber-reinforced silicon carbide (C/SiC composites were well-established light weight materials combining high specific strength and damage tolerance. For high-temperature applications, protective coatings had to provide oxidation and corrosion resistance. The literature data introduced various technologies and materials, which were suitable for the application of coatings. Coating procedures and conditions, materials design limitations related to the reactivity of the components of C/SiC composites, new approaches and coating systems to the selection of protective coatings materials were examined. The focus of future work was on optimization by further multilayer coating systems and the anti-oxidation ability of C/SiC composites at temperatures up to 2073 K or higher in water vapor.

  11. Impact of organic overlayers on a-Si:H/c-Si surface potential

    KAUST Repository

    Seif, Johannes P.

    2017-04-11

    Bilayers of intrinsic and doped hydrogenated amorphous silicon, deposited on crystalline silicon (c-Si) surfaces, simultaneously provide contact passivation and carrier collection in silicon heterojunction solar cells. Recently, we have shown that the presence of overlaying transparent conductive oxides can significantly affect the c-Si surface potential induced by these amorphous silicon stacks. Specifically, deposition on the hole-collecting bilayers can result in an undesired weakening of contact passivation, thereby lowering the achievable fill factor in a finished device. We test here a variety of organic semiconductors of different doping levels, overlaying hydrogenated amorphous silicon layers and silicon-based hole collectors, to mitigate this effect. We find that these materials enhance the c-Si surface potential, leading to increased implied fill factors. This opens opportunities for improved device performance.

  12. Identification of nasopharyngeal carcinoma from photoluminescence spectra of 3C-SiC nanocrystals

    Science.gov (United States)

    Wang, Li-Fen; Guo, Jun-Hong; Huang, Zhi-Chun; Gu, Jian-Sen; Feng, Li-Ren; Liu, Li-Zhe

    2017-09-01

    The identification of intracellular pH (pHi) during carcinogenesis progression plays a crucial role in the studies of biochemistry, cytology, and clinical medicine. In this work, 3C-SiC nanocrystals (NCs), which can effectively monitor the pH environment by using the linear relation between photoluminescence intensity and surface OH- and H+ concentration, are adapted as fluorescent probes for monitoring carcinogenesis progression of nasopharyngeal carcinoma. Our results demonstrated that 3C-SiC NCs are compatible with living cells and have low cytotoxicity. The pHi measurements in different carcinogenesis environments indicate the validity and sensitivity of this technology in identifying nasopharyngeal carcinoma in application.

  13. Specimen size effect considerations for irradiation studies of SiC/SiC

    Energy Technology Data Exchange (ETDEWEB)

    Youngblood, G.E.; Henager, C.H. Jr.; Jones, R.H. [Pacific Northwest National Lab., Richland, WA (United States)

    1996-10-01

    For characterization of the irradiation performance of SiC/SiC, limited available irradiation volume generally dictates that tests be conducted on a small number of relatively small specimens. Flexure testing of two groups of bars with different sizes cut from the same SiC/SiC plate suggested the following lower limits for flexure specimen number and size: Six samples at a minimum for each condition and a minimum bar size of 30 x 6.0 x 2.0 mm{sup 3}.

  14. Electrical Conductivity of SiC/Si Composites Obtained from Wood Preforms

    Science.gov (United States)

    Béjar, Marco Antonio; Mena, Rodrigo; Toro, Juan Esteban

    2011-02-01

    Biomorphic SiC/Si composites were produced from pine and beech wood, and the corresponding electrical conductivity was determined as a function of the temperature. Firstly, wood preforms were pyrolized at 1050 °C in nitrogen. Then, the pyrolized preforms were impregnated with liquid silicon and kept at 1600 °C for 2 h in vacuum. The SiC/Si composites were obtained due to the produced carbothermal reaction. As expected, the resulting electrical conductivity of these composites increased with the temperature and with the silicon content.

  15. Evaluation of CVI SiC/SiC Composites for High Temperature Applications

    Science.gov (United States)

    Kiser, D.; Almansour, A.; Smith, C.; Gorican, D.; Phillips, R.; Bhatt, R.; McCue, T.

    2017-01-01

    Silicon carbide fiber reinforced silicon carbide (SiC/SiC) composites are candidate materials for various high temperature turbine engine applications because of their high specific strength and good creep resistance at temperatures of 1400 C (2552 F) and higher. Chemical vapor infiltration (CVI) SiC/SiC ceramic matrix composites (CMC) incorporating Sylramic-iBN SiC fiber were evaluated via fast fracture tensile tests (acoustic emission damage characterization to assess cracking behavior), tensile creep testing, and microscopy. The results of this testing and observed material behavior degradation mechanisms are reviewed.

  16. Total synthesis of feglymycin based on a linear/convergent hybrid approach using micro-flow amide bond formation

    Science.gov (United States)

    Fuse, Shinichiro; Mifune, Yuto; Nakamura, Hiroyuki; Tanaka, Hiroshi

    2016-11-01

    Feglymycin is a naturally occurring, anti-HIV and antimicrobial 13-mer peptide that includes highly racemizable 3,5-dihydroxyphenylglycines (Dpgs). Here we describe the total synthesis of feglymycin based on a linear/convergent hybrid approach. Our originally developed micro-flow amide bond formation enabled highly racemizable peptide chain elongation based on a linear approach that was previously considered impossible. Our developed approach will enable the practical preparation of biologically active oligopeptides that contain highly racemizable amino acids, which are attractive drug candidates.

  17. 2-nitroveratryl as a photocleavable thiol-protecting group for directed disulfide bond formation in the chemical synthesis of insulin.

    Science.gov (United States)

    Karas, John A; Scanlon, Denis B; Forbes, Briony E; Vetter, Irina; Lewis, Richard J; Gardiner, James; Separovic, Frances; Wade, John D; Hossain, Mohammed A

    2014-07-28

    Chemical synthesis of peptides can allow the option of sequential formation of multiple cysteines through exploitation of judiciously chosen regioselective thiol-protecting groups. We report the use of 2-nitroveratryl (oNv) as a new orthogonal group that can be cleaved by photolysis under ambient conditions. In combination with complementary S-pyridinesulfenyl activation, disulfide bonds are formed rapidly in situ. The preparation of Fmoc-Cys(oNv)-OH is described together with its use for the solid-phase synthesis of complex cystine-rich peptides, such as insulin. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Formation and Reactivity of a Molecular Magnesium Hydride with a Terminal Mg-H Bond.

    Science.gov (United States)

    Schnitzler, Silvia; Spaniol, Thomas P; Maron, Laurent; Okuda, Jun

    2015-08-03

    A complex featuring a terminal magnesium hydride bond supported by an NNNN macrocyclic ligand, [Mg{Me3 TACD⋅Al(iBu)3}H] (3), was formed from its labile Al(iBu)3 adduct. Use of Al(iBu)3 to block the amido nitrogen of the NNNN macrocyclic ligand was essential to prevent aggregation. The structurally characterized compound 3 reacted with BH3 to give the BH4 derivative, whereas Me3 SiCCH and PhSiH3 led to the corresponding acetylide and silyl derivative under H2 elimination. Pyridine is inserted into the MgH bond to give selectively the 1,4-dihydropyridinate. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Mechanistic insight into benzenethiol catalyzed amide bond formations from thioesters and primary amines

    DEFF Research Database (Denmark)

    Stuhr-Hansen, Nicolai; Bork, Nicolai; Strømgaard, Kristian

    2014-01-01

    The influence of arylthiols on cysteine-free ligation, i.e. the reaction between an alkyl thioester and a primary amine forming an amide bond, was studied in a polar aprotic solvent. We reacted the ethylthioester of hippuric acid with cyclohexylamine in the absence or presence of various quantities...... of thiophenol (PhSH) in a slurry of disodium hydrogen phosphate in dry DMF. Quantitative conversions into the resulting amide were observed within a few hours in the presence of equimolar amounts of thiophenol. Ab initio calculations showed that the reaction mechanism in DMF is similar to the well-known aqueous...... reaction mechanism. The energy barrier of the catalyzed amidation reaction is approximately 40 kJ mol(-1) lower than the non-catalyzed amidation reaction. At least partially this can be explained by a hydrogen bond from the amine to the π-electrons of the thiophenol, stabilizing the transition state...

  20. A quantum-chemical validation about the formation of hydrogen bonds and secondary interactions in intermolecular heterocyclic systems

    Directory of Open Access Journals (Sweden)

    Boaz Galdino Oliveira

    2009-08-01

    Full Text Available We have performed a detailed theoretical study in order to understand the charge density topology of the C2H4O···C2H2 and C2H4S···C2H2 heterocyclic hydrogen-bonded complexes. Through the calculations derived from Quantum Theory of Atoms in Molecules (QTAIM, it was observed the formation of hydrogen bonds and secondary interactions. Such analysis was performed through the determination of optimized geometries at B3LYP/6-31G(d,p level of theory, by which is that QTAIM topological operators were computed, such as the electronic density ρ(r, Laplacian Ñ2ρ(r, and ellipticity ε. The examination of the hydrogen bonds has been performed through the measurement of ρ(r, Ñ2ρ(r and ε between (O···H—C and (S···H—C, whereas the secondary interaction between axial hydrogen atoms Hα and carbon of acetylene. In this insight, it was verified the existence of secondary interaction only in C2H4S···C2H2 complex because its structure is propitious to form multiple interactions.

  1. Pair bond formation leads to a sustained increase in global cerebral glucose metabolism in monogamous male titi monkeys (Callicebus cupreus).

    Science.gov (United States)

    Maninger, Nicole; Hinde, Katie; Mendoza, Sally P; Mason, William A; Larke, Rebecca H; Ragen, Benjamin J; Jarcho, Michael R; Cherry, Simon R; Rowland, Douglas J; Ferrer, Emilio; Bales, Karen L

    2017-04-21

    Social bonds, especially attachment relationships, are crucial to our health and happiness. However, what we know about the neural substrates of these bonds is almost exclusively limited to rodent models and correlational experiments in humans. Here, we used socially monogamous non-human primates, titi monkeys (Callicebus cupreus) to experimentally examine changes in regional and global cerebral glucose metabolism (GCGM) during the formation and maintenance of pair bonds. Baseline positron emission tomography (PET) scans were taken of thirteen unpaired male titi monkeys. Seven males were then experimentally paired with females, scanned and compared, after one week, to six age-matched control males. Five of the six control males were then also paired and scanned after one week. Scans were repeated on all males after four months of pairing. PET scans were coregistered with structural magnetic resonance imaging (MRI), and region of interest (ROI) analysis was carried out. A primary finding was that paired males showed a significant increase in [18F]-fluorodeoxyglucose (FDG) uptake in whole brain following one week of pairing, which is maintained out to four months. Dopaminergic, "motivational" areas and those involved in social behavior showed the greatest change in glucose uptake. In contrast, control areas changed only marginally more than GCGM. These findings confirm the large effects of social bonds on GCGM. They also suggest that more studies should examine how social manipulations affect whole-brain FDG uptake, as opposed to assuming that it does not change across condition. Copyright © 2017 IBRO. Published by Elsevier Ltd. All rights reserved.

  2. Emotional experiences of preservice science teachers in online learning: the formation, disruption and maintenance of social bonds

    Science.gov (United States)

    Bellocchi, Alberto; Mills, Kathy A.; Ritchie, Stephen M.

    2016-09-01

    The enactment of learning to become a science teacher in online mode is an emotionally charged experience. We attend to the formation, maintenance and disruption of social bonds experienced by online preservice science teachers as they shared their emotional online learning experiences through blogs, or e-motion diaries, in reaction to videos of face-to-face lessons. A multi-theoretic framework drawing on microsociological perspectives of emotion informed our hermeneutic interpretations of students' first-person accounts reported through an e-motion diary. These accounts were analyzed through our own database of emotion labels constructed from the synthesis of existing literature on emotion across a range of fields of inquiry. Preservice science teachers felt included in the face-to-face group as they watched videos of classroom transactions. The strength of these feelings of social solidarity were dependent on the quality of the video recording. E-motion diaries provided a resource for interactions focused on shared emotional experiences leading to formation of social bonds and the alleviation of feelings of fear, trepidation and anxiety about becoming science teachers. We offer implications to inform practitioners who wish to improve feelings of inclusion amongst their online learners in science education.

  3. Alcohol and Group Formation: A Multimodal Investigation of the Effects of Alcohol on Emotion and Social Bonding

    Science.gov (United States)

    Sayette, Michael A.; Creswell, Kasey G.; Dimoff, John D.; Fairbairn, Catharine E.; Cohn, Jeffrey F.; Heckman, Bryan W.; Kirchner, Thomas R.; Levine, John M.; Moreland, Richard L.

    2017-01-01

    We integrated research on emotion and on small groups to address a fundamental and enduring question facing alcohol researchers: What are the specific mechanisms that underlie the reinforcing effects of drinking? In one of the largest alcohol-administration studies yet conducted, we employed a novel group-formation paradigm to evaluate the socioemotional effects of alcohol. Seven hundred twenty social drinkers (360 male, 360 female) were assembled into groups of 3 unacquainted persons each and given a moderate dose of an alcoholic, placebo, or control beverage, which they consumed over 36 min. These groups’ social interactions were video recorded, and the duration and sequence of interaction partners’ facial and speech behaviors were systematically coded (e.g., using the Facial Action Coding System). Alcohol consumption enhanced individual- and group-level behaviors associated with positive affect, reduced individual-level behaviors associated with negative affect, and elevated self-reported bonding. Our results indicate that alcohol facilitates bonding during group formation. Assessing nonverbal responses in social contexts offers new directions for evaluating the effects of alcohol. PMID:22760882

  4. Formation of the First Peptide Bond: The Structure of EF-P Bound to the 70S Ribosome

    Energy Technology Data Exchange (ETDEWEB)

    Blaha, Gregor; Stanley, Robin E.; Steitz, Thomas A.; Yale

    2009-10-21

    Elongation factor P (EF-P) is an essential protein that stimulates the formation of the first peptide bond in protein synthesis. Here we report the crystal structure of EF-P bound to the Thermus thermophilus 70S ribosome along with the initiator transfer RNA N-formyl-methionyl-tRNAi (fMet-tRNA{sub i}{sup fMet}) and a short piece of messenger RNA (mRNA) at a resolution of 3.5 angstroms. EF-P binds to a site located between the binding site for the peptidyl tRNA (P site) and the exiting tRNA (E site). It spans both ribosomal subunits with its amino-terminal domain positioned adjacent to the aminoacyl acceptor stem and its carboxyl-terminal domain positioned next to the anticodon stem-loop of the P site-bound initiator tRNA. Domain II of EF-P interacts with the ribosomal protein L1, which results in the largest movement of the L1 stalk that has been observed in the absence of ratcheting of the ribosomal subunits. EF-P facilitates the proper positioning of the fMet-tRNA{sub i}{sup fMet} for the formation of the first peptide bond during translation initiation.

  5. Susceptibility towards intramolecular disulphide-bond formation affects conformational stability and folding of human basic fibroblast growth factor.

    Science.gov (United States)

    Estapé, D; van den Heuvel, J; Rinas, U

    1998-01-01

    The conformational stability and the folding properties of the all-beta-type protein human basic fibroblast growth factor (hFGF-2) were studied by means of fluorescence spectroscopy. The results show that the instability of the biological activity of hFGF-2 is also reflected in a low conformational stability of the molecule. The reversibility of the unfolding and refolding process was established under reducing conditions. Determination of the free-energy of unfolding in the presence of reducing agents revealed that the conformational stability of hFGF-2 (DeltaGH2Oapp congruent with21 kJ. mol-1, 25 degreesC) is low compared with other globular proteins under physiological conditions (20-60 kJ.mol-1). However, the conformational stability of hFGF-2 is particularly low under non-reducing conditions. This instability is attributed to intramolecular disulphide-bond formation, rendering the molecule more susceptible to denaturant-induced unfolding. In addition, denaturant-induced unfolding of hFGF-2 renders the protein more susceptible to irreversible oxidative denaturation. Experimental evidence is provided that the irreversibility of the unfolding and refolding process in the absence of reducing agents is linked to the formation of an intramolecular disulphide bond involving cysteines 96 and 101. PMID:9761733

  6. Palladium- and copper-mediated N-aryl bond formation reactions for the synthesis of biological active compounds

    Directory of Open Access Journals (Sweden)

    Burkhard Koenig

    2011-01-01

    Full Text Available N-Arylated aliphatic and aromatic amines are important substituents in many biologically active compounds. In the last few years, transition-metal-mediated N-aryl bond formation has become a standard procedure for the introduction of amines into aromatic systems. While N-arylation of simple aromatic halides by simple amines works with many of the described methods in high yield, the reactions may require detailed optimization if applied to the synthesis of complex molecules with additional functional groups, such as natural products or drugs. We discuss and compare in this review the three main N-arylation methods in their application to the synthesis of biologically active compounds: Palladium-catalysed Buchwald–Hartwig-type reactions, copper-mediated Ullmann-type and Chan–Lam-type N-arylation reactions. The discussed examples show that palladium-catalysed reactions are favoured for large-scale applications and tolerate sterically demanding substituents on the coupling partners better than Chan–Lam reactions. Chan–Lam N-arylations are particularly mild and do not require additional ligands, which facilitates the work-up. However, reaction times can be very long. Ullmann- and Buchwald–Hartwig-type methods have been used in intramolecular reactions, giving access to complex ring structures. All three N-arylation methods have specific advantages and disadvantages that should be considered when selecting the reaction conditions for a desired C–N bond formation in the course of a total synthesis or drug synthesis.

  7. Effect of copper salts on peptide bond formation using peptide thioesters.

    Science.gov (United States)

    Ingenito, Raffaele; Wenschuh, Holger

    2003-11-27

    [reaction: see text] In the present paper, systematic studies revealed that Cu(I) salts in general and Cu(II) salts under certain circumstances promote effective reaction between peptide thiol esters and the N-terminal amino function of a second peptide segment to give the native amide bond for both solution- and solid-phase syntheses. Chiral integrity was retained. Reaction conditions were optimized and applied to the synthesis of a small protein, the identity of which was confirmed by NMR analysis.

  8. Ab initio elastic constants for the lonsdaleite phases of C, Si and Ge

    Energy Technology Data Exchange (ETDEWEB)

    Wang, S Q [Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, 72 Wenhua Road, Shenyang 110016 (China); Ye, H Q [Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, 72 Wenhua Road, Shenyang 110016 (China)

    2003-08-06

    The elastic constants of lonsdaleite C, Si and Ge are calculated by using the plane-wave pseudopotential method in the scheme of density functional theory and the local density approximation. For comparison, the elastic constants of the cubic diamond phases of these elements, zincblende SiC and 6H-SiC, are also calculated.

  9. Ab initio elastic constants for the lonsdaleite phases of C, Si and Ge

    Science.gov (United States)

    Wang, S. Q.; Ye, H. Q.

    2003-08-01

    The elastic constants of lonsdaleite C, Si and Ge are calculated by using the plane-wave pseudopotential method in the scheme of density functional theory and the local density approximation. For comparison, the elastic constants of the cubic diamond phases of these elements, zincblende SiC and 6H-SiC, are also calculated.

  10. CVD growth and characterization of 3C-SiC thin films

    Indian Academy of Sciences (India)

    Unknown

    5000 V (Morkoc et al 1994; Casady and Johnson 1996). Most of these developments have occurred in the hexa- gonal polytypes of SiC. The rapid development of 6H- and 4H-SiC substrates has resulted in the progress of device development in these materials. While homoepi- taxial growth of 3C-SiC has not developed ...

  11. Thermographic Characterization of Impact Damage in SiC/SiC Composite Materials

    Science.gov (United States)

    Fox, Dennis S.; Cosgriff, Laura M.; Bhatt, Ramakrishna; Choi, Sung R.

    2005-01-01

    SiC/SiC composite materials targeted as turbine components for next-generation aero-engines are being investigated at NASA Glenn Research Center. In order to examine damage mechanisms in these materials, SiC/SiC coupons were impacted with 1.59 mm diameter steel spheres at increasing velocities from 115 m/s to 400 m/s. Pulsed thermography, a nondestructive evaluation technique that monitors the thermal response of a sample over time, was utilized to characterize the impact damage. A thermal standard of similar material was fabricated to aid in the interpretation of the thermographic data and to provide information regarding thermography system detection capabilities in 2.4 mm thick SiC/SiC composite materials. Flat bottom holes at various depths with aspect ratios greater than 2.5 were detectable in the thermal images. In addition, the edges of holes at depths of 1.93 mm into the sample were not as resolvable as flat bottom holes closer to the surface. Finally, cooling behavior was characterized in SiC/SiC materials and used to determine impact damage depth within an 8.5% error of a known depth.

  12. SiC-Si as a support material for oxygen evolution electrode in PEM steam electrolysers

    DEFF Research Database (Denmark)

    Nikiforov, Aleksey; Tomás García, Antonio Luis; Petrushina, Irina

    2011-01-01

    The need of higher energy efficiency in hydrogen production has promoted the research on improved catalysts for water electrolysis. In this work, a novel supported catalyst for oxygen evolution electrodes was prepared and characterized with different techniques. IrO2 supported on a SiC/Si composi...

  13. Decoupled front/back dielectric textures for flat ultra-thin c-Si solar cells

    NARCIS (Netherlands)

    Isabella, O.; Vismara, R.; Ingenito, A.; Rezaei, N.; Zeman, M.

    2016-01-01

    The optical analysis of optically-textured and electrically-flat ultra-thin crystalline silicon (c-Si) slabs is presented. These slabs were endowed with decoupled front titanium-dioxide (TiO2) / back silicon-dioxide (SiO2) dielectric textures and were studied as function of two types of back

  14. Fabrication and Characteristics of an nc-Si/c-Si Heterojunction MOSFETs Pressure Sensor

    Directory of Open Access Journals (Sweden)

    Xiaofeng Zhao

    2012-05-01

    Full Text Available A novel nc-Si/c-Si heterojunction MOSFETs pressure sensor is proposed in this paper, with four p-MOSFETs with nc-Si/c-Si heterojunction as source and drain. The four p-MOSFETs are designed and fabricated on a square silicon membrane by CMOS process and MEMS technology where channel resistances of the four nc-Si/c-Si heterojunction MOSFETs form a Wheatstone bridge. When the additional pressure is P, the nc-Si/c-Si heterojunction MOSFETs pressure sensor can measure this additional pressure P. The experimental results show that when the supply voltage is 3 V, length-width (L:W ratio is 2:1, and the silicon membrane thickness is 75 μm, the full scale output voltage of the pressure sensor is 15.50 mV at room temperature, and pressure sensitivity is 0.097 mV/kPa. When the supply voltage and L:W ratio are the same as the above, and the silicon membrane thickness is 45 μm, the full scale output voltage is 43.05 mV, and pressure sensitivity is 2.153 mV/kPa. Therefore, the sensor has higher sensitivity and good temperature characteristics compared to the traditional piezoresistive pressure sensor.

  15. Fabrication and characteristics of an nc-Si/c-Si heterojunction MOSFETs pressure sensor.

    Science.gov (United States)

    Zhao, Xiaofeng; Wen, Dianzhong; Li, Gang

    2012-01-01

    A novel nc-Si/c-Si heterojunction MOSFETs pressure sensor is proposed in this paper, with four p-MOSFETs with nc-Si/c-Si heterojunction as source and drain. The four p-MOSFETs are designed and fabricated on a square silicon membrane by CMOS process and MEMS technology where channel resistances of the four nc-Si/c-Si heterojunction MOSFETs form a Wheatstone bridge. When the additional pressure is P, the nc-Si/c-Si heterojunction MOSFETs pressure sensor can measure this additional pressure P. The experimental results show that when the supply voltage is 3 V, length-width (L:W) ratio is 2:1, and the silicon membrane thickness is 75 μm, the full scale output voltage of the pressure sensor is 15.50 mV at room temperature, and pressure sensitivity is 0.097 mV/kPa. When the supply voltage and L:W ratio are the same as the above, and the silicon membrane thickness is 45 μm, the full scale output voltage is 43.05 mV, and pressure sensitivity is 2.153 mV/kPa. Therefore, the sensor has higher sensitivity and good temperature characteristics compared to the traditional piezoresistive pressure sensor.

  16. Detection of Potential Induced Degradation in c-Si PV Panels Using Electrical Impedance Spectroscopy

    DEFF Research Database (Denmark)

    Oprea, Matei-lon; Spataru, Sergiu; Sera, Dezso

    2016-01-01

    ) in c-Si PV panels. The method has been experimentally tested using an automated PID test bed, and the IS results were confirmed using traditional current-voltage characterization methods, as well as electroluminescence imaging. The corroborated results confirm the effectiveness of the new approach...

  17. Detection of Potential Induced Degradation in c-Si PV Panels Using Electrical Impedance Spectroscopy

    DEFF Research Database (Denmark)

    Oprea, Matei-lon; Spataru, Sergiu; Sera, Dezso

    This work, for the first time, investigates an Impedance Spectroscopy (IS) based method for detecting potential-induced degradation (PID) in crystalline silicon photovoltaic (c-Si PV) panels. The method has been experimentally tested on a set of panels that were confirmed to be affected by PID...

  18. Numerical Simulation of C/SiC Plain Weave Composites with Defects under Unidirectional Tension

    Directory of Open Access Journals (Sweden)

    ZENG Xianglong

    2017-08-01

    Full Text Available The second time develop of the ANSYS was realized by using APDL language, and an ovoid sectional multi-scale unit cell model for fiber bundle section with pre-made defects was established. At first the initial modulus, the strength and the ultimate strain of fiber bundle were calculated. Then the unit cell model of C/SiC woven composites was established according to the SEM photographs. By introducing the periodic boundary conditions, the initial anisotropic constants of C/SiC woven composites were predicted. The failure criteria proposed by Linde was utilized to set up the progressive damage mode,and the C/SiC plain weave composites with defects under unidirectional tension was simulated. So,the damage evolution process of the fiber bundle could be interpreted, when the unit cell of C/SiC plain weave composites was under the unidirection load. The numerical results show that the proposed model accurately captures the data from the experiments, which demonstrates the validity of the present analytical model. Furthermore, the numerical model provides an alternate way to design and predict the mechanical properties of plain weave composites.

  19. Chemical compatibility issues associated with use of SiC/SiC in advanced reactor concepts

    Energy Technology Data Exchange (ETDEWEB)

    Wilson, Dane F. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

    2015-09-01

    Silicon carbide/silicon carbide (SiC/SiC) composites are of interest for components that will experience high radiation fields in the High Temperature Gas Cooled Reactor (HTGR), the Very High Temperature Reactor (VHTR), the Sodium Fast Reactor (SFR), or the Fluoride-cooled High-temperature Reactor (FHR). In all of the reactor systems considered, reactions of SiC/SiC composites with the constituents of the coolant determine suitability of materials of construction. The material of interest is nuclear grade SiC/SiC composites, which consist of a SiC matrix [high-purity, chemical vapor deposition (CVD) SiC or liquid phase-sintered SiC that is crystalline beta-phase SiC containing small amounts of alumina-yttria impurity], a pyrolytic carbon interphase, and somewhat impure yet crystalline beta-phase SiC fibers. The interphase and fiber components may or may not be exposed, at least initially, to the reactor coolant. The chemical compatibility of SiC/SiC composites in the three reactor environments is highly dependent on thermodynamic stability with the pure coolant, and on reactions with impurities present in the environment including any ingress of oxygen and moisture. In general, there is a dearth of information on the performance of SiC in these environments. While there is little to no excess Si present in the new SiC/SiC composites, the reaction of Si with O2 cannot be ignored, especially for the FHR, in which environment the product, SiO2, can be readily removed by the fluoride salt. In all systems, reaction of the carbon interphase layer with oxygen is possible especially under abnormal conditions such as loss of coolant (resulting in increased temperature), and air and/ or steam ingress. A global outline of an approach to resolving SiC/SiC chemical compatibility concerns with the environments of the three reactors is presented along with ideas to quickly determine the baseline compatibility performance of SiC/SiC.

  20. A protocol for amide bond formation with electron deficient amines and sterically hindered substrates

    DEFF Research Database (Denmark)

    Due-Hansen, Maria E; Pandey, Sunil K; Christiansen, Elisabeth

    2016-01-01

    A protocol for amide coupling by in situ formation of acyl fluorides and reaction with amines at elevated temperature has been developed and found to be efficient for coupling of sterically hindered substrates and electron deficient amines where standard methods failed.......A protocol for amide coupling by in situ formation of acyl fluorides and reaction with amines at elevated temperature has been developed and found to be efficient for coupling of sterically hindered substrates and electron deficient amines where standard methods failed....

  1. Formation of sulfido ciobium complexes through C-S bond activation

    Directory of Open Access Journals (Sweden)

    Azevedo Nélio Pires

    1998-01-01

    Full Text Available Upon reacting (eta5-C5H52NbCl2, eta5-C5H5 = Cp, and (Ph3Sn(SPh, in THF, (eta5-C5H52Nb(Cl(mu-SSn(Ph3(Cl, 1, and (eta5-C5H52Nb(SCl, 2, were obtained. Complexes 1 and 2 were characterized by IR, ¹H-NMR, 13C-NMR, Mössbauer spectroscopies, elemental analysis as well as by atomic absorption. Hydrolysis of 1 yielded the mu-oxo species, (eta5-C5H52Nb(Cl(mu-OSn(Ph3Cl, 3, which was characterized by IR, ¹H-NMR, 13C-NMR and Mössbauer spectroscopies, elemental analysis, atomic absorption as well as by X-ray crystallography. It crystallizes in the space group Pca2(1 with a = 17.282(3, b = 18.122(4, c = 17.3269(2, V = 5426.2(16 ų, and Z = 8. Additional studies indicated that the complexes were formed as a result of the nucleophilic displacement of the niobium-chloride bond by the thiolate ligand followed by a C-S bond cleavage. The cleavage occurs with an excess of the thiolate compound equal to or greater than 2:1.

  2. 3C-SiC nanocrystal growth on 10° miscut Si(001) surface

    Energy Technology Data Exchange (ETDEWEB)

    Deokar, Geetanjali, E-mail: gitudeo@gmail.com [INSP, UPMC, CNRS UMR 7588, 4 place Jussieu, Paris F-75005 (France); D' Angelo, Marie; Demaille, Dominique [INSP, UPMC, CNRS UMR 7588, 4 place Jussieu, Paris F-75005 (France); Cavellin, Catherine Deville [INSP, UPMC, CNRS UMR 7588, 4 place Jussieu, Paris F-75005 (France); Faculté des Sciences et Technologie UPEC, 61 av. De Gaulle, Créteil F-94010 (France)

    2014-04-01

    The growth of 3C-SiC nano-crystal (NC) on 10° miscut Si(001) substrate by CO{sub 2} thermal treatment is investigated by scanning and high resolution transmission electron microscopies. The vicinal Si(001) surface was thermally oxidized prior to the annealing at 1100 °C under CO{sub 2} atmosphere. The influence of the atomic steps at the vicinal SiO{sub 2}/Si interface on the SiC NC growth is studied by comparison with the results obtained for fundamental Si(001) substrates in the same conditions. For Si miscut substrate, a substantial enhancement in the density of the SiC NCs and a tendency of preferential alignment of them along the atomic step edges is observed. The SiC/Si interface is abrupt, without any steps and epitaxial growth with full relaxation of 3C-SiC occurs by domain matching epitaxy. The CO{sub 2} pressure and annealing time effect on NC growth is analyzed. The as-prepared SiC NCs can be engineered further for potential application in optoelectronic devices and/or as a seed for homoepitaxial SiC or heteroepitaxial GaN film growth. - Highlights: • Synthesis of 3C-SiC nanocrystals epitaxied on miscut-Si using a simple technique • Evidence of domain matching epitaxy at the SiC/Si interface • SiC growth proceeds along the (001) plane of host Si. • Substantial enhancement of the SiC nanocrystal density due to the miscut • Effect of the process parameters (CO{sub 2} pressure and annealing duration)

  3. Effects of the gas feeding method on the properties of 3C-SiC/Si(111) grown by rapid thermal chemical vapor deposition

    CERN Document Server

    Shim, H W; Suh, E K

    1998-01-01

    High-quality crystalline 3C-SiC thin films are grown by rapid thermal chemical vapor deposition (RTCVD) on Si(111) by using two different growth processes. The films are grown along the [111] direction at 1200 .deg. C. The quality of the films are investigated by X-ray diffraction, transmission electron microscopy, and transmission electron diffraction. The SiC film grown by flowing the tetramethylsilane (TMS) gas before heating the substrate up to the growth temperature does not contain many voids at the SiC/Si interface, while the SiC grown by heating the substrate before supplying the TMS gas possesses many voids at the interface. The unintentionally doped SiC film grown by gas flow before heating the substrate appears to be n-type with a carrier concentration of 1.48 x 10 sup 1 sup 6 cm sup - sup 3 , a electron mobility of 884 cm sup 2 /V centre dot s, and a resistivity of 0.462 OMEGA centre dot cm. The physical properties, such as the electrical properties, the surface morphology, and the crystallinity, ...

  4. Bamboo-like 3C-SiC nanowires with periodical fluctuating diameter: Homogeneous synthesis, synergistic growth mechanism, and their luminescence properties

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Meng; Zhao, Jian [School of Electromechanical Engineering, Qingdao University of Science and Technology, Qingdao, Shandong Province 266061 (China); Li, Zhenjiang, E-mail: zhenjiangli@qust.edu.cn [School of Sino-German Science and Technology, Qingdao University of Science and Technology, Qingdao 266061, China (China); Yu, Hongyuan [School of Electromechanical Engineering, Qingdao University of Science and Technology, Qingdao, Shandong Province 266061 (China); Wang, Yaqi [School of Chemistry and Molecular Engineering, Qingdao University of Science and Technology, Qingdao, Shandong Province 266042 (China); Meng, Alan, E-mail: alanmengqust@163.com [School of Chemistry and Molecular Engineering, Qingdao University of Science and Technology, Qingdao, Shandong Province 266042 (China); Li, Qingdang [School of Sino-German Science and Technology, Qingdao University of Science and Technology, Qingdao 266061, China (China)

    2016-11-15

    Herein, bamboo-like 3C-SiC nanowires have been successfully fabricated on homogeneous 6H-SiC substrate by a simple chemical vapor reaction (CVR) approach. The obtained 3C-SiC nanostructure with periodical fluctuating diameter, is composed of two alternating structure units, the typical normal-sized stem segment with perfect crystallinity and obvious projecting nodes segment having high-density stacking faults. The formation of the interesting morphology is significantly subjected to the peculiar growth condition provided by the homogeneous substrate as well as the varying growth elastic energy. Furthermore, the photoluminescence (PL) performance measured on the bamboo-like SiC nanowire shows an intensive emission peaks centered at 451 nm and 467 nm, which has been expected to make a positive progress toward the optical application of the SiC-based one-dimensional (1D) nanostructures, such as light emission diode (LED). - Graphical abstract: Based on the synergistic growth mechanism from homogeneous substrate and elastic energy, bamboo-like 3C-SiC nanowires with periodically fluctuating diameter have been synthesized on 6H-SiC. The blue-violet light emission properties of the bamboo-like nanowires have also been investigated for exploring their peculiar optical application. - Highlights: • Bamboo-like 3C-SiC nanowires with periodically fluctuating diameter have been synthesized on 6H-SiC. • A synergistic growth mechanism from homogeneous substrate and elastic energy has been proposed firstly. • The blue-violet light emission properties of the products displayed peculiar optical application.

  5. Enantioselective formation of a dynamic hydrogen-bonded assembly based on the chiral memory concept

    NARCIS (Netherlands)

    Ish-i Tsutomu, T.I.; Crego Calama, Mercedes; Timmerman, P.; Reinhoudt, David; Shinkai, Seiji

    2002-01-01

    In this paper, we report the enantioselective formation of a dynamic noncovalent double rosette assembly 1a3·(CYA)6 composed of three 2-pyridylcalix[4]arene dimelamines (1a) and six butylcyanuric acid molecules (BuCYA). The six 2-pyridyl functionalities of the assembly interact stereoselectively

  6. Heat-induced whey protein isolate fibrils: Conversion, hydrolysis, and disulphide bond formation

    NARCIS (Netherlands)

    Bolder, S.G.; Vasbinder, A.; Sagis, L.M.C.; Linden, van der E.

    2007-01-01

    Fibril formation of individual pure whey proteins and whey protein isolate (WPI) was studied. The heat-induced conversion of WPI monomers into fibrils at pH 2 and low ionic strength increased with heating time and protein concentration. Previous studies, using a precipitation method, size-exclusion

  7. Termolecular proton transfer reactions assisted by ionic hydrogen bond formation: Reactions of aromatic cations with polar molecules

    Science.gov (United States)

    Daly, G. M.; Meot-Ner, M.; Pithawalla, Y. B.; El-Shall, M. S.

    1996-05-01

    We present a new method that applies resonant-two-photon ionization to generate reactant ions selectively in the source of a high-pressure mass spectrometer (R2PI-HPMS) for kinetic and equilibrium studies. Applications to reactions that would be obscured otherwise in a complex system are illustrated in mixtures of benzene with polar solvent molecules (S). We observe a novel type of proton transfer reactions from C6H6+• to two S molecules where S=CH3CN, CH3OH, C2H5OH and CH3COOC2H5, and from C6H5CH3+• to two S molecules where S=CH3OH and C2H5OH to form protonated solvent S2H+ dimers. The reactions are driven by the strong hydrogen bonds in the S2H+ dimers and therefore require the formation of the hydrogen bond concertedly with proton transfer, to make the process energetically feasible. The adducts (C6H6+•)S are observed with blocked solvent molecules where the subsequent switching reaction to yield S2H+ is slow, but not with alcohol reactants that can form hydrogen-bonded chains that facilitate fast subsequent proton extraction. Correspondingly, kinetic simulations suggest that the mechanism proceeds through (C6H6+•)S+S→S2H++C6H5• and C6H6+•+2S→S2H++C6H5• reactions, respectively. The rate coefficients of these reactions are in the range 10-13-10-12 cm3 s-1 for the reaction through a bimolecular switching channel and in the range 10-26-10-28 cm6 s-1 for reaction through a direct termolecular proton extraction mechanism. The relation to energetics and reactant structure is examined.

  8. Electrical activation of nitrogen heavily implanted 3C-SiC(1 0 0)

    Energy Technology Data Exchange (ETDEWEB)

    Li, Fan, E-mail: f.li.1@warwick.ac.uk [School of Engineering, University of Warwick, Coventry CV4 7AL (United Kingdom); Sharma, Yogesh; Shah, Vishal; Jennings, Mike [School of Engineering, University of Warwick, Coventry CV4 7AL (United Kingdom); Pérez-Tomás, Amador [ICN2 – Institut Catala de Nanociència i Nanotecnologia, Campus UAB, 08193 Bellaterra, Barcelona (Spain); Myronov, Maksym [Physics Department, University of Warwick, Coventry CV4 7AL (United Kingdom); Fisher, Craig [School of Engineering, University of Warwick, Coventry CV4 7AL (United Kingdom); Leadley, David [Physics Department, University of Warwick, Coventry CV4 7AL (United Kingdom); Mawby, Phil [School of Engineering, University of Warwick, Coventry CV4 7AL (United Kingdom)

    2015-10-30

    Highlights: • Nitrogen is fully activated by 1175 °C annealing for 1.5 × 10{sup 19} cm{sup −3} doped 3C-SiC. • Free donor concentration is found to readily saturate in 3C-SiC at ∼7 × 10{sup 19} cm{sup −3}. • 3C-SiC is found to have complete donor thermal ionization above 150 K. • Donor in 1.5 × 10{sup 19} cm{sup −3} nitrogen implanted 3C-SiC has an energy level ∼15 meV. • The SiO{sub 2} cap is found to have a bigger influence on low and medium doped samples. - Abstract: A degenerated wide bandgap semiconductor is a rare system. In general, implant levels lie deeper in the band-gap and carrier freeze-out usually takes place at room temperature. Nevertheless, we have observed that heavily doped n-type degenerated 3C-SiC films are achieved by nitrogen implantation level of ∼6 × 10{sup 20} cm{sup −3} at 20 K. According to temperature dependent Hall measurements, nitrogen activation rates decrease with the doping level from almost 100% (1.5 × 10{sup 19} cm{sup −3}, donor level 15 meV) to ∼12% for 6 × 10{sup 20} cm{sup −3}. Free donors are found to saturate in 3C-SiC at ∼7 × 10{sup 19} cm{sup −3}. The implanted film electrical performances are characterized as a function of the dopant doses and post implantation annealing (PIA) conditions by fabricating Van der Pauw structures. A deposited SiO{sub 2} layer was used as the surface capping layer during the PIA process to study its effect on the resultant film properties. From the device design point of view, the lowest sheet resistivity (∼1.4 mΩ cm) has been observed for medium doped (4 × 10{sup 19} cm{sup −3}) sample with PIA 1375 °C 2 h without a SiO{sub 2} cap.

  9. Determination of the mobility gap of intrinsic ?c-Si:H in p-i-n solar cells

    NARCIS (Netherlands)

    Pieters, B.E.; Stiebig, H.; Zeman, M.; Van Swaaij, R.A.C.M.M.

    2009-01-01

    Microcrystalline silicon (?c-Si:H) is a promising material for application in multijunction thin-film solar cells. A detailed analysis of the optoelectronic properties is impeded by its complex microstructural properties. In this work we will focus on determining the mobility gap of ?c-Si:H

  10. Methods of radiation effects evaluation of SiC/SiC composite and SiC fibers

    Energy Technology Data Exchange (ETDEWEB)

    Youngblood, G.E.; Jones, R.H. [Pacific Northwest National Lab., Richland, WA (United States)

    1998-03-01

    This report covers material presented at the IEA/Jupiter Joint International Workshop on SiC/SiC Composites for Fusion structural Applications held in conjunction with ICFRM-8, Sendai, Japan, Oct. 23--24, 1997. Several methods for radiation effects evaluation of SiC fibers and fiber-reinforced SiC/SiC composite are presented.

  11. Minimizing optical losses in monolithic perovskite/c-Si tandem solar cells with a flat top cell

    NARCIS (Netherlands)

    Santbergen, R.; Mishima, Ryoto; Meguro, Tomomi; Hino, Masashi; Uzu, Hisashi; Blanker, A.J.; Yamamoto, Kenji; Zeman, M.

    2016-01-01

    In a monolithic perovskite/c-Si tandem device, the perovskite top cell has to be deposited onto a flat c-Si bottom cell without anti-reflective front side texture, to avoid fabrication issues. We use optical simulations to analyze the reflection losses that this induces. We then systematically

  12. Reversible Cleavage/Formation of the Chromium-Chromium Quintuple Bond in the Highly Regioselective Alkyne Cyclotrimerization.

    Science.gov (United States)

    Huang, Yu-Siang; Huang, Gou-Tao; Liu, Yao-Lun; Yu, Jen-Shiang K; Tsai, Yi-Chou

    2017-11-27

    Herein we report the employment of the quintuply bonded dichromium amidinates [Cr{κ(2) -HC(N-2,6-(i) Pr2 C6 H3 )(N-2,6-R2 C6 H3 )}]2 (R=iPr (1), Me (7)) as catalysts to mediate the [2+2+2] cyclotrimerization of terminal alkynes giving 1,3,5-trisubstituted benzenes. During the catalysis, the ultrashort Cr-Cr quintuple bond underwent reversible cleavage/formation, corroborated by the characterization of two inverted arene sandwich dichromium complexes (μ-η(6) :η(6) -1,3,5-(Me3 Si)3 C6 H3 )[Cr{κ(2) -HC(N-2,6-(i) Pr2 C6 H3 )(N-2,6-R2 C6 H3 )}]2 (R=(i) Pr (5), Me (8)). In the presence of σ donors, such as THF and 2,4,6-Me3 C6 H2 CN, the bridging arene 1,3,5-(Me3 Si)3 C6 H3 in 5 and 8 was extruded and 1 and 7 were regenerated. Theoretical calculations were employed to disclose the reaction pathways of these highly regioselective [2+2+2] cylcotrimerization reactions of terminal alkynes. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Ab-initio modeling of oxygen on the surface passivation of 3C-SiC nanostructures

    Energy Technology Data Exchange (ETDEWEB)

    Cuevas, J.L.; Trejo, A.; Calvino, M.; Carvajal, E. [Instituto Politecnico Nacional, ESIME-Culhuacan, Av. Santa Ana 1000, 04430, D.F. (Mexico); Cruz-Irisson, M., E-mail: irisson@ipn.mx [Instituto Politecnico Nacional, ESIME-Culhuacan, Av. Santa Ana 1000, 04430, D.F. (Mexico)

    2012-08-15

    In this work the effect of OH on the electronic states of H-passivated 3C-SiC nanostructures, was studied by means of Density Functional Theory. We compare the electronic band structure for a [1 1 1]-oriented nanowire with total H, OH passivation and a combination of both. Also the electronic states of a porous silicon carbide case (PSiC) a C-rich pore surface in which the dangling bonds on the surface are saturated with H and OH was studied. The calculations show that the surface replacement of H with OH radicals is always energetically favorable and more stable. In all cases the OH passivation produced a similar effect than the H passivation, with electronic band gap of lower energy value than the H-terminated phase. When the OH groups are attached to C atoms, the band gap feature is changed from direct to indirect. The results indicate the possibility of band gap engineering on SiC nanostructures through the surface passivation species.

  14. Formation, structure and bonding of metalloid Al and Ga clusters. A challenge for chemical efforts in nanosciences.

    Science.gov (United States)

    Schnöckel, Hansgeorg

    2008-09-07

    The renaissance of Al and Ga cluster chemistry is presented in three steps: on the grounds of boron hydride chemistry and the Wade concept, the first step starts in the early nineties of the last century with the formation of single Al-Al and Ga-Ga bonds in molecular entities, obtained by different synthetic approaches. The special method via reaction of high-temperature molecules like AlCl and its disproportionation to Al metal and AlX(3) leads to the second step which started about 10 years ago: the formation of nanoscaled metalloid Al and Ga clusters as intermediates on the way to the metal. Based on the structure of several recent examples, bonding is discussed with respect to the structure of the elements and the generation of naked metal atom clusters. After discussion of the individual metalloid clusters including experiments of the gaseous species and discussion about the jellium model, the third step and main part of this review starts only a few years ago. This latest period hardly can be called a renaissance period as, so far, interactions of nanoscaled metal atom clusters in a perfect 1-, 2- or 3-dimensional arrangement of a crystal have never been investigated before. The most remarkable result in this perspective is the superconducting behaviour of a Ga(84) cluster compound in the crystalline state which had never been observed in metal atom clusters before. However, these experiments show that superconductivity is only observed if the clusters in the crystal are perfectly orientated: as a cluster arrangement of this type can hardly be fabricated by physical methods, these results, which have been predicted by theory, may be called a disillusionment for nanosciences; for chemistry, however, these conclusions pose a challenge.

  15. Synthesis of Reusable Silica Nanosphere-Supported Pt(IV Complex for Formation of Disulfide Bonds in Peptides

    Directory of Open Access Journals (Sweden)

    Xiaonan Hou

    2017-02-01

    Full Text Available Some peptide-based drugs, including oxytocin, vasopressin, ziconotide, pramlintide, nesiritide, and octreotide, contain one intramolecular disulfide bond. A novel and reusable monodispersed silica nanosphere-supported Pt(IV complex (SiO2@TPEA@Pt(IV; TPEA: N-[3-(trimethoxysilylpropyl]ethylenediamine was synthesized via a four-step procedure and was used for the formation of intramolecular disulfide bonds in peptides. Transmission electron microscopy (TEM and chemical mapping results for the Pt(II intermediates and for SiO2@TPEA@Pt(IV show that the silica nanospheres possess a monodisperse spherical structure and contain uniformly-distributed Si, O, C, N, Cl, and Pt. The valence state of Pt on the silica nanospheres was characterized by X-ray photoelectron spectroscopy (XPS. The Pt(IV loaded on SiO2@TPEA@Pt(IV was 0.15 mmol/g, as determined by UV-VIS spectrometry. The formation of intramolecular disulfides in six dithiol-containing peptides of variable lengths by the use of SiO2@TPEA@Pt(IV was investigated, and the relative oxidation yields were determined by high-performance liquid chromatography (HPLC. In addition, peptide 1 (Ac-CPFC-NH2 was utilized to study the reusability of SiO2@TPEA@Pt(IV. No significant decrease in the relative oxidation yield was observed after ten reaction cycles. Moreover, the structure of SiO2@TPEA@Pt(IV after being used for ten cycles was determined to be similar to its initial one, demonstrating the cycling stability of the complex.

  16. Carbon clusters as possible defects at the SiC-SiO2 interface

    Science.gov (United States)

    Liu, Yingdi; Dang, Hongli; Liu, Yang; Li, Ying; Chisholm, Matthew; Biggerstaff, Trinity; Duscher, Gerd; Wang, Sanwu

    2009-03-01

    High state densities in the band gap of the SiC-SiO2 interface significantly reduce the channel mobilities in SiC-based high-temperature/high-power microelectronics. Investigations of the nature of the interface defects are thus of great importance. While several possible defects including very small carbon clusters with up to four carbon atoms have been identified by first-principles theory, larger carbon clusters as possible defects have attracted less attention. Here, we report first-principles quantum-mechanical calculations for two larger carbon clusters, the C10 ring and the C20 fullerence, at the SiC-SiO2 interface. We find that both carbon clusters introduce significant states in the band gap. The states extend over the entire band gap with higher densities in the upper half of the gap, thus accounting for some of the interface trap densities observed experimentally.

  17. Carbon Clusters as Possible Defects in the SiC-SiO2 Interface

    Energy Technology Data Exchange (ETDEWEB)

    Dang, Hongli [ORNL; Ramkumar, Gudipati [unknown; Yang, Liu [unknown; Li, Ying [ORNL; Peterson, Heather [unknown; Chisholm, Matthew F [ORNL; Biggerstaff, Trinity Leigh [ORNL; Duscher, Gerd [University of Tennessee, Knoxville (UTK); Wang, Sanwu [ORNL

    2009-01-01

    High state densities in the band gap of the SiC-SiO2 interface significantly reduce the channel mobilities in SiC-based high-temperature/high-power microelectronics. Investigations of the nature of the interface defects are thus of great importance. While several possible defects including very small carbon clusters with up to four carbon atoms have been identified by first-principles theory, larger carbon clusters as possible defects have attracted less attention. Here, we report first-principles quantum-mechanical calculations for two larger carbon clusters, the C10 ring and the C20 fullerence, in the SiC-SiO2 interface. We find that both carbon clusters introduce significant states in the band gap. The states extend over the entire band gap with higher densities in the upper half of the gap, thus accounting for some of the interface trap densities observed experimentally

  18. High-temperature tensile strength of near-stoichiometric SiC/SiC composites

    Science.gov (United States)

    Hironaka, K.; Nozawa, T.; Hinoki, T.; Igawa, N.; Katoh, Y.; Snead, L. L.; Kohyama, A.

    2002-12-01

    In an attempt to characterize mechanical properties of near-stoichiometric SiC/SiC composites, tensile tests were conducted at room temperature in air and at elevated temperature under mild oxidizing gases atmosphere. SiC/SiC composites were fabricated by forced-flow chemical vapor infiltration method using two-dimensional fabrics of carbon coated near-stoichiometric Tyranno™SA fibers. Tensile tests were conducted on composites with two types of lay-up schemes using edge-loading small specimens. The effect of lay-up orientation on the mechanical properties and fracture behavior of composites were also examined. Tensile strength of composite was slightly decreased at 1573 K, while it retained approximately 80% of the strength at room temperature. Porosity dependence on elastic modulus was clearly exhibited.

  19. Magnetohydrodynamic (MHD) considerations for liquid metal blanket and a SiC/SiC composite structure

    Energy Technology Data Exchange (ETDEWEB)

    Scholz, R.; Greeff, J. de; Vinche, C. [Commission Europeenne Community, JRC, Vatican City State, Holy See (Italy)

    1998-07-01

    The electrical conductivity was measured on SiC/SiC composite specimens, in the as-received conditions and after neutron irradiation, for temperatures between 20 deg. C and 1000 deg. C. The tests were aimed at estimating the magnitude of MHD effects in liquid metal blankets and a SiC/SiC composites structure. The electrical conductivity of the unirradiated samples increased continuously with temperature and ranged from 330 ({omega} m){sup -1} at 20 deg. C to 550 ({omega} m){sup -1} at 1000 deg.C. The irradiation reduced only slightly the magnitude of {sigma} indicating the materials tested cannot be treated as an electrical insulator in a MHD analysis for liquid metal blankets. (authors)

  20. Optimization of laser fired contact processes in c-Si solar cells

    Science.gov (United States)

    Sánchez-Aniorte, I.; Colina, M.; Perales, F.; Molpeceres, C.

    In this work, we study the optimization of aluminium laser-fired contacts (LFC) [1] in combination with c-Si passivated solar cell [2,3]. The samples consist in p-type Fz c-Si wafers with two different passivating configurations; both thermally-grown silicon oxide (SiO2) and plasma deposited silicon carbide (SiCx) were used as the passivating rear layer. Finally, a 2 μ m Aluminum layer was deposited at the front and rear surface. A nanosecond Nd:YAG laser operating at 532 nm was used to fire the aluminum locally through the thin passivating layer. Green lasers offer the possibility to obtain a selective removal of the passivating layer, since the underlying silicon results typically less affected than when using IR radiation. Morphological and electrical analysis permitted to identify the optimal laser parameters to achieve good ohmic contacts and to reduce the laser-damaged area.

  1. Behind the Nature of Titanium Oxide Excellent Surface Passivation and Carrier Selectivity of c-Si

    DEFF Research Database (Denmark)

    Plakhotnyuk, Maksym; Crovetto, Andrea; Hansen, Ole

    We present an expanded study of the passivation properties of titanium dioxide (TiO2) on p-type crystalline silicon (c-Si). We report a low surface recombination velocity (16 cm/s) for TiO2 passivation layers with a thin tunnelling oxide interlayer (SiO2 or Al2O3) on p-type crystalline silicon (c......-Si). The TiO2 films were deposited by thermal atomic layer deposition (ALD) at temperatures in the range of 80-300  ̊C using titanium tetrachloride (TiCl4) as Ti precursor and water as the oxidant. The influence of TiO2 thickness (5, 10, 20 nm), presence of additional tunneling interlayer (SiO2 or Al2O3...

  2. Betavoltaic device in por-SiC/Si C-Nuclear Energy Converter

    Science.gov (United States)

    Akimchenko, Alina; Chepurnov, Victor; Dolgopolov, Mikhail; Gurskaya, Albina; Kuznetsov, Oleg; Mashnin, Alikhan; Radenko, Vitaliy; Radenko, Alexander; Surnin, Oleg; Zanin, George

    2017-10-01

    The miniature and low-power devices with long service life in hard operating conditions like the Carbon-14 beta-decay energy converters indeed as eternal resource for integrated MEMS and NEMS are considered. Authors discuss how to create the power supply for MEMS/NEMS devices, based on porous SiC/Si structure, which are tested to be used as the beta-decay energy converters of radioactive C-14 into electrical energy. This is based on the silicon carbide obtaining by self-organizing mono 3C-SiC endotaxy on the Si substrate. The new idea is the C-14 atoms including in molecules in the silicon carbide porous structure by this technology, which will increase the efficiency of the converter due to the greater intensity of electron-hole pairs generation rate in the space charge region. The synthesis of C-14 can be also performed by using the electronically controlled magneto-optic chamber.

  3. High-temperature tensile strength of near-stoichiometric SiC/SiC composites

    Energy Technology Data Exchange (ETDEWEB)

    Hironaka, K. E-mail: keisuke@iae.kyoto-u.ac.jp; Nozawa, T.; Hinoki, T.; Igawa, N.; Katoh, Y.; Snead, L.L.; Kohyama, A

    2002-12-01

    In an attempt to characterize mechanical properties of near-stoichiometric SiC/SiC composites, tensile tests were conducted at room temperature in air and at elevated temperature under mild oxidizing gases atmosphere. SiC/SiC composites were fabricated by forced-flow chemical vapor infiltration method using two-dimensional fabrics of carbon coated near-stoichiometric Tyranno SA fibers. Tensile tests were conducted on composites with two types of lay-up schemes using edge-loading small specimens. The effect of lay-up orientation on the mechanical properties and fracture behavior of composites were also examined. Tensile strength of composite was slightly decreased at 1573 K, while it retained approximately 80% of the strength at room temperature. Porosity dependence on elastic modulus was clearly exhibited.

  4. Fundamental and overtone vibrational spectroscopy, enthalpy of hydrogen bond formation and equilibrium constant determination of the methanol-dimethylamine complex.

    Science.gov (United States)

    Du, Lin; Mackeprang, Kasper; Kjaergaard, Henrik G

    2013-07-07

    We have measured gas phase vibrational spectra of the bimolecular complex formed between methanol (MeOH) and dimethylamine (DMA) up to about 9800 cm(-1). In addition to the strong fundamental OH-stretching transition we have also detected the weak second overtone NH-stretching transition. The spectra of the complex are obtained by spectral subtraction of the monomer spectra from spectra recorded for the mixture. For comparison, we also measured the fundamental OH-stretching transition in the bimolecular complex between MeOH and trimethylamine (TMA). The enthalpies of hydrogen bond formation (ΔH) for the MeOH-DMA and MeOH-TMA complexes have been determined by measurements of the fundamental OH-stretching transition in the temperature range from 298 to 358 K. The enthalpy of formation is found to be -35.8 ± 3.9 and -38.2 ± 3.3 kJ mol(-1) for MeOH-DMA and MeOH-TMA, respectively, in the 298 to 358 K region. The equilibrium constant (Kp) for the formation of the MeOH-DMA complex has been determined from the measured and calculated transition intensities of the OH-stretching fundamental transition and the NH-stretching second overtone transition. The transition intensities were calculated using an anharmonic oscillator local mode model with dipole moment and potential energy curves calculated using explicitly correlated coupled cluster methods. The equilibrium constant for formation of the MeOH-DMA complex was determined to be 0.2 ± 0.1 atm(-1), corresponding to a ΔG value of about 4.0 kJ mol(-1).

  5. Determination of material properties for short fibre reinforced C/C-SiC

    Directory of Open Access Journals (Sweden)

    Hausherr J.-M.

    2015-01-01

    Full Text Available Determining the mechanical properties of short fibre reinforced CMC using standard sized coupons has always been a challenge due to a high statistical scattering of the measured values. Although the random orientation of short fibres results in a quasi-isotropic material behavior of 2D-structures with a sufficiently large volume, the small volume typical for test coupons usually results in a non-isotropic fibre orientation in the tested volume. This paper describes a method for manufacturing unidirectional oriented short fibre reinforced CMC materials and presents material properties of UD-C/C-SiC. After verifying the fibre orientation of the CMC using micro-computed tomography, coupons were extracted to determine the orthotropic material properties. These orthotropic material properties were then used to predict the properties of C/C-SiC with randomly distributed short fibres. To validate the method, micro-computed tomography is used to quantitatively determine the fibre orientation within coupons extracted from randomly distributed short fibre C/C-SiC. After mechanical three-point-bending tests, the measured stiffness and bending strength is compared with the predicted properties. Finally, the data are used to devise a method suited for reducing the inherent large spread of material properties associated with the measurement of CMC materials with randomly distributed short fibres.

  6. Fracture Characteristics of C/SiC Composites for Rocket Nozzle at Elevated Temperature

    Energy Technology Data Exchange (ETDEWEB)

    Yoon, Dong Hyun; Lee, Jeong Won; Kim, Jae Hoon [Chungnam Nat’l Univ., Daejeon (Korea, Republic of); Sihn, Ihn Cheol; Lim, Byung Joo [Dai-Yang Industries Co., Daejeon (Korea, Republic of)

    2016-11-15

    In a solid propulsion system, the rocket nozzle is exposed to high temperature combustion gas. Hence, choosing an appropriate material that could demonstrate adequate performance at high temperature is important. As advanced materials, carbon/silicon carbide composites (C/SiC) have been studied with the aim of using them for the rocket nozzle throat. However, when compared with typical structural materials, C/SiC composites are relatively weak in terms of both strength and toughness, owing to their quasi-brittle behavior and oxidation at high temperatures. Therefore, it is important to evaluate the thermal and mechanical properties of this material before using it in this application. This study presents an experimental method to investigate the fracture behavior of C/SiC composite material manufactured using liquid silicon infiltration (LSI) method at elevated temperatures. In particular, the effects of major parameters, such as temperature, loading, oxidation conditions, and fiber direction on strength and fracture characteristics were investigated. Fractography analysis of the fractured specimens was performed using an SEM.

  7. Optical properties of GaN films grown on SiC/Si

    Energy Technology Data Exchange (ETDEWEB)

    Devrajan, J.; Steckl, A.J. [Cincinnati Univ., OH (United States); Tran, C.A.; Stall, R.A. [EMCORE Corp., Somerset, NJ (United States)

    1998-08-01

    3C SiC grown on Si and on SOI wafers have been used as substrates for GaN growth. The optical properties of GaN/3C SiC are compared to those of GaN grown on the commonly used sapphire substrates and on 6H SiC substrates. Mapping of the PL characteristics over {proportional_to}1 inch substrates indicate a fairly strong edge effect in terms of peak intensity for GaN/3C SiC. Interestingly, the wavelength of the peak intensity was quite uniform over the entire wafer area, with an average value of 365 nm and a standard deviation of {proportional_to}3.3 nm. Mapping of the FWHM of the emission peak exhibited some edge effect, with the lowest values in the center of the wafer. The average PL FWHM was {proportional_to}17 nm, with a standard deviation of {proportional_to}1.4 nm. (orig.) 3 refs.

  8. Effect of surface morphology and densification on the infrared emissivity of C/SiC composites

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Fuyuan, E-mail: wangfy1986@gmail.com; Cheng, Laifei; Zhang, Qing, E-mail: zhangqing@nwpu.edu.cn; Zhang, Litong

    2014-09-15

    Highlights: • The cauliflower-like microstructure improved the infrared emissivity multiply. • The infrared emissivity decreased continually with the improving surface flatness. • The densification process boosted the infrared emissivity. - Abstract: The effects of surface morphology and densification on the infrared emissivity of 2D C/SiC composites were investigated in 6–16 μm from 1000 °C to 1600 °C. As the sample surface was polished, the reflection and scattering for the electromagnetic waves of thermal radiation were reduced, causing a sustained decrease in the infrared emissivity. The space-variant polarizations caused by the cauliflower-like microstructure were enervated in the smooth surface, which enhanced the reduction trendy in the infrared emissivity. In densification process, the increasing SiC content and the growing amount of the cauliflower-like microstructure on sample surface improved the infrared emissivity of C/SiC composites, while the decreasing porosity decreased it. Due to the greater positive effects on the thermal radiation during the densification process, the infrared emissivity of C/SiC composites increased successively with density.

  9. C/C-SiC Composites for Nozzle of Solid Propellant Ramjet

    Directory of Open Access Journals (Sweden)

    WANG Lingling

    2017-01-01

    Full Text Available Carbon fiber reinforced carbon and silicon carbide matrix composites for nozzle inner of solid propellant ramjet were prepared by using the hybrid process of "chemical vapor infiltration + precursor impregnation pyrolysis (CVI+PIP". The microstructure, flexural and anti-ablation properties of the C/C-SiC composites and hydraulic test and rocket motor hot firing test for nozzle inner of solid propellant ramjet were comprehensively investigated. The results show that when the flexural strength of the composite reachs 197 MPa, the fracture damage behavior of the composites presents typical toughness mode.Also the composites has excellent anti-ablative property, i.e., linear ablation rate is only 0.0063 mm·s-1 after 200 s ablation. The C/C-SiC component have excellent integral bearing performance with the hydraulic bursting pressure of 6.5 MPa, and the high temperature combination property of the C/C-SiC composite nozzle inner is verified through motor hot firing of solid propellant ramjet.

  10. Fiber creep rate and high-temperature properties of SiC/SiC composites

    Energy Technology Data Exchange (ETDEWEB)

    Lewinsohn, C.A.; Jones, R.H.; Youngblood, G.E.; Henager, C.H. Jr. [Pacific Northwest National Lab., Richland, WA (United States)

    1998-03-01

    Results of studies aimed at relating the fiber creep rate to the subcritical crack growth rate and fracture properties of SiC/SiC composites have demonstrated that the crack growth rate in a bulk composite is controlled by the fiber creep rate. This result was demonstrated for Nicalon-CG and Hi-Nicalon fiber reinforced material where a 50--75 c shift in the creep strength of the fiber resulted in a similar shift in the crack growth rate of the composite. Irradiation enhanced creep of SiC fibers and matrix must also be considered in the performance assessment of SiC/SiC composites. The shape of the displacement versus time curve for composites containing Hi-Nicalon fibers were similar to those of the previously tested materials, containing Ceramic-grade fibers, that exhibited subcritical crack growth controlled by time-dependent relaxation of the fiber-bridging stresses due to fiber creep. The crack velocity in the CG-C composites at 1100 C in argon was very close to that of the Hi-C materials at 1150--1175 C, this roughly corresponds to the temperature differential shown by DiCarlo et al. to obtain the same relaxation in 1 hour bend stress relaxation (BSR) tests in the two fibers. This supports the hypothesis that subcritical crack growth in SiC/SiC composites is controlled by fiber creep.

  11. σ Bond activation through tunneling: formation of the boron hydride cations BHn(+) (n = 2, 4, 6).

    Science.gov (United States)

    Qiu, Yudong; Wu, Chia-Hua; Schaefer, Henry F; Allen, Wesley D; Agarwal, Jay

    2016-02-07

    The network of H2 additions to B(+) and subsequent insertion reactions serve as a tractable model for hydrogen storage in elementary boron-containing compounds. Here, they are investigated using state-of-the-art ab initio methods (up to CCSDTQ and cc-pCV6Z basis sets). The binding energies of H2 to HBH(+) (14.9 kcal mol(-1)) and HBH(H2)(+) (18.1 kcal mol(-1)) are determined to be much higher than those for B(H2)(+) (3.8 kcal mol(-1)), B(H2)2(+) (3.0 kcal mol(-1)), and B(H2)3(+) (2.5 kcal mol(-1)) at the CCSDTQ/CBS level of theory. These predictions are in agreement with the experiments of Kemper, Bushnell, Weis, and Bowers (J. Am. Chem. Soc., 1998, 120, 7577). Molecular orbital analyses show that the enhanced binding in HBH(H2)m(+) complexes originates from the strong interaction between the 1σu HOMO of HBH(+) and the 1σu LUMO of H2. For the insertion reactions B(H2)n(+) → HBH(H2)n-1(+), activation barriers are determined to be 58.3 kcal mol(-1) [Mk-MRCCSD(T)/CBS], 12.2 kcal mol(-1) (CCSDTQ/CBS) and 4.6 kcal mol(-1) (CCSDTQ/CBS) for n = 1, 2, and 3, respectively. After using theoretical results to remove tunneling effects from the experimental rate constants, new Arrhenius fits yield activation barriers of 4.6(3) kcal mol(-1) and 3.8(1) kcal mol(-1) for the BH6(+) and BD6(+) insertion reactions, respectively, which are in near perfect agreement with converged theoretical values (4.6 kcal mol(-1) and 3.9 kcal mol(-1)). These findings demonstrate that earlier Arrhenius fits considerably underestimate these barriers, and that quantum tunneling dominates the σ bond activation mechanism witnessed in previous experiments involving BH6(+).

  12. "The cancer bond": exploring the formation of cancer risk perception in families with Lynch syndrome.

    Science.gov (United States)

    Palmquist, Aunchalee E L; Koehly, Laura M; Peterson, Susan K; Shegog, Margarette; Vernon, Sally W; Gritz, Ellen R

    2010-10-01

    This study explores the social context of hereditary cancer risk perception in three families, an African-American family, a Mexican-American family, and a Caucasian family, each with Lynch Syndrome documented by a mismatch repair gene mutation. Communication network assessments measured family communication about cancer experiences and genetic testing information among a total of 26 participants. Participant narratives were evaluated to gain insight into how family cancer experiences and genetic testing information have shaped perceptions of cancer risk. Analysis of communication networks indicated that some families discussed cancer experiences to a greater extent than genetic testing information, and vice-versa. Interviews elucidated that sharing both types of health information led participants to conceptualize linkages among a strong family history of cancer, genetic testing information, and cancer prevention strategies. Understanding how different types of family communication influence the formation of perceived hereditary disease risk may enhance efforts to tailor genetic counseling services for families.

  13. A large scale enzyme screen in the search for new methods of silicon-oxygen bond formation.

    Science.gov (United States)

    Abbate, Vincenzo; Bassindale, Alan R; Brandstadt, Kurt F; Taylor, Peter G

    2011-02-01

    Biotransformations make use of biological systems to catalyze or promote specific chemical reactions. Transformations that utilize enzymes as "greener" and milder catalysts compared to traditional reaction conditions are of particular interest. Recently, organosilicon compounds have begun to be explored as non-natural enzymatic substrates for biotransformations. The aims of this study were to screen readily available (approximately eighty) enzymes for their ability to catalyze in vitro siloxane bond formation under mild reaction conditions using a model monoalkoxysilane as the substrate and to make a preliminary evaluation of potential factors that might lead to activity or inactivity of a particular enzyme. Several new hydrolase enzymes were observed to catalyze the formation of the condensation product when compared to peptide controls, or buffer solutions at the same pH, as judged from quantitative analyses by gas chromatography. Aspergillus ficuum phytase, Aspergillus niger phytase, chicken egg white lysozyme, porcine gastric mucosa pepsin, and Rhizopus oryzae lipase all catalyzed the condensation of silanols in aqueous media. Factors involved in determining the activity of an enzyme towards silanol condensation appear to include: the presence of imidazole and hydroxyl functions in the active site; solvent; the presence of water; the surface properties of the enzyme; possible covalent inhibition; and steric factors in the substrate. Copyright © 2010 Elsevier Inc. All rights reserved.

  14. Mineral catalysis of the formation of the phosphodiester bond in aqueous solution - The possible role of montmorillonite clays

    Science.gov (United States)

    Ferris, James P.; Ertem, Gozen; KAMALUDDIN; Agarwal, Vipin; Hua, Lu Lin

    1989-01-01

    The possible role of montmorillonite clays in the spontaneous formation on the primitive earth of the phosphodiester bond in the presence of water was investigated in experiments measuring the binding of various nucleosides and nucleotides with Na(+)-montmorillonite 22A and the reactions of these compounds with a water-soluble carbodiimide. It was found that, at neutral pH, adenine derivatives bind stronger than the corresponding uracil derivatives, consistent with the protonation of the adenine by the acidic clay surface and a cationic binding of the protonated ring to the anionic clay surface. The reaction of the 5-prime-AMP with carbodiimide resulted in the formation of 2-prime,5-prime-pApA (18.9 percent), 3-prime,5-prime-pApA (11 percent), and AppA (4.8 percent). The yields of these oligomers obtained when poly(U) was used in place of the clay were 15.5 percent, 3.7 percent, and 14.9 percent AppA, respectively.

  15. Controlling the optical properties of monocrystalline 3C-SiC heteroepitaxially grown on silicon at low temperatures

    Science.gov (United States)

    Colston, Gerard; Myronov, Maksym

    2017-11-01

    Cubic silicon carbide (3C-SiC) offers an alternative wide bandgap semiconductor to conventional materials such as hexagonal silicon carbide (4H-SiC) or gallium nitride (GaN) for the detection of UV light and can offer a closely lattice matched virtual substrate for subsequent GaN heteroepitaxy. As 3C-SiC can be heteroepitaxially grown on silicon (Si) substrates its optical properties can be manipulated by controlling the thickness and doping concentrations. The optical properties of 3C-SiC epilayers have been characterized by measuring the transmission of light through suspended membranes. Decreasing the thickness of the 3C-SiC epilayers is shown to shift the absorbance edge to lower wavelengths, a result of the indirect bandgap nature of silicon carbide. This property, among others, can be exploited to fabricate very low-cost, tuneable 3C-SiC based UV photodetectors. This study investigates the effect of thickness and doping concentration on the optical properties of 3C-SiC epilayers grown at low temperatures by a standard Si based growth process. The results demonstrate the potential photonic applications of 3C-SiC and its heterogeneous integration into the Si industry.

  16. Controlling the Formation of Ionic-Liquid-based Aqueous Biphasic Systems by Changing the Hydrogen Bonding Ability of Polyethylene Glycol End Groups

    Science.gov (United States)

    Pereira, Jorge F. B.; Kurnia, Kiki A.; Freire, Mara G.; Coutinho, João A. P.; Rogers, Robin D.

    2017-01-01

    The formation of aqueous biphasic systems (ABS) when mixing aqueous solutions of polyethylene glycol (PEG) and an ionic liquid (IL) can be controlled by modification of the hydrogen bond ability of the polymer’s end groups. It is shown that the miscibility/immiscibility on these systems stems from both the solvation of the ether groups in the oxygen chain and the ability of the PEG terminal groups to preferably hydrogen bond with water or the salt anion. The reduction of even one hydrogen bond in PEG can noticeably affect the phase behavior, especially in those regions of the phase diagram where all the ethylene oxide (EO) units of the polymeric chain are completely solvated. In this region, removing or weakening the hydrogen bond donating ability of PEG results in greater immiscibility, i.e., in a higher ability to form ABS, as a result of the much weaker interactions between the IL anion and the PEG end groups. PMID:25943332

  17. Active Metal Brazing and Characterization of Brazed Joints in C-C and C-SiC Composites to Copper-Clad-Molybdenum System

    Science.gov (United States)

    Singh, M.; Asthana, R.

    2008-01-01

    Carbon/carbon composites with CVI and resin-derived matrices, and C/SiC composites reinforced with T-300 carbon fibers in a CVI SiC matrix were joined to Cu-clad Mo using two Ag-Cu braze alloys, Cusil-ABA (1.75% Ti) and Ticusil (4.5% Ti). The brazed joints revealed good interfacial bonding, preferential precipitation of Ti at the composite/braze interface, and a tendency toward delamination in resin-derived C/C composite. Extensive braze penetration of the inter-fiber channels in the CVI C/C composites was observed. The Knoop microhardness (HK) distribution across the C/C joints indicated sharp gradients at the interface, and a higher hardness in Ticusil than in Cusil-ABA. For the C/SiC composite to Cu-clad-Mo joints, the effect of composite surface preparation revealed that ground samples did not crack whereas unground samples cracked. Calculated strain energy in brazed joints in both systems is comparable to the strain energy in a number of other ceramic/metal systems. Theoretical predictions of the effective thermal resistance suggest that such joined systems may be promising for thermal management applications.

  18. From Molecules to Surfaces: Radical-Based Mechanisms of Si-S and Si-Se Bond Formation on Silicon.

    Science.gov (United States)

    Buriak, Jillian M; Sikder, Md Delwar H

    2015-08-05

    The derivatization of silicon surfaces can have profound effects on the underlying electronic properties of the semiconductor. In this work, we investigate the radical surface chemistry of silicon with a range of organochalcogenide reagents (comprising S and Se) on a hydride-terminated silicon surface, to cleanly and efficiently produce surface Si-S and Si-Se bonds, at ambient temperature. Using a diazonium-based radical initiator, which induces formation of surface silicon radicals, a group of organochalcogenides were screened for reactivity at room temperature, including di-n-butyl disulfide, diphenyl disulfide, diphenyl diselenide, di-n-butyl sulfide, diphenyl selenide, diphenyl sulfide, 1-octadecanethiol, t-butyl disulfide, and t-butylthiol, which comprises the disulfide, diselenide, thiol, and thioether functionalities. The surface reactions were monitored by transmission mode Fourier transform infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy, and time-of-flight secondary ionization mass spectrometry. Calculation of Si-Hx consumption, a semiquantitative measure of yield of production of surface-bound Si-E bonds (E = S, Se), was carried out via FTIR spectroscopy. Control experiments, sans the BBD diazonium radical initiator, were all negative for any evident incorporation, as determined by FTIR spectroscopy. The functional groups that did react with surface silicon radicals included the dialkyl/diphenyl disulfides, diphenyl diselenide, and 1-octadecanethiol, but not t-butylthiol, diphenyl sulfide/selenide, and di-n-butyl sulfide. Through a comparison with the rich body of literature regarding molecular radicals, and in particular, silyl radicals, reaction mechanisms were proposed for each. Armed with an understanding of the reaction mechanisms, much of the known chemistry within the extensive body of radical-based reactivity has the potential to be harnessed on silicon and could be extended to a range of technologically relevant semiconductor

  19. Surface treatment with methyl formate-methyl acetate increased the shear bond strength between reline resins and denture base resin.

    Science.gov (United States)

    Osathananda, Rachanee; Wiwatwarrapan, Chairat

    2016-06-01

    Chemical surface treatment increases the shear bond strength (SBS) between hard reline resins (HRRs) and denture base resin. To evaluate the effect of methyl formate-methyl acetate (MF-MA), when used as a surface treatment agent, on the SBS between denture base resin and different HRRs. One hundred and twenty specimens of heat-polymerised acrylic resin denture base (Meliodent(®) ) were divided into 12 groups. These groups comprised denture base relined with three self-polymerised HRRs [Unifast trad(®) (UT), Tokuyama(®) RebaseII Fast (TR), Ufi gel hard(®) (UG)], and treated with their respective Bonding Agent (BA) or by MF:MA solutions at ratios of 35:65, 25:75, and 15:85 for 15 s. The SBS was measured using a Universal Testing Machine. The data were analysed using two-way anova and post hoc Tukey's analysis at p < 0.05. The highest SBS was in the UT treated with MF:MA at a ratio of 25:75 group, followed by UT treated with MF:MA at ratios of 15:85, 35:65, UT treated with BA, and all UG treated with MF:MA groups. The SBS of the UT treated with MF:MA at a ratio of 25:75 group was significantly higher than those of the groups treated with BA. The SBS of the UG treated with MF:MA groups was significantly higher than control. The TR groups treated with BA or MF:MA groups showed no significant difference in SBS. Surface treatment with MF-MA significantly enhanced the SBS of denture base resin and UT and UG compared to that of the groups treated with BA. © 2014 John Wiley & Sons A/S and The Gerodontology Association. Published by John Wiley & Sons Ltd.

  20. Synthetic Methods for Ester Bond Formation and Conformational Analysis of Ester-Containing Carbohydrates

    Science.gov (United States)

    Hackbusch, Sven

    This dissertation encompasses work related to synthetic methods for the formation of ester linkages in organic compounds, as well as the investigation of the conformational influence of the ester functional group on the flexibility of inter-saccharide linkages, specifically, and the solution phase structure of ester-containing carbohydrate derivatives, in general. Stereoselective reactions are an important part of the field of asymmetric synthesis and an understanding of their underlying mechanistic principles is essential for rational method development. Here, the exploration of a diastereoselective O-acylation reaction on a trans-2-substituted cyclohexanol scaffold is presented, along with possible reasons for the observed reversal of stereoselectivity dependent on the presence or absence of an achiral amine catalyst. In particular, this work establishes a structure-activity relationship with regard to the trans-2-substituent and its role as a chiral auxiliary in the reversal of diastereoselectivity. In the second part, the synthesis of various ester-linked carbohydrate derivatives, and their conformational analysis is presented. Using multidimensional NMR experiments and computational methods, the compounds' solution-phase structures were established and the effect of the ester functional group on the molecules' flexibility and three-dimensional (3D) structure was investigated and compared to ether or glycosidic linkages. To aid in this, a novel Karplus equation for the C(sp2)OCH angle in ester-linked carbohydrates was developed on the basis of a model ester-linked carbohydrate. This equation describes the sinusoidal relationship between the C(sp2)OCH dihedral angle and the corresponding 3JCH coupling constant that can be determined from a J-HMBC NMR experiment. The insights from this research will be useful in describing the 3D structure of naturally occurring and lab-made ester-linked derivatives of carbohydrates, as well as guiding the de novo-design of

  1. Initial Carbon-Carbon Bond Formation during the Early Stages of the Methanol-to-Olefin Process Proven by Zeolite-Trapped Acetate and Methyl Acetate

    NARCIS (Netherlands)

    Chowdhury, Abhishek Dutta; Houben, Klaartje; Whiting, Gareth T; Mokhtar, Mohamed; Asiri, Abdullah M; Al-Thabaiti, Shaeel A; Basahel, Suliman N; Baldus, Marc; Weckhuysen, Bert M

    2016-01-01

    Methanol-to-olefin (MTO) catalysis is a very active field of research because there is a wide variety of sometimes conflicting mechanistic proposals. An example is the ongoing discussion on the initial C-C bond formation from methanol during the induction period of the MTO process. By employing a

  2. Remarkably Efficient Synthesis of 2H-Indazole 1-oxides and 2H-Indazoles via Tandem Carbon–Carbon Followed by Nitrogen–Nitrogen Bond Formation

    Science.gov (United States)

    Bouillon, Isabelle; Zajíček, Jaroslav; Pudelová, Naděžda; Krchňák, Viktor

    2009-01-01

    Synthesis of Indazoles Base-catalyzed tandem carbon–carbon followed by nitrogen–nitrogen bond formations quantitatively converted N-alkyl-2-nitro-N-(2-oxo-2-aryl-ethyl)-benzenesulfonamides to 2H-indazoles 1-oxides under mild conditions. Triphenylphosphine or mesyl chloride/triethylamine-mediated deoxygenation afforded 2H-indazoles. PMID:18937414

  3. The influence of elongational flow on hydrogen bond formation and stability of the homogeneous phase of binary hydrogen- bonded polymer blends

    NARCIS (Netherlands)

    Dormidontova, Elena E.; Brinke, Gerrit ten

    2000-01-01

    Macrophase separation tendency induced by flow in binary blends of polymers capable of single hydrogen bonding between one of the chain ends is studied analytically. To describe the conformational and orientational properties of a polymer chain a simple dumbbell model is applied. It is demonstrated

  4. Unusual C-C bond cleavage in the formation of amine-bis(phenoxy) group 4 benzyl complexes: Mechanism of formation and application to stereospecific polymerization

    KAUST Repository

    Gowda, Ravikumar R.

    2014-08-11

    Group 4 tetrabenzyl compounds MBn4 (M = Zr, Ti), upon protonolysis with an equimolar amount of the tetradentate amine-tris(phenol) ligand N[(2,4-tBu2C6H2(CH 2)OH]3 in toluene from -30 to 25 °C, unexpectedly lead to amine-bis(phenoxy) dibenzyl complexes, BnCH2N[(2,4- tBu2C6H2(CH2)O] 2MBn2 (M = Zr (1), Ti (2)) in 80% (1) and 75% (2) yields. This reaction involves an apparent cleavage of the >NCH2-ArOH bond (loss of the phenol in the ligand) and formation of the >NCH 2-CH2Bn bond (gain of the benzyl group in the ligand). Structural characterization of 1 by X-ray diffraction analysis confirms that the complex formed is a bis(benzyl) complex of Zr coordinated by a newly derived tridentate amine-bis(phenoxy) ligand arranged in a mer configuration in the solid state. The abstractive activation of 1 and 2 with B(C6F 5)3·THF in CD2Cl2 at room temperature generates the corresponding benzyl cations {BnCH2N[(2,4- tBu2C6H2(CH2)O] 2MBn(THF)}+[BnB(C6F5) 3]- (M = Zr (3), Ti, (4)). These cationic complexes, along with their analogues derived from (imino)phenoxy tri- and dibenzyl complexes, [(2,6-iPr2C6H3)N=C(3,5- tBu2C6H2)O]ZrBn3 (5) and [2,4-Br2C6H2(O)(6-CH2(NC 5H9))CH2N=CH(2-adamantyl-4-MeC 6H2O)]ZrBn2 (6), have been found to effectively polymerize the biomass-derived renewable β-methyl-α-methylene- γ-butyrolactone (βMMBL) at room temperature into the highly stereoregular polymer PβMMBL with an isotacticity up to 99% mm. A combined experimental and DFT study has yielded a mechanistic pathway for the observed unusual C-C bond cleavage in the present protonolysis reaction between ZrBn4 and N[(2,4-tBu2C 6H2(CH2)OH]3 for the formation of complex 1, which involves the benzyl radical and the Zr(III) species, resulting from thermal and photochemical decomposition of ZrBn4, followed by a series of reaction sequences consisting of protonolysis, tautomerization, H-transfer, oxidation, elimination, and radical coupling. © 2014 American Chemical Society.

  5. Physical Properties of C-Si Alloys in C2/m Structure

    Science.gov (United States)

    Wang, Qian-Kun; Chai, Chang-Chun; Fan, Qing-Yang; Yang, Yin-Tang

    2017-08-01

    Using the first principles calculations based on density functional theory, the crystal structure, elastic anisotropy, and electronic properties of carbon, silicon and their alloys (C 12 Si 4, C 8 Si 8, and C 4 Si 12 ) in a monoclinic structure (C2/m) are investigated. The calculated results such as lattice parameters, elastic constants, bulk modulus, and shear modulus of C 16 and Si 16 in C2/m structure are in good accord with previous work. The elastic constants show that C 16, Si 16, and their alloys in C2/m structure are mechanically stable. The calculated results of universal anisotropy index, compression and shear anisotropy percent factors indicate that C-Si alloys present elastic anisotropy, and C 8 Si 8 shows a greater anisotropy. The Poisson’s ratio and the B/G value show that C 8 Si 8 is ductile material and other four C-Si alloys are brittle materials. In addition, Debye temperature and average sound velocity are predicted utilizing elastic modulus and density of C-Si alloys. The band structure and the partial density of states imply that C 16 and Si 16 are indirect band gap semiconductors, while C 12 Si 4, C 8 Si 8, and C 4 Si 12 are semi-metallic alloys. Supported by the Natural Science Foundation of China under Grant No. 61474089, Open Fund of Key Laboratory of Complex Electromagnetic Environment Science and Technology, China Academy of Engineering Physics under Grant No. 2015-0214. YY.K

  6. Performance and Durability of Environmental Barrier Coatings on SiC/SiC Ceramic Matrix Composites

    Science.gov (United States)

    Zhu, Dongming; Harder, Bryan; Bhatt, Ramakrishna

    2016-01-01

    This presentation highlights advanced environmental barrier coating (EBC) and SiC-SiC Ceramic Matrix Composites (CMC) systems for next generation turbine engines. The emphasis will be placed on fundamental coating and CMC property evaluations; and the integrated system performance and degradation mechanisms in simulated laboratory turbine engine testing environments. Long term durability tests in laser rig simulated high heat flux the rmomechanical creep and fatigue loading conditions will also be presented. The results can help improve the future EBC-CMC system designs, validating the advanced EBC-CMC technologies for hot section turbine engine applications.

  7. Thermophysical and mechanical properties of SiC/SiC composites

    Energy Technology Data Exchange (ETDEWEB)

    Zinkle, S.J.; Snead, L.L. [Oak Ridge National Lab., TN (United States)

    1998-09-01

    The key thermophysical and mechanical properties for SiC/SiC composites are summarized, including temperature-dependent tensile properties, elastic constants, thermal conductivity, thermal expansion, and specific heat. The effects of neutron irradiation on the thermal conductivity and dimensional stability (volumetric swelling, creep) of SiC is discussed. The estimated lower and upper temperatures limits for structural applications in high power density fusion applications are 400 and 1000 C due to thermal conductivity degradation and void swelling considerations, respectively. Further data are needed to more accurately determine these estimated temperature limits.

  8. Rapid preparation of branched and degradable AIE-active fluorescent organic nanoparticles via formation of dynamic phenyl borate bond.

    Science.gov (United States)

    Long, Zi; Liu, Meiying; Mao, Liucheng; Zeng, Guangjian; Wan, Qing; Xu, Dazhuang; Deng, Fengjie; Huang, Hongye; Zhang, Xiaoyong; Wei, Yen

    2017-02-01

    The fluorescent organic nanoparticles (FNPs) with aggregation-induced emission (AIE) feature have received increasing attention for their advanced optical properties. Although many efforts have been devoted to the fabrication and biomedical applications of AIE-active FNPs, the preparation of branched AIE-active FNPs with degradability through formation of dynamic bonds have rarely been reported. In this work, branched AIE-active FNPs were fabricated via dynamic linkage of hydrophobic hyperbranched and degradable Boltorn H40 (H40) with phenylboronic acid terminated AIE dye (PhB(OH)2) and mPEG (mPEG-B(OH)2), which relied on a facile one-pot strategy between phenylboronic acid and diol group of H40. The branched H40-star-mPEG-PhB(OH)2 FNPs were characterized using nuclear magnetic resonance spectroscopy, Fourier transform infrared spectroscopy, and fluorescence spectroscopy. Benefiting from their highly branched structure and amphiphilic properties, H40-star-mPEG-PhB(OH)2 could self-assemble into micelles and emit strong orange-red fluorescence. More importantly, cell viability results demonstrated that H40-star-mPEG-PhB(OH)2 FNPs showed good biocompatibility and promising candidates for bio-imaging. Taken together, we developed a one-pot strategy for preparation of branched AIE-active FNPs through the formation of dynamic phenyl borate. The resultant H40-star-mPEG-PhB(OH)2 FNPs should be promising biomaterials for different applications for biodegradability of H40 and responsiveness of phenyl borate. Copyright © 2016 Elsevier B.V. All rights reserved.

  9. Chemically fixed p-n heterojunctions for polymer electronics by means of covalent B-F bond formation.

    Science.gov (United States)

    Hoven, Corey V; Wang, Huiping; Elbing, Mark; Garner, Logan; Winkelhaus, Daniel; Bazan, Guillermo C

    2010-03-01

    Widely used solid-state devices fabricated with inorganic semiconductors, including light-emitting diodes and solar cells, derive much of their function from the p-n junction. Such junctions lead to diode characteristics and are attained when p-doped and n-doped materials come into contact with each other. Achieving bilayer p-n junctions with semiconducting polymers has been hindered by difficulties in the deposition of thin films with independent p-doped and n-doped layers. Here we report on how to achieve permanently fixed organic p-n heterojunctions by using a cationic conjugated polyelectrolyte with fluoride counteranions and an underlayer composed of a neutral conjugated polymer bearing anion-trapping functional groups. Application of a bias leads to charge injection and fluoride migration into the neutral layer, where irreversible covalent bond formation takes place. After the initial charging and doping, one obtains devices with no delay in the turn on of light-emitting electrochemical behaviour and excellent current rectification. Such devices highlight how mobile ions in organic media can open opportunities to realize device structures in ways that do not have analogies in the world of silicon and promise new opportunities for integrating organic materials within technologies now dominated by inorganic semiconductors.

  10. Catalytic C-N, C-O, and C-S Bond Formation Promoted by Organoactinide Complexes

    Science.gov (United States)

    Eisen, Moris S.

    Throughout this last decade, we have witnessed impressively how the chemistry of electrophilic d0/fn actinides has been prospering either in their new synthetic approaches reaching very interesting compounds or in their use in stoichiometric and catalytic reactions leading to high levels of complexity. The unique rich and complex features of organoactinides prompted the development of this field toward catalysis in demanding chemical transformations. In this review, we present a brief and selective survey of the recent developments in homogenous catalysis of organoactinide complexes, especially toward the formation of new C-N, C-O, and C-S bonds. We start by presenting the synthesis and characterization of the corresponding organoactinide complexes, followed by the homogeneous catalytic chemical transformations that include the hydroamination of terminal alkynes, the polymerization of ɛ-caprolactone and L-lactide, the reduction of azides and hydrazines by high-valent organouranium complexes, the hydrothiolation of terminal alkynes, and the catalytic Tishchenko reaction. For each reaction, the scope and the thermodynamic, kinetic, and mechanistic aspects are presented.

  11. Constructing safe and durable antibacterial textile surfaces using a robust graft-to strategy via covalent bond formation

    Science.gov (United States)

    He, Liang; Li, Sha; Chung, Cordelia T. W.; Gao, Chang; Xin, John H.

    2016-01-01

    Recently zwitterionic materials have been widely applied in the biomedical and bioengineering fields due to their excellent biocompatibility. Inspired by these, this study presents a graft-to strategy via covalent bond formation to fabricate safe and durable antibacterial textile surfaces. A novel zwitterionic sulfobetaine containing triazine reactive group was specifically designed and synthesized. MTT assay showed that it had no obvious cytotoxicity to human skin HaCaT cells as verified by ca. 89.9% relative viability at a rather high concentration of 0.8 mg·mL−1. In the evaluation for its skin sensitization, the maximum score for symptoms of erythema and edema in all tests were 0 in all observation periods. The sulfobetaine had a hydrophilic nature and the hydrophilicity of the textiles was enhanced by 43.9% when it was covalently grafted onto the textiles. Moreover, the textiles grafted with the reactive sulfobetaine exhibited durable antibacterial activities, which was verified by the fact that they showed antibacterial rates of 97.4% against gram-positive S. aureus and 93.2% against gram-negative E. coli even after they were laundered for 30 times. Therefore, the titled zwitterionic sulfobetaine is safe to human for healthcare and wound dressing and shows a promising prospect on antibacterial textile application. PMID:27808248

  12. Double Core-Shell Si@C@SiO2 for Anode Material of Lithium-Ion Batteries with Excellent Cycling Stability.

    Science.gov (United States)

    Yang, Tao; Tian, Xiaodong; Li, Xiao; Wang, Kai; Liu, Zhanjun; Guo, Quangui; Song, Yan

    2017-02-10

    Lithium-ion batteries (LIBs) composed of silicon (Si) anodes suffer from severe capacity decay because of the volume expansion deriving from the formation of Li15 Si4 alloy. In this study, we prepared a double core-shell Si@C@SiO2 nanostructure by the modified Stöber method. In the process of Si lithiation, the carbon layer alleviates the large pressure slightly then the silica shell restricts the lithiation degree of Si. The combination of carbon interlayer and silica shell guarantees structural integrity and avoids further decay of capacity because of the formation of stable solid-electrolyte interphase (SEI) films. The resultant Si@C@SiO2 presents remarkable cycling stability with capacity decay of averagely 0.03 % per cycle over 305 cycles at 200 mA g(-1) , an improvement on Si@C (0.22 %) by more than a factor of 7. This encouraging result demonstrates that the designation involved in this work is effective for mitigating the capacity decay of Si-based anodes for LIBs. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Technique development for modulus, microcracking, hermeticity, and coating evaluation capability characterization of SiC/SiC tubes

    Energy Technology Data Exchange (ETDEWEB)

    Hu, Xunxiang [Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States); Ang, Caen K. [Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States); Singh, Gyanender P. [Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States); Katoh, Yutai [Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

    2016-08-01

    Driven by the need to enlarge the safety margins of nuclear fission reactors in accident scenarios, research and development of accident-tolerant fuel has become an important topic in the nuclear engineering and materials community. A continuous-fiber SiC/SiC composite is under consideration as a replacement for traditional zirconium alloy cladding owing to its high-temperature stability, chemical inertness, and exceptional irradiation resistance. An important task is the development of characterization techniques for SiC/SiC cladding, since traditional work using rectangular bars or disks cannot directly provide useful information on the properties of SiC/SiC composite tubes for fuel cladding applications. At Oak Ridge National Laboratory, experimental capabilities are under development to characterize the modulus, microcracking, and hermeticity of as-fabricated, as-irradiated SiC/SiC composite tubes. Resonant ultrasound spectroscopy has been validated as a promising technique to evaluate the elastic properties of SiC/SiC composite tubes and microcracking within the material. A similar technique, impulse excitation, is efficient in determining the basic mechanical properties of SiC bars prepared by chemical vapor deposition; it also has potential for application in studying the mechanical properties of SiC/SiC composite tubes. Complete evaluation of the quality of the developed coatings, a major mitigation strategy against gas permeation and hydrothermal corrosion, requires the deployment of various experimental techniques, such as scratch indentation, tensile pulling-off tests, and scanning electron microscopy. In addition, a comprehensive permeation test station is being established to assess the hermeticity of SiC/SiC composite tubes and to determine the H/D/He permeability of SiC/SiC composites. This report summarizes the current status of the development of these experimental capabilities.

  14. Initial Carbon-Carbon Bond Formation during the Early Stages of the Methanol-to-Olefin Process Proven by Zeolite-Trapped Acetate and Methyl Acetate.

    Science.gov (United States)

    Chowdhury, Abhishek Dutta; Houben, Klaartje; Whiting, Gareth T; Mokhtar, Mohamed; Asiri, Abdullah M; Al-Thabaiti, Shaeel A; Basahel, Suliman N; Baldus, Marc; Weckhuysen, Bert M

    2016-12-19

    Methanol-to-olefin (MTO) catalysis is a very active field of research because there is a wide variety of sometimes conflicting mechanistic proposals. An example is the ongoing discussion on the initial C-C bond formation from methanol during the induction period of the MTO process. By employing a combination of solid-state NMR spectroscopy with UV/Vis diffuse reflectance spectroscopy and mass spectrometry on an active H-SAPO-34 catalyst, we provide spectroscopic evidence for the formation of surface acetate and methyl acetate, as well as dimethoxymethane during the MTO process. As a consequence, new insights in the formation of the first C-C bond are provided, suggesting a direct mechanism may be operative, at least in the early stages of the MTO reaction. © 2016 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

  15. Reduction of interface states by hydrogen treatment at the aluminum oxide/4H-SiC Si-face interface

    Directory of Open Access Journals (Sweden)

    Hironori Yoshioka

    2016-10-01

    Full Text Available Processes to form aluminum oxide as a gate insulator on the 4H-SiC Si-face are investigated to eliminate the interface state density (DIT and improve the mobility. Processes that do not involve the insertion or formation of SiO2 at the interface are preferential to eliminate traps that may be present in SiO2. Aluminum oxide was formed by atomic layer deposition with hydrogen plasma pretreatment followed by annealing in forming gas. Hydrogen treatment was effective to reduce DIT at the interface of aluminum oxide and SiC without a SiO2 interlayer. Optimization of the process conditions resulted in DIT for the metal oxide semiconductor (MOS capacitor of 1.7×1012 cm−2eV−1 at 0.2 eV, and the peak field-effect mobility of the MOS field-effect transistor (MOSFET was approximately 57 cm2V−1s−1.

  16. Light trapping in a-Si/c-Si heterojunction solar cells by embedded ITO nanoparticles at rear surface

    Science.gov (United States)

    Dhar, Sukanta; Mandal, Sourav; Mitra, Suchismita; Ghosh, Hemanta; Mukherjee, Sampad; Banerjee, Chandan; Saha, Hiranmoy; Barua, A. K.

    2017-12-01

    The advantages of the amorphous silicon (a-Si)/crystalline silicon (c-Si) hetero junction technology are low temperature (<200 °C) processing and fewer process steps to fabricate the device. In this work, we used indium tin oxide (ITO) nanoparticles embedded in amorphous silicon material at the rear side of the crystalline wafer. The nanoparticles were embedded in silicon to have higher scattering efficiency, as has been established by simulation studies. It has been shown that significant photocurrent enhancements (32.8 mA cm‑2 to 35.1 mA cm‑2) are achieved because of high scattering and coupling efficiency of the embedded nanoparticles into the silicon device, leading to an increase in efficiency from 13.74% to 15.22%. In addition, we have observed a small increase in open circuit voltage. This may be due to the surface passivation during the ITO nanoparticle formation with hydrogen plasma treatment. We also support our experimental results by simulation, with the help of a commercial finite-difference time-domain (FDTD) software solution.

  17. Carenium—Calkyl Bond Making and Breaking: Key Process in the Platinum-Mediated Caryl—Calkyl Bond Formation. Analogies to Organic Electrophilic Aromatic Substitution

    NARCIS (Netherlands)

    Koten, G. van; Albrecht, M.A.; Spek, A.L.

    2001-01-01

    The reaction of cationic platinum aqua complexes 2 [Pt(C6H2{CH2NMe2}2-E-4)(OH2)](X') (X' = SO3CF3, BF4) with alkyl halides RX gave various air-stable arenium complexes 3-5 containing a new C-C bond (R = Me, 3; Et, 4; Bn, 5). Electron-releasing oxo-substituents on the aromatic ligand (E = e.g., OH,

  18. A theoretical model investigation of peptide bond formation involving two water molecules in ribosome supports the two-step and eight membered ring mechanism

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Qiang [School of Chemistry & Chemical Engineering, Shandong University, Jinan 250100 (China); Gao, Jun, E-mail: gaojun@sdu.edu.cn [Agricultural Bioinformatics Key Laboratory of Hubei Province, College of Informatics, Huazhong Agricultural University, Wuhan 430070 (China); School of Chemistry & Chemical Engineering, Shandong University, Jinan 250100 (China); Zhang, Dongju; Liu, Chengbu [School of Chemistry & Chemical Engineering, Shandong University, Jinan 250100 (China)

    2015-04-01

    Highlights: • We theoretical studied peptide bond formation reaction mechanism with two water molecules. • The first water molecule can decrease the reaction barriers by forming hydrogen bonds. • The water molecule mediated three-proton transfer mechanism is the favorable mechanism. • Our calculation supports the two-step and eight membered ring mechanism. - Abstract: The ribosome is the macromolecular machine that catalyzes protein synthesis. The kinetic isotope effect analysis reported by Strobel group supports the two-step mechanism. However, the destination of the proton originating from the nucleophilic amine is uncertain. A computational simulation of different mechanisms including water molecules is carried out using the same reaction model and theoretical level. Formation the tetrahedral intermediate with proton transfer from nucleophilic nitrogen, is the rate-limiting step when two water molecules participate in peptide bond formation. The first water molecule forming hydrogen bonds with O9′ and H15′ in the A site can decrease the reaction barriers. Combined with results of the solvent isotope effects analysis, we conclude that the three-proton transfer mechanism in which water molecule mediate the proton shuttle between amino and carbon oxygen in rate-limiting step is the favorable mechanism. Our results will shield light on a better understand the reaction mechanism of ribosome.

  19. Physical origin of hydrogen-adsorption-induced metallization of the SiC surface: n-type doping via formation of hydrogen bridge bond.

    Science.gov (United States)

    Chang, Hao; Wu, Jian; Gu, Bing-Lin; Liu, Feng; Duan, Wenhui

    2005-11-04

    We perform first-principles calculations to explore the physical origin of hydrogen-induced semiconductor surface metallization observed in beta-SiC(001)-3 x 2 surface. We show that the surface metallization arises from a novel mechanism of n-type doping of surface band via formation of hydrogen bridge bonds (i.e., Si-H-Si complex). The hydrogen strengthens the weak Si-Si dimers in the subsurface by forming hydrogen bridge bonds, and donates electron to the surface conduction band.

  20. Density functional study of hydrogen bond formation between methanol and organic molecules containing Cl, F, NH2, OH, and COOH functional groups.

    Science.gov (United States)

    Kolev, Stefan K; St Petkov, Petko; Rangelov, Miroslav A; Vayssilov, Georgi N

    2011-12-08

    Various hydrogen-bonded complexes of methanol with different proton accepting and proton donating molecules containing Cl, F, NH(2), OH, OR, and COOH functional groups have been modeled using DFT with hybrid B3LYP and M05-2X functionals. The latter functional was found to provide more accurate estimates of the structural and thermodynamic parameters of the complexes of halides, amines, and alcohols. The characteristics of these complexes are influenced not only by the principle hydrogen bond of the methanol OH with the proton acceptor heteroatom, but also by additional hydrogen bonds of a C-H moiety with methanol oxygen as a proton acceptor. The contribution of the former hydrogen bond in the total binding enthalpy increases in the order chlorides hydrogen bond increases in the reverse order. A general correlation was found between the binding enthalpy of the complex and the electrostatic potential at the hydrogen center participating in the formation of the hydrogen bond. The calculated binding enthalpies of different complexes were used to clarify which functional groups can potentially form a hydrogen bond to the 2'-OH hydroxyl group in ribose, which is strong enough to block it from participation in the intramolecular catalytic activation of the peptide bond synthesis. Such blocking could result in inhibition of the protein biosynthesis in the living cell if the corresponding group is delivered as a part of a drug molecule in the vicinity of the active site in the ribosome. According to our results, such activity can be accomplished by secondary or tertiary amines, alkoxy groups, deprotonated carboxyl groups, and aliphatic fluorides, but not by the other modeled functional groups.

  1. Ablation behavior and mechanism analysis of C/SiC composites

    Directory of Open Access Journals (Sweden)

    Yang Wang

    2016-04-01

    Full Text Available Ablation is an erosive phenomenon with removal of material by a combination of thermo-mechanical, thermo-chemical, and thermo-physical factors with high temperature, pressure, and velocity of combustion flame. Materials with outstanding thermo-mechanical and thermo-chemical properties are required for future high-temperature components. C/SiC is a kind of great potential high-temperature structural material in aeronautics and astronautics with low specific weight, high specific strength, good thermal stability, oxidation resistance and excellent resistance to ablation. In this paper, the ablation phenomenon and mechanisms were summarized adequately. The ablated surface of C/SiC composites could be divided into three regions from center to external. In general, the higher the density, the lower the ablation rate; the lower the ablation temperature and less time, the lower the ablation rate, and the preparation methods also had a great influence on the ablation property. Thermo-physical and thermo-mechanical attacks were the main ablation behavior in the center region; oxidation was the main ablation behavior in the transition region and the border oxidation region.

  2. Ultrafast laser direct hard-mask writing for high efficiency c-Si texture designs

    Directory of Open Access Journals (Sweden)

    Nogami Jun

    2013-03-01

    Full Text Available This study reports a high-resolution hard-mask laser writing technique to facilitate the selective etching of crystalline silicon (c-Si into an inverted-pyramidal texture with feature size and periodicity on the order of the wavelength which, thus, provides for both anti-reflection and effective light-trapping of infrared and visible light. The process also enables engineered positional placement of the inverted-pyramid thereby providing another parameter for optimal design of an optically efficient pattern. The proposed technique, a non-cleanroom process, is scalable for large area micro-fabrication of high-efficiency thin c-Si photovoltaics. Optical wave simulations suggest the fabricated textured surface with 1.3 μm inverted-pyramids and a single anti-reflective coating increases the relative energy conversion efficiency by 11% compared to the PERL-cell texture with 9 μm inverted pyramids on a 400 μm thick wafer. This efficiency gain is anticipated to improve further for thinner wafers due to enhanced diffractive light trapping effects.

  3. Influence of Constituents on Creep Properties of SiC/SiC Composites

    Science.gov (United States)

    Bhatt, R.; DiCarlo, J.

    2016-01-01

    SiC-SiC composites are being considered as potential candidate materials for next generation turbine components such as combustor liners, nozzle vanes and blades because of their low density, high temperature capability, and tailorable mechanical properties. These composites are essentially fabricated by infiltrating matrix into a stacked array of fibers or fiber preform by one or a combination of manufacturing methods such as, Melt Infiltration (MI) of molten silicon metal, Chemical Vapor Infiltration (CVI), Polymer Infiltration and Pyrolysis (PIP). To understand the influence of constituents, the SiC-SiC composites fabricated by MI, CVI, and PIP methods were creep tested in air between 12000 and 14500 degrees Centigrade for up to 500 hours. The failed specimens were analyzed under a scanning electron microscope to assess damage mechanisms. Also, knowing the creep deformation parameters of the fiber and the matrix under the testing conditions, the creep behavior of the composites was modeled and compared with the measured data. The implications of the results on the long term durability of these composites will be discussed.

  4. The effect of hydrogen/deuterium introduction on photoluminescence of 3C-SiC crystals

    Energy Technology Data Exchange (ETDEWEB)

    Lee, B.K.; Steckl, A.J. [Univ. of Cincinnati, OH (United States). Nanoelectronics Lab.; Zavada, J.M. [Army Research Office, Research Triangle Park, NC (United States); Wilson, R.G. [Hughes Research Labs., Malibu, CA (United States)

    1998-12-31

    The effect of the incorporation and annealing of deuterium in 3C-SiC on its photoluminescence is reported. A 3C-SiC crystal has been implanted with 100 kev deuterium and subsequently annealed at temperatures between 1015 C and 1220 C for 1 to 5 minutes. SIMS depth profiles indicate hydrogen is strongly trapped by defects generated through ion bombardment, but a gradual damage repairing occurs during annealing. Photoluminescence was measured with 488 nm Ar laser excitation for sample temperatures from 89 K to 400 K. The PL peak wavelength of 540 nm at room temperature has shifted to 538 nm at 89 K. The peak PL intensity decreases with measurement temperature while its full width at half maximum (FWHM) exhibits an increasing trend. PL data were taken at five annealing stages. The post-implantation peak PL intensity and its integrated area increase initially with annealing temperature and time. After the final annealing at 1218 C for 2 minute, PL intensity and its integrated area exhibit a decrease in level.

  5. Advanced Environmental Barrier Coating Development for SiC-SiC Ceramic Matrix Composite Components

    Science.gov (United States)

    Zhu, Dongming; Harder, Bryan; Hurst, Janet B.; Halbig, Michael Charles; Puleo, Bernadette J.; Costa, Gustavo; Mccue, Terry R.

    2017-01-01

    This presentation reviews the NASA advanced environmental barrier coating (EBC) system development for SiC-SiC Ceramic Matrix Composite (CMC) combustors particularly under the NASA Environmentally Responsible Aviation, Fundamental Aeronautics and Transformative Aeronautics Concepts Programs. The emphases have been placed on the current design challenges of the 2700-3000F capable environmental barrier coatings for low NOX emission combustors for next generation turbine engines by using advanced plasma spray based processes, and the coating processing and integration with SiC-SiC CMCs and component systems. The developments also have included candidate coating composition system designs, degradation mechanisms, performance evaluation and down-selects; the processing optimizations using TriplexPro Air Plasma Spray Low Pressure Plasma Spray (LPPS), Plasma Spray Physical Vapor Deposition and demonstration of EBC-CMC systems. This presentation also highlights the EBC-CMC system temperature capability and durability improvements under the NASA development programs, as demonstrated in the simulated engine high heat flux, combustion environments, in conjunction with high heat flux, mechanical creep and fatigue loading testing conditions.

  6. Betavoltaic device in por-SiC/Si C-Nuclear Energy Converter

    Directory of Open Access Journals (Sweden)

    Akimchenko Alina

    2017-01-01

    Full Text Available The miniature and low-power devices with long service life in hard operating conditions like the Carbon-14 beta-decay energy converters indeed as eternal resource for integrated MEMS and NEMS are considered. Authors discuss how to create the power supply for MEMS/NEMS devices, based on porous SiC/Si structure, which are tested to be used as the beta-decay energy converters of radioactive C-14 into electrical energy. This is based on the silicon carbide obtaining by self-organizing mono 3C-SiC endotaxy on the Si substrate. The new idea is the C-14 atoms including in molecules in the silicon carbide porous structure by this technology, which will increase the efficiency of the converter due to the greater intensity of electron-hole pairs generation rate in the space charge region. The synthesis of C-14 can be also performed by using the electronically controlled magneto-optic chamber.

  7. Simulation of Complex Cracking in Plain Weave C/SiC Composite under Biaxial Loading

    Science.gov (United States)

    Cheng, Ron-Bin; Hsu, Su-Yuen

    2012-01-01

    Finite element analysis is performed on a mesh, based on computed geometry of a plain weave C/SiC composite with assumed internal stacking, to reveal the pattern of internal damage due to biaxial normal cyclic loading. The simulation encompasses intertow matrix cracking, matrix cracking inside the tows, and separation at the tow-intertow matrix and tow-tow interfaces. All these dissipative behaviors are represented by traction-separation cohesive laws. Not aimed at quantitatively predicting the overall stress-strain relation, the simulation, however, does not take the actual process of fiber debonding into account. The fiber tows are represented by a simple rule-of-mixture model where the reinforcing phase is a hypothetical one-dimensional material. Numerical results indicate that for the plain weave C/SiC composite, 1) matrix-crack initiation sites are primarily determined by large intertow matrix voids and interlayer tow-tow contacts, 2) the pattern of internal damage strongly depends on the loading path and initial stress, 3) compressive loading inflicts virtually no damage evolution. KEY WORDS: ceramic matrix composite, plain weave, cohesive model, brittle failure, smeared crack model, progressive damage, meso-mechanical analysis, finite element.

  8. Probabilistic Analysis of a SiC/SiC Ceramic Matrix Composite Turbine Vane

    Science.gov (United States)

    Murthy, Pappu L. N.; Nemeth, Noel N.; Brewer, David N.; Mital, Subodh

    2004-01-01

    To demonstrate the advanced composite materials technology under development within the Ultra-Efficient Engine Technology (UEET) Program, it was planned to fabricate, test, and analyze a turbine vane made entirely of silicon carbide-fiber-reinforced silicon carbide matrix composite (SiC/SiC CMC) material. The objective was to utilize a five-harness satin weave melt-infiltrated (MI) SiC/SiC composite material developed under this program to design and fabricate a stator vane that can endure 1000 hours of engine service conditions. The vane was designed such that the expected maximum stresses were kept within the proportional limit strength of the material. Any violation of this design requirement was considered as the failure. This report presents results of a probabilistic analysis and reliability assessment of the vane. Probability of failure to meet the design requirements was computed. In the analysis, material properties, strength, and pressure loading were considered as random variables. The pressure loads were considered normally distributed with a nominal variation. A temperature profile on the vane was obtained by performing a computational fluid dynamics (CFD) analysis and was assumed to be deterministic. The results suggest that for the current vane design, the chance of not meeting design requirements is about 1.6 percent.

  9. Influence of oxygen doping on resistive-switching characteristic of a-Si/c-Si device

    Science.gov (United States)

    Zhang, Jiahua; Chen, Da; Huang, Shihua

    2017-12-01

    The influence of oxygen doping on resistive-switching characteristics of Ag/a-Si/p+-c-Si device was investigated. By oxygen doping in the growth process of amorphous silicon, the device resistive-switching performances, such as the ON/OFF resistance ratios, yield and stability were improved, which may be ascribed to the significant reduction of defect density because of oxygen incorporation. The device I–V characteristics are strongly dependent on the oxygen doping concentration. As the oxygen doping concentration increases, the Si-rich device gradually transforms to an oxygen-rich device, and the device yield, switching characteristics, and stability may be improved for silver/oxygen-doped a-Si/p+-c-Si device. Finally, the device resistive-switching mechanism was analyzed. Project supported by the Zhejiang Provincial Natural Science Foundation of China (No. LY17F040001), the Open Project Program of Surface Physics Laboratory (National Key Laboratory) of Fudan University (No. KF2015_02), the Open Project Program of National Laboratory for Infrared Physics, Chinese Academy of Sciences (No. M201503), the Zhejiang Provincial Science and Technology Key Innovation Team (No. 2011R50012), and the Zhejiang Provincial Key Laboratory (No. 2013E10022).

  10. CS Bond formation by

    Indian Academy of Sciences (India)

    2017-02-02

    Feb 2, 2017 ... catalyzed transformation is maximized when combined with straight-forward reaction conditions and the for- mation of widely utilized synthetic building blocks. Recent work in the Chan,8 Cundy,9 and Evans10 laboratories have revealed the efficiency of copper(II) acetate in mediation of the cross-coupling ...

  11. Ester-Mediated Amide Bond Formation Driven by Wet-Dry Cycles: A Possible Path to Polypeptides on the Prebiotic Earth.

    Science.gov (United States)

    Forsythe, Jay G; Yu, Sheng-Sheng; Mamajanov, Irena; Grover, Martha A; Krishnamurthy, Ramanarayanan; Fernández, Facundo M; Hud, Nicholas V

    2015-08-17

    Although it is generally accepted that amino acids were present on the prebiotic Earth, the mechanism by which α-amino acids were condensed into polypeptides before the emergence of enzymes remains unsolved. Here, we demonstrate a prebiotically plausible mechanism for peptide (amide) bond formation that is enabled by α-hydroxy acids, which were likely present along with amino acids on the early Earth. Together, α-hydroxy acids and α-amino acids form depsipeptides-oligomers with a combination of ester and amide linkages-in model prebiotic reactions that are driven by wet-cool/dry-hot cycles. Through a combination of ester-amide bond exchange and ester bond hydrolysis, depsipeptides are enriched with amino acids over time. These results support a long-standing hypothesis that peptides might have arisen from ester-based precursors. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. C(arenium)-C(alkyl) bond making and breaking: key process in the platinum-mediated C(aryl)-C(alkyl) bond formation. Analogies to organic electrophilic aromatic substitution.

    Science.gov (United States)

    Albrecht, M; Spek, A L; van Koten, G

    2001-08-01

    The reaction of cationic platinum aqua complexes 2 [Pt(C(6)H(2)[CH(2)NMe(2)](2)-E-4)(OH(2))](X') (X' = SO(3)CF(3), BF(4)) with alkyl halides RX gave various air-stable arenium complexes 3-5 containing a new C-C bond (R = Me, 3; Et, 4; Bn, 5). Electron-releasing oxo-substituents on the aromatic ligand (E = e.g., OH, b; OMe, c) enhance the reactivity of the aqua complex 2 and were essential for arenium formation from alkyl halides different from MeX. This process is initiated by oxidative addition of alkyl halides to the platinum(II) center of 2, which affords (alkyl)(aryl) platinum(IV) complexes (e.g., 9, alkyl = benzyl) as intermediates. Spectroscopic analyses provided direct evidence for a subsequent reversible 1,2-sigmatropic shift of the alkyl group along the Pt-C(aryl) bond, which is identical to repetitive C(arenium)-C(alkyl) bond making and breaking and concerted metal reduction and oxidation. Temperature-dependent NMR spectroscopy revealed DeltaH degrees = -1.3 (+/- 0.1) kJ mol(-1), DeltaS degrees = +3.8 (+/- 0.2) J mol(-1) K(-1), and DeltaG degrees (298) = -2.4 (+/- 0.1) kJ mol(-1) for the formation of the arenium complex 5b from 9 involving the migration of a benzyl group. The arenium complexes were transformed to cyclohexadiene-type addition products 7 or to demetalated alkyl-substituted arenes, 8, thus completing the platinum-mediated formation of a sp(2)-sp(3) C-C bond which is analogous to the aromatic substitution of a [PtX](+) unit by an alkyl cation R(+). The formation of related trimethylsilyl arenium complexes 6 suggests arenium complexes as key intermediates, not only in (metal-mediated) sp(2)-sp(3) C-C bond making and breaking but also in silyl-directed cyclometalation.

  13. Epitaxial growth of 3C-SiC by using C{sub 60} as a carbon source; Untersuchungen zum epitaktischen Wachstum von 3C-SiC bei Verwendung einer C{sub 60}-Kohlenstoffquelle

    Energy Technology Data Exchange (ETDEWEB)

    Schreiber, Sascha

    2006-01-15

    Within this work epitaxial 3C-SiC-films were grown on Si(001) substrates and on ion beam synthesized 3C-SiC(001) pseudo substrates. A rather new process was used which is based on the simultaneous deposition of C60 and Si. In order to set up the necessary experimental conditions an ultra-high vacuum chamber has been designed and built. A RHEED system was used to examine SiC film growth in-situ. Using the described technique 3C-SiC films were grown void-free on Si(001) substrates. Deposition rates of C60 and Si were chosen adequately to maintain a Si:C ratio of approximately one during the deposition process. It was shown that stoichiometric and epitaxial 3C-SiC growth with the characteristic relationship (001)[110]Si(001)[110]3C-SiC could be achieved. TEM investigations revealed that the grown 3C-SiC films consist of individual grains that extend from the Si substrate to the film surface. Two characteristic grain types could be identified. The correlation between structure and texture of void-free grown 3C-SiC films and film thickness was studied by X-ray diffraction (XRD). Pole figure measurements showed that thin films only contain first-order 3C-SiC twins. With higher film thickness also second-order twins are found which are located as twin lamellae in grain type 2. Improvement of polar texture with increasing film thickness couldn't be observed in the investigated range of up to 550 nm. On ion beam synthesized 3C-SiC pseudo substrates homoepitaxial 3C-SiC growth could be demonstrated for the first time by using a C{sub 60} carbon source. In respect to the crystalline quality of the grown films the surface quality of the used substrates was identified as a crucial factor. Furthermore a correlation between the ratio of deposition rates of C{sub 60} and Si and 3C-SiC film quality could be found. Under silicon-rich conditions, i.e. with a Si:C ratio of slightly greater one, homoepitaxial 3C-SiC layer-by-layer growth can be achieved. Films grown under these

  14. Tomographic Evaluation of Reparative Dentin Formation after Direct Pulp Capping with Ca(OH)2, MTA, Biodentine, and Dentin Bonding System in Human Teeth.

    Science.gov (United States)

    Nowicka, Alicja; Wilk, Grażyna; Lipski, Mariusz; Kołecki, Janusz; Buczkowska-Radlińska, Jadwiga

    2015-08-01

    New materials can increase the efficiency of pulp capping through the formation of a complete reparative dentin bridge with no toxic effects. The present study involved tomographic evaluations of reparative dentin bridge formation after direct pulp capping with calcium hydroxide, mineral trioxide aggregate (MTA), Biodentine (Septodont, Saint Maur des Fossés, France), and Single Bond Universal (3M ESPE, Seefeld, Germany) in human teeth. Forty-four caries-free, intact, human third molars scheduled for extraction were subjected to mechanical pulp exposure and assigned to 1 of 4 experimental groups depending on the pulp capping agent used: calcium hydroxide, MTA, Biodentine, or Single Bond Universal. After 6 weeks, the teeth were extracted and processed for cone-beam computed tomographic imaging and histologic examination. Tomographic data, including the density and volume of formed reparative dentin bridges, were evaluated using a scoring system. The reparative dentin formed in the calcium hydroxide, MTA, and Biodentine groups was significantly superior to that formed in the Single Bond Universal group in terms of thickness and volume. The dentin bridges in the Biodentine group showed the highest average and maximum volumes. The mean density of dentin bridges was the highest in the MTA group and the lowest in the Single Bond Universal group. The volume of reparative dentin bridges formed after direct pulp capping is dependent on the material used. Biodentine and MTA resulted in the formation of bridges with a significantly higher average volume compared with Single Bond Universal, and cone-beam computed tomographic imaging allowed for the identification of the location of dentin bridges. Copyright © 2015 American Association of Endodontists. Published by Elsevier Inc. All rights reserved.

  15. Initial assessment of environmental effects on SiC/SiC composites in helium-cooled nuclear systems

    Energy Technology Data Exchange (ETDEWEB)

    Contescu, Cristian I [ORNL

    2013-09-01

    This report summarized the information available in the literature on the chemical reactivity of SiC/SiC composites and of their components in contact with the helium coolant used in HTGR, VHTR and GFR designs. In normal operation conditions, ultra-high purity helium will have chemically controlled impurities (water, oxygen, carbon dioxide, carbon monoxide, methane, hydrogen) that will create a slightly oxidizing gas environment. Little is known from direct experiments on the reactivity of third generation (nuclear grade) SiC/SiC composites in contact with low concentrations of water or oxygen in inert gas, at high temperature. However, there is ample information about the oxidation in dry and moist air of SiC/SiC composites at high temperatures. This information is reviewed first in the next chapters. The emphasis is places on the improvement in material oxidation, thermal, and mechanical properties during three stages of development of SiC fibers and at least two stages of development of the fiber/matrix interphase. The chemical stability of SiC/SiC composites in contact with oxygen or steam at temperatures that may develop in off-normal reactor conditions supports the conclusion that most advanced composites (also known as nuclear grade SiC/SiC composites) have the chemical resistance that would allow them maintain mechanical properties at temperatures up to 1200 1300 oC in the extreme conditions of an air or water ingress accident scenario. Further research is needed to assess the long-term stability of advanced SiC/SiC composites in inert gas (helium) in presence of very low concentrations (traces) of water and oxygen at the temperatures of normal operation of helium-cooled reactors. Another aspect that needs to be investigated is the effect of fast neutron irradiation on the oxidation stability of advanced SiC/SiC composites in normal operation conditions.

  16. Ion beam synthesis and characterization of large area 3C-SiC pseudo substrates for homo- and heteroepitaxy; Ionenstrahlsynthese und Charakterisierung grossflaechiger 3C-SiC-Pseudosubstrate fuer die Homo- und Heteroepitaxie

    Energy Technology Data Exchange (ETDEWEB)

    Haeberlen, Maik

    2006-12-15

    In this work, large area epitaxial 3C-SiC films on Si(100) and Si(111) were formed by ion beam synthesis and subsequently characterized for their structural and crystalline properties. These SiC/Si structures are meant to be used as SiC pseudosubstrates for the homo- and heteroepitaxial growth of other compound semiconductors. The suitability of these pseudosubstrates for this purpose was tested using various epitaxial systems and thin film growth methods. For this the homoepitaxial growth of 3C-SiC employing C{sub 60}-MBE and the heteroepitaxial growth of hexagonal GaN films grown by MOCVD and IBAMBA was studied in detail. The comparison of the structural and crystalline properties with data from literature enabled a qualified judgement of the potential of the 3C-SiC pseudosubstrates as an alternative substrate for the epitaxial growth of such films. These new 3C-SiC pseudosubstrates also enabled studies of other little known epitaxial systems: For the first time hexagonal ZnO films on (111) oriented pseudosubstrates were grown using PLD. The method if IBAMBE enabled the growth of cubic GaN layers on (100)-oriented pseudosubstrates. (orig.)

  17. Femtosecond X-ray solution scattering reveals that bond formation mechanism of a gold trimer complex is independent of excitation wavelength

    Directory of Open Access Journals (Sweden)

    Kyung Hwan Kim

    2016-07-01

    Full Text Available The [Au(CN2−]3 trimer in water experiences a strong van der Waals interaction between the d10 gold atoms due to large relativistic effect and can serve as an excellent model system to study the bond formation process in real time. The trimer in the ground state (S0 exists as a bent structure without the covalent bond between the gold atoms, and upon the laser excitation, one electron in the antibonding orbital goes to the bonding orbital, thereby inducing the formation of a covalent bond between gold atoms. This process has been studied by various time-resolved techniques, and most of the interpretation on the structure and dynamics converge except that the structure of the first intermediate (S1 has been debated due to different interpretations between femtosecond optical spectroscopy and femtosecond X-ray solution scattering. Recently, the excitation wavelength of 267 nm employed in our previous scattering experiment was suggested as the culprit for misinterpretation. Here, we revisited this issue by performing femtosecond X-ray solution scattering with 310 nm excitation and compared the results with our previous study employing 267 nm excitation. The data show that a linear S1 structure is formed within 500 fs regardless of excitation wavelength and the structural dynamics observed at both excitation wavelengths are identical to each other within experimental errors.

  18. A theoretical model investigation of peptide bond formation involving two water molecules in ribosome supports the two-step and eight membered ring mechanism

    Science.gov (United States)

    Wang, Qiang; Gao, Jun; Zhang, Dongju; Liu, Chengbu

    2015-04-01

    The ribosome is the macromolecular machine that catalyzes protein synthesis. The kinetic isotope effect analysis reported by Strobel group supports the two-step mechanism. However, the destination of the proton originating from the nucleophilic amine is uncertain. A computational simulation of different mechanisms including water molecules is carried out using the same reaction model and theoretical level. Formation the tetrahedral intermediate with proton transfer from nucleophilic nitrogen, is the rate-limiting step when two water molecules participate in peptide bond formation. The first water molecule forming hydrogen bonds with O9‧ and H15‧ in the A site can decrease the reaction barriers. Combined with results of the solvent isotope effects analysis, we conclude that the three-proton transfer mechanism in which water molecule mediate the proton shuttle between amino and carbon oxygen in rate-limiting step is the favorable mechanism. Our results will shield light on a better understand the reaction mechanism of ribosome.

  19. Nickel-Catalyzed C-S Bond Formation via Decarbonylative Thioetherification of Esters, Amides and Intramolecular Recombination Fragment Coupling of Thioesters

    KAUST Repository

    Lee, Shao-Chi

    2018-01-15

    A nickel catalyzed cross-coupling protocol for the straightforward C-S bond formation has been developed. Various mercaptans and a wide range of ester and amide substrates bearing various substituents were tolerated in this process which afforded products in good to excellent yields. Furthermore, an intramolecular protocol for the synthesis of thioethers starting from thioesters has been developed. The utility of this protocol has been demonstrated in the synthesis of benzothiophene on the bench top.

  20. First-principles study on the lonsdaleite phases of C, Si and Ge

    CERN Document Server

    Wang, S Q

    2003-01-01

    Crystalline C, Si and Ge in a lonsdaleite (hexagonal diamond) structure are studied by plane-wave pseudopotential calculations in the scheme of density-functional theory and the local density approximation. The same calculations with generalized gradient corrections and also for the cubic diamond phases of these elements are also performed for comparison. Our results show that the bulk moduli are quite similar between the diamond and lonsdaleite polytypes of these elements. The theoretical bulk modulus of lonsdaleite C is 0.2-0.3% higher than diamond. It is expected to replace diamond as the hardest material in the world. The LDA result shows lonsdaleite Ge as a semimetal for its zero band gap at its GAMMA point. Considering the exchange-correlation energy correction, it is estimated that lonsdaleite Ge is a semiconductor with a small direct band gap. (letter to the editor)

  1. First-principles study on the lonsdaleite phases of C, Si and Ge

    Energy Technology Data Exchange (ETDEWEB)

    Wang, S Q; Ye, H Q [Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, 72 Wenhua Road, Shenyang 110016 (China)

    2003-04-02

    Crystalline C, Si and Ge in a lonsdaleite (hexagonal diamond) structure are studied by plane-wave pseudopotential calculations in the scheme of density-functional theory and the local density approximation. The same calculations with generalized gradient corrections and also for the cubic diamond phases of these elements are also performed for comparison. Our results show that the bulk moduli are quite similar between the diamond and lonsdaleite polytypes of these elements. The theoretical bulk modulus of lonsdaleite C is 0.2-0.3% higher than diamond. It is expected to replace diamond as the hardest material in the world. The LDA result shows lonsdaleite Ge as a semimetal for its zero band gap at its {gamma} point. Considering the exchange-correlation energy correction, it is estimated that lonsdaleite Ge is a semiconductor with a small direct band gap. (letter to the editor)

  2. Relationship between 4H-SiC/SiO2 transition layer thickness and mobility

    Science.gov (United States)

    Biggerstaff, T. L.; Reynolds, C. L.; Zheleva, T.; Lelis, A.; Habersat, D.; Haney, S.; Ryu, S.-H.; Agarwal, A.; Duscher, G.

    2009-07-01

    The interfacial region between silicon carbide (SiC) and its native oxide contains a high density of interfacial traps, which is considered a major problem leading to a lower mobility that has hindered SiC metal oxide semiconductor field effect transistors from reaching their theoretical expectations. We investigate the microstructure and chemistry of the 4H-SiC/SiO2 interface due to variations in nitric oxide annealing and aluminum implantation using Z-contrast imaging and electron energy loss spectroscopy. A transition layer with a carbon to silicon ratio greater than 1 is consistently observed on the SiC side of the interface in each of these samples, and the width of this transition layer is found to be inversely related to the effective channel mobility measured on fabricated devices.

  3. Progress in the medicinal chemistry of silicon: C/Si exchange and beyond.

    Science.gov (United States)

    Fujii, Shinya; Hashimoto, Yuichi

    2017-04-01

    Application of silyl functionalities is one of the most promising strategies among various 'elements chemistry' approaches for the development of novel and distinctive drug candidates. Replacement of one or more carbon atoms of various biologically active compounds with silicon (so-called sila-substitution) has been intensively studied for decades, and is often effective for alteration of activity profile and improvement of metabolic profile. In addition to simple C/Si exchange, several novel approaches for utilizing silicon in medicinal chemistry have been suggested in recent years, focusing on the intrinsic differences between silicon and carbon. Sila-substitution offers great potential for enlarging the chemical space of medicinal chemistry, and provides many options for structural development of drug candidates.

  4. Porphyrin conjugated SiC/SiOx nanowires for X-ray-excited photodynamic therapy

    Science.gov (United States)

    Rossi, F.; Bedogni, E.; Bigi, F.; Rimoldi, T.; Cristofolini, L.; Pinelli, S.; Alinovi, R.; Negri, M.; Dhanabalan, S. C.; Attolini, G.; Fabbri, F.; Goldoni, M.; Mutti, A.; Benecchi, G.; Ghetti, C.; Iannotta, S.; Salviati, G.

    2015-01-01

    The development of innovative nanosystems opens new perspectives for multidisciplinary applications at the frontier between materials science and nanomedicine. Here we present a novel hybrid nanosystem based on cytocompatible inorganic SiC/SiOx core/shell nanowires conjugated via click-chemistry procedures with an organic photosensitizer, a tetracarboxyphenyl porphyrin derivative. We show that this nanosystem is an efficient source of singlet oxygen for cell oxidative stress when irradiated with 6 MV X-Rays at low doses (0.4–2 Gy). The in-vitro clonogenic survival assay on lung adenocarcinoma cells shows that 12 days after irradiation at a dose of 2 Gy, the cell population is reduced by about 75% with respect to control cells. These results demonstrate that our approach is very efficient to enhance radiation therapy effects for cancer treatments. PMID:25556299

  5. Oxidation-resistant interface coatings for SiC/SiC composites

    Energy Technology Data Exchange (ETDEWEB)

    Stinton, D.P.; Kupp, E.R.; Hurley, J.W. [and others

    1996-06-01

    The characteristics of the fiber-matrix interfaces in ceramic matrix composites control the mechanical behavior of these composites. Finite element modeling (FEM) was performed to examine the effect of interface coating modulus and coefficient of thermal expansion on composite behavior. Oxide interface coatings (mullite and alumina-titania) produced by a sol-gel method were chosen for study as a result of the FEM results. Amorphous silicon carbide deposited by chemical vapor deposition (CVD) is also being investigated for interface coatings in SiC-matrix composites. Processing routes for depositing coatings of these materials were developed. Composites with these interfaces were produced and tested in flexure both as-processed and after oxidation to examine the suitability of these materials as interface coatings for SiC/SiC composites in fossil energy applications.

  6. High-performance a -Si/c-Si heterojunction photoelectrodes for photoelectrochemical oxygen and hydrogen evolution

    KAUST Repository

    Wang, Hsin Ping

    2015-05-13

    Amorphous Si (a-Si)/crystalline Si (c-Si) heterojunction (SiHJ) can serve as highly efficient and robust photoelectrodes for solar fuel generation. Low carrier recombination in the photoelectrodes leads to high photocurrents and photovoltages. The SiHJ was designed and fabricated into both photoanode and photocathode with high oxygen and hydrogen evolution efficiency, respectively, by simply coating of a thin layer of catalytic materials. The SiHJ photoanode with sol-gel NiOx as the catalyst shows a current density of 21.48 mA/cm2 at the equilibrium water oxidation potential. The SiHJ photocathode with 2 nm sputter-coated Pt catalyst displays excellent hydrogen evolution performance with an onset potential of 0.640 V and a solar to hydrogen conversion efficiency of 13.26%, which is the highest ever reported for Si-based photocathodes. © 2015 American Chemical Society.

  7. Evaluation of microindentation properties of epitaxial 3C–SiC/Si thin films

    Energy Technology Data Exchange (ETDEWEB)

    Geetha, D. [Department of Physics, Anna University, Chennai 600025 (India); Sophia, P. Joice [UIST, St. Paul the Apostle, Ohrid 6000 (Macedonia, The Former Yugoslav Republic of); Arivuoli, D. [Crystal Growth Centre, Anna University, Chennai 600025 (India)

    2016-06-01

    The microhardness characteristics of 3C–SiC/Si films grown by vapor phase epitaxy were investigated using Vickers and Knoop indenters. The observed hardness behavior at lower load range is being attributed to indentation size effect while the substrate hardness effect is found to be prominent at higher loads. The related mechanical properties such as fracture toughness, brittleness index, and yield stress were also evaluated. In order to study the nature and behavior of the surface topography during the deformation process for the applied load, detailed atomic force microscopy images were obtained around the indented regions of the samples. It revealed that the indents formed at higher loads showed fracture characteristics with a pattern of radial cracks propagating from the indent corners.

  8. Oxidation-resistant interface coatings for SiC/SiC composites

    Energy Technology Data Exchange (ETDEWEB)

    Stinton, D.P.; Kupp, E.R.; Hurley, J.W.; Lowden, R.A. [Oak Ridge National Lab., TN (United States)] [and others

    1996-08-01

    The characteristics of the fiber-matrix interfaces in ceramic matrix composites control the mechanical behavior of these composites. Finite element modeling (FEM) was performed to examine the effect of interface coating modulus and coefficient of thermal expansion on composite behavior. Oxide interface coatings (mullite and alumina-titania) produced by a sol-gel method were chosen for study as a result of the FEM results. Amorphous silicon carbide deposited by chemical vapor deposition (CVD) is also being investigated for interface coatings in SiC-matrix composites. Processing routes for depositing coatings of these materials were developed. Composites with these interfaces were produced and tested in flexure both as-processed and after oxidation to examine the suitability of these materials as interface coatings for SiC/SiC composites in fossil energy applications.

  9. Characterization on C/SiC Ceramic Matrix Composites with Novel Fiber Coatings

    Science.gov (United States)

    Petko, Jeanne; Kiser, J. Douglas; McCue, Terry; Verrilli, Michael

    2002-01-01

    Ceramic Matrix Composites (CMCs) are attractive candidate materials in the aerospace industry due to their high specific strength, low density and higher temperature capabilities. The National Aeronautics and Space Administration (NASA) is pursuing the use of CMC components in advanced Reusable Launch Vehicle (RLV) propulsion applications. Carbon fiber-reinforced silicon carbide (C/SiC) is the primary material of interest for a variety of RLV propulsion applications. These composites offer high- strength carbon fibers and a high modulus, oxidation-resistant matrix. For comparison, two types of carbon fibers were processed with novel types of interface coatings (multilayer and pseudoporous). For RLV propulsion applications, environmental durability will be critical. The coatings show promise of protecting the carbon fibers from the oxidizing environment. The strengths and microstructures of these composite materials are presented.

  10. Mechanical Behavior and Analytical Modeling of Melt-Infiltrated SiC/SiC Woven Composite

    Science.gov (United States)

    Lang, J.; Sankar, J.; Kelkar, A. D.; Bhatt, R. T.; Baaklini, G.; Lua, J.

    1998-01-01

    The desirable properties in ceramic matrix composites (CMCs), such as high temperature strength, corrosion resistance, high toughness, low density, or good creep resistance have led to increased use of CMCs in high-speed engine structural components and structures that operate in extreme temperature and hostile aero-thermo-chemical environments. Ceramic matrix composites have been chosen for turbine material in the design of 21st century civil propulsion systems to achieve high fuel economy, improved reliability, extended life, and reduced cost. Most commercial CMCs are manufactured using a chemical vapor infiltration (CVI) process. However, a lower cost fabrication known as melt-infiltration process is also providing CMCs marked for use in hot sections of high-speed civil transports. Limited samples of a SiC/SiC melt-infiltrated woven composites are being investigated at room and elevated temperature below and above matrix cracking. These samples show graceful failure and toughness at room temperature with a reduction in strength and modulus at elevated temperatures. A generic finite element model is also being developed to predict monotonic and cyclic loading behavior of the woven composite. Use of the initial test data from the woven composite is being used for the development of the analytical model. This model is the first of a iterative process leading towards the development the model's capability to predict behavior at room and elevated temperature for monotonic and cyclic loading. The purpose of this paper is to report on the material and mechanical findings of the SiC/SiC melt-infiltrated woven composite and progress on the development of the finite element model.

  11. Electronic properties of {mu}c-Si:H layers investigated with Hall measurements

    Energy Technology Data Exchange (ETDEWEB)

    Bronger, T.

    2007-02-28

    In the present work, the electronic properties of thin layers of PECVD-grown {mu}c-Si:H have been examined using the Hall effect. The main focus was on the mobility of the carriers because this is a crucial limiting factor for the electronic quality of this material, however, the density of free carriers as well as the conductivity were also determined. In order to get a picture as comprehensive as possible, a sample matrix was studied consisting of samples with different n-type doping levels and different crystallinities. Additionally, doped samples with artificially implanted defects which could be annealed gradually were investigated. All measurements have been made temperature-dependently. During the work, a new computer control and analysis program was developed from scratch for the Hall setup. It allows for high automation as well as comprehensive error estimation, both of which being very important for high ohmic samples. All samples showed a thermally activated mobility and carrier concentration, however, there is no single activation energy. Instead, all Arrhenius plots exhibited a more or less pronounced convex curvature. This curvature was identified with the parallel connection of a broad distribution of barriers in the material, which are limiting to the transport and are overcome by thermoionic emission. From this, the model of normally distributed barriers (NDB) was derived, mathematically investigated, and successfully applied to the experimental data of this work and (for not too highly doped samples) of other works. As a significant validation of the NDB model, the relative room-temperature mobility values could be calculated just from the Arrhenius slopes and curvatures. A very important dependence turned out to be mobility versus carrier concentration. In particular the annealed sample showed a clear {mu} {proportional_to} n{sup 1/2} behaviour, which could be backed with the sample matrix. Additionally, Hall measurements on HWCVD-grown {mu}c-Si

  12. Overview of C/C-SiC Composite Development for the Orion Launch Abort System

    Science.gov (United States)

    Allen, Lee R.; Valentine, Peter G.; Schofield, Elizabeth S.; Beshears, Ronald D.; Coston, James E.

    2012-01-01

    Past and present efforts by the authors to further understanding of the ceramic matrix composite (CMC) material used in the valve components of the Orion Launch Abort System (LAS) Attitude Control Motor (ACM) will be presented. The LAS is designed to quickly lift the Orion Crew Exploration Vehicle (CEV) away from its launch vehicle in emergency abort scenarios. The ACM is a solid rocket motor which utilizes eight throttleable nozzles to maintain proper orientation of the CEV during abort operations. Launch abort systems have not been available for use by NASA on manned launches since the last Apollo ]Saturn launch in 1975. The CMC material, carbon-carbon/silicon-carbide (C/C-SiC), is manufactured by Fiber Materials, Inc. and consists of a rigid 4-directional carbon-fiber tow weave reinforced with a mixed carbon plus SiC matrix. Several valve and full system (8-valve) static motor tests have been conducted by the motor vendor. The culmination of these tests was the successful flight test of the Orion LAS Pad Abort One (PA ]1) vehicle on May 6, 2010. Due to the fast pace of the LAS development program, NASA Marshall Space Flight Center assisted the LAS community by performing a series of material and component evaluations using fired hardware from valve and full ]system development motor tests, and from the PA-1 flight ACM motor. Information will be presented on the structure of the C/C-SiC material, as well as the efficacy of various non ]destructive evaluation (NDE) techniques, including but not limited to: radiography, computed tomography, nanofocus computed tomography, and X-ray transmission microscopy. Examinations of the microstructure of the material via scanning electron microscopy and energy dispersive spectroscopy will also be discussed. The findings resulting from the subject effort are assisting the LAS Project in risk assessments and in possible modifications to the final ACM operational design.

  13. High-efficient production of SiC/SiO2 core-shell nanowires for effective microwave absorption

    KAUST Repository

    Zhong, Bo

    2017-02-21

    In the current report, we have demonstrated that the high-efficient production of SiC/SiO2 core-shell nanowires can be achieved through the introduction of trace of water vapor during the chemical vapor deposition process. The yield of the SiC/SiO2 core-shell nanowires is dramatically improved due to the introduction of water vapor. The SiC/SiO2 core-shell nanowires exhibit an excellent microwave absorption property in the frequency range of 2.0–18.0GHz with a very low weight percentage of 0.50wt.% in the absorbers. A minimum reflection loss value of −32.72dB (>99.99% attenuation) at 13.84GHz has been observed with the absorber thickness of 3.0mm. Moreover, the SiC/SiO2 core-shell nanowires based absorber can reach an effective absorption bandwidth (<−10dB) of 5.32GHz with the absorber thickness of 3.5mm. Furthermore, a possible absorption mechanism is also proposed in detail for such effective attenuation of microwave which can be attributed to the dielectric loss and magnetic loss of SiC/SiO2 core-shell nanowires.

  14. High-Temperature (1200-1400°C) Dry Oxidation of 3C-SiC on Silicon

    Science.gov (United States)

    Sharma, Y. K.; Li, F.; Jennings, M. R.; Fisher, C. A.; Pérez-Tomás, A.; Thomas, S.; Hamilton, D. P.; Russell, S. A. O.; Mawby, P. A.

    2015-11-01

    In a novel approach, high temperatures (1200-1400°C) were used to oxidize cubic silicon carbide (3C-SiC) grown on silicon substrate. High-temperature oxidation does not significantly affect 3C-SiC doping concentration, 3C-SiC structural composition, or the final morphology of the SiO2 layer, which remains unaffected even at 1400°C (the melting point of silicon is 1414°C). Metal-oxide-semiconductor capacitors (MOS-C) and lateral channel metal-oxide-semiconductor field-effect-transistors (MOSFET) were fabricated by use of the high-temperature oxidation process to study 3C-SiC/SiO2 interfaces. Unlike 4H-SiC MOSFET, there is no extra benefit of increasing the oxidation temperature from 1200°C to 1400°C. All the MOSFET resulted in a maximum field-effect mobility of approximately 70 cm2/V s.

  15. SiC/Si heterojunction diodes fabricated by self-selective and by blanket rapid thermal chemical vapor deposition

    Energy Technology Data Exchange (ETDEWEB)

    Yih, P.H.; Li, J.P.; Steckl, A.J. (Univ. of Cincinnati, OH (United States). Dept. of Electrical and Computer Engineering)

    1994-03-01

    SiC/Si heterojunction diodes have been fabricated by two different rapid thermal chemical vapor deposition (RTCVD) processes: a localized self-selective growth and blanket growth. The self-selective growth of crystalline cubic ([beta]) SiC was obtained by propane carbonization of the Si substrate in regions unprotected by an SiO[sub 2] layer, producing planar diodes. Mesa diodes were fabricated using the blanket growth of polycrystalline [beta]-SiC produced by the decomposition of methylsilane (CH[sub 3]SiH[sub 3]). The SiC/Si heterojunction diodes show good rectifying properties for both device structures. Reverse breakdown voltage of 50 V was obtained with the self-selective SiC/Si diode. The mesa diodes exhibited even higher breakdown voltages (V[sub br]) of 150 V and excellent ideality factors of 1.06 at 25 C. The high V[sub br] and good forward rectifying characteristics indicate that the SiC/Si heterojunction diode represents a promising approach for the fabrication of wide-gap emitter SiC/Si heterojunction bipolar transistors.

  16. Monoiron hydrogenase catalysis: hydrogen activation with the formation of a dihydrogen, Fe-H(delta-)...H(delta+)-O, bond and methenyl-H4MPT+ triggered hydride transfer.

    Science.gov (United States)

    Yang, Xinzheng; Hall, Michael B

    2009-08-12

    A fully optimized resting state model with a strong Fe-H(delta-)...H(delta+)-O dihydrogen bond for the active site of the third type of hydrogenase, [Fe]-hydrogenase, is proposed from density functional theory (DFT) calculations on the reformulated active site from the recent X-ray crystal structure study of C176A (Cys176 was mutated to an alanine) mutated [Fe]-hydrogenase in the presence of dithiothreitol. The computed vibrational frequencies for this new active site model possess an average error of only +/-4.5 cm(-1) with respect to the wild-type [Fe]-hydrogenase. Based on this resting state model, a new mechanism with the following unusual aspects for hydrogen activation catalyzed by [Fe]-hydrogenase is also proposed from DFT calculations. (1) Unexpected dual pathways for H(2) cleavage with proton transfer to Cys176-sulfur or 2-pyridinol's oxygen for the formation and regeneration of the resting state with an Fe-H(delta-)...H(delta+)-O dihydrogen bond before the appearance of methenyl-H(4)MPT(+) (MPT(+)). (2) The strong dihydrogen bond in this resting state structure prevents D(2)/H(2)O exchange. (3) Only upon the arrival of MPT(+) with its strong hydride affinity can D(2)/H(2)O exchange take place as the arrival of MPT(+) triggers the breaking of the strong Fe-H(delta-)...H(delta+)-O dihydrogen bond by taking a hydride from the iron center and initiating the next H(2) (D(2)) cleavage. This new mechanism is completely different than that previously proposed (J. Am. Chem. Soc. 2008, 130, 14036) which was based on an active site model related to an earlier crystal structure. Here, Fe's role is H(2) capture and hydride formation without MPT(+) while the pyridone's special role involves the protection of the hydride by the dihydrogen bond.

  17. Catalytic-site mapping of pyruvate formate lyase. Hypophosphite reaction on the acetyl-enzyme intermediate affords carbon-phosphorus bond synthesis (1-hydroxyethylphosphonate).

    Science.gov (United States)

    Plaga, W; Frank, R; Knappe, J

    1988-12-15

    Pyruvate formate-lyase of Escherichia coli cells, a homodimeric protein of 2 x 85 kDa, is distinguished by the property of containing a stable organic free radical (g = 2.0037) in its resting state. The enzyme (E-SH) achieves pyruvate conversion to acetyl-CoA via two distinct half-reactions (E-SH + pyruvate in equilibrium E-S-acetyl + formate; E-S-acetyl + CoA in equilibrium E-SH + acetyl-CoA), the first of which has been proposed to involve reversible homolytic carbon-carbon bond cleavage [J. Knappe et al. (1984) Proc. Natl Acad. Sci. USA 81, 1332-1335]. Present studies identified Cys-419 as the covalent-catalytic cysteinyl residue via CNBr fragmentation of E-S-[14C]acetyl and radio-sequencing of the isolated peptide CB-Ac (amino acid residues 406-423). Reaction of the formate analogue hypophosphite with E-S-acetyl was investigated and found to produce 1-hydroxyethylphosphonate with a thioester linkage to the adjacent Cys-418. The structure was determined from the chymotryptic peptide CH-P (amino acid residues 415-425), using 31P-NMR spectroscopy (delta = 44 ppm) and by chemical characterisation through degradation into 1-hydroxyethylphosphonate with phosphodiesterase or bromine. This novel P-C-bond synthesis involves the enzyme-based free radical and is proposed to resemble the physiological C-C-bond synthesis (pyruvate production) from formate and E-S-acetyl. These findings are interpreted as proof of a radical mechanism for the action of pyruvate formate-lyase. The central Cys-418/Cys-419 pair of the active site shows a distinctive thiolate property even in the inactive (nonradical) form of the enzyme, as determined using an iodoacetate probe.

  18. Study on Mechanical Behavior of CVD-SiC Coated C/SiC Composites under Simulated Space Environments

    Science.gov (United States)

    Yang, Xiang; Feng, Cao; Yi, Wang; Guang-de, Li; Jie, Cao

    2017-10-01

    SiC coating was prepared on the surface of C/SiC composites by chemical vapor deposition (CVD) method, and then mechanical behavior of CVD-SiC coated C/SiC composites under cold and thermal cycling had been investigated. Specimens were thermally cycled between the temperatures of -100 °C and 100 °C for up to 200 cycles, respectively. The coating was characterized by XRD, SEM and EDS. The results showed that there were no significant changes in the flexural property. CVD-SiC coated C/SiC composites had good mechanical stability in above simulated space environments. While great changes occurred on both elements and structure of the coating, from homogeneous single-phase of SiC into the inner layer of SiC and the outer of C, which caused the change of the bending strength.

  19. PIE of nuclear grade SiC/SiC flexural coupons irradiated to 10 dpa at LWR temperature

    Energy Technology Data Exchange (ETDEWEB)

    Koyanagi, Takaaki [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Katoh, Yutai [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

    2017-03-01

    Silicon carbide fiber-reinforced SiC matrix (SiC/SiC) composites are being actively investigated for accident-tolerant core structures of light water reactors (LWRs). Owing to the limited number of irradiation studies previously conducted at LWR-coolant temperature, this study examined SiC/SiC composites following neutron irradiation at 230–340°C to 2.0 and 11.8 dpa in the High Flux Isotope Reactor. The investigated materials are chemical vapor infiltrated (CVI) SiC/SiC composites with three different reinforcement fibers. The fiber materials were monolayer pyrolytic carbon (PyC)-coated Hi-NicalonTM Type-S (HNS), TyrannoTM SA3 (SA3), and SCS-UltraTM (SCS) SiC fibers. The irradiation resistance of these composites was investigated based on flexural behavior, dynamic Young’s modulus, swelling, and microstructures. There was no notable mechanical properties degradation of the irradiated HNS and SA3 SiC/SiC composites except for reduction of the Young’s moduli by up to 18%. The microstructural stability of these composites supported the absence of degradation. In addition, no progressive swelling from 2.0 to 11.8 dpa was confirmed for these composites. On the other hand, the SCS composite showed significant mechanical degradation associated with cracking within the fiber. This study determined that SiC/SiC composites with HNS or SA3 SiC/SiC fibers, a PyC interphase, and a CVI SiC matrix retain their properties beyond the lifetime dose for LWR fuel cladding at the relevant temperature.

  20. Controlling the Formation of Ionic-Liquid-based Aqueous Biphasic Systems by Changing the Hydrogen-Bonding Ability of Polyethylene Glycol End Groups.

    Science.gov (United States)

    Pereira, Jorge F B; Kurnia, Kiki A; Freire, Mara G; Coutinho, João A P; Rogers, Robin D

    2015-07-20

    The formation of aqueous biphasic systems (ABS) when mixing aqueous solutions of polyethylene glycol (PEG) and an ionic liquid (IL) can be controlled by modifying the hydrogen-bond-donating/-accepting ability of the polymer end groups. It is shown that the miscibility/immiscibility in these systems stems from both the solvation of the ether groups in the oxygen chain and the ability of the PEG terminal groups to preferably hydrogen bond with water or the anion of the salt. The removal of even one hydrogen bond in PEG can noticeably affect the phase behavior, especially in the region of the phase diagram in which all the ethylene oxide (EO) units of the polymeric chain are completely solvated. In this region, removing or weakening the hydrogen-bond-donating ability of PEG results in greater immiscibility, and thus, in a higher ability to form ABS, as a result of the much weaker interactions between the IL anion and the PEG end groups. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Biofilm formation on stainless steel and gold wires for bonded retainers in vitro and in vivo and their susceptibility to oral antimicrobials.

    Science.gov (United States)

    Jongsma, Marije A; Pelser, Floris D H; van der Mei, Henny C; Atema-Smit, Jelly; van de Belt-Gritter, Betsy; Busscher, Henk J; Ren, Yijin

    2013-05-01

    Bonded retainers are used in orthodontics to maintain treatment result. Retention wires are prone to biofilm formation and cause gingival recession, bleeding on probing and increased pocket depths near bonded retainers. In this study, we compare in vitro and in vivo biofilm formation on different wires used for bonded retainers and the susceptibility of in vitro biofilms to oral antimicrobials. Orthodontic wires were exposed to saliva, and in vitro biofilm formation was evaluated using plate counting and live/dead staining, together with effects of exposure to toothpaste slurry alone or followed by antimicrobial mouthrinse application. Wires were also placed intra-orally for 72 h in human volunteers and undisturbed biofilm formation was compared by plate counting and live/dead staining, as well as by denaturing gradient gel electrophoresis for compositional differences in biofilms. Single-strand wires attracted only slightly less biofilm in vitro than multi-strand wires. Biofilms on stainless steel single-strand wires however, were much more susceptible to antimicrobials from toothpaste slurries and mouthrinses than on single-strand gold wires and biofilms on multi-strand wires. Also, in vivo significantly less biofilm was found on single-strand than on multi-strand wires. Microbial composition of biofilms was more dependent on the volunteer involved than on wire type. Biofilms on single-strand stainless steel wires attract less biofilm in vitro and are more susceptible to antimicrobials than on multi-strand wires. Also in vivo, single-strand wires attract less biofilm than multi-strand ones. Use of single-strand wires is preferred over multi-strand wires, not because they attract less biofilm, but because biofilms on single-strand wires are not protected against antimicrobials as in crevices and niches as on multi-strand wires.

  2. Scatter in Carbon/Silicon Carbide (C/SiC) Composites Quantified

    Science.gov (United States)

    Murthy, Pappu L. N.; Gyekenyesi, John P.; Mital, Subodh K.

    2004-01-01

    Carbon-fiber-reinforced silicon carbide matrix (C/SiC) composites processed by chemical vapor infiltration are candidate materials for aerospace thermal structures. Carbon fibers can retain properties at very high temperatures, but they are known to have poor oxidation resistance in adverse, high-temperature environments. Nevertheless, the combination of CVI-SiC matrix with higher stiffness and oxidation resistance, the interfacial coating, and additional surface-seal coating provides the necessary protection to the carbon fibers, and makes the material viable for high-temperature space applications operating under harsh environments. Furthermore, C/SiC composites, like other ceramic matrix composites (CMCs), exhibit graceful non-catastrophic failure because of various inherent energy dissipating mechanisms. The material exhibits nonlinearity in deformation even at very low stress levels. This is the result of the severe matrix microcracking present in the as processed composite because of large differences between the coefficients of thermal expansion of the fiber and the matrix. Utilization of these advanced composites in next generation space vehicles will require innovative structural configurations, updated materials, and refined analyses. Structural safety issues for these vehicles are in direct competition with performance and cost. One would have to quantify the uncertainties associated with the design using formal probabilistic methods. Specifically four fundamental aspects on which analyses are based-- (1) loading conditions, (2) material behavior, (3) geometrical configurations, and (4) structural connections between the composite components and baseline structure--are stochastic in nature. A direct way to formally account for uncertainties is to develop probabilistic structural analysis methods where all participating variables are described by appropriate probability density functions. The present work, however, focuses on analyzing the stochastic

  3. Experimental and theoretical evaluation of the reactions leading to formation of internal double bonds in suspension PVC

    NARCIS (Netherlands)

    Purmova, Jindra; Pauwels, Kim F. D.; Agostini, Michela; Bruinsma, Maarten; Vorenkamp, Eltio J.; Schouten, Arend J.; Coote, Michelle L.

    2008-01-01

    The number of internal double bonds in poly(vinyl chloride) (PVC) samples was studied as a function of molecular weight at various monomer conversions. These defect structures were found to exhibit end-group-like characteristics: their concentration per chain was largely constant as a function of

  4. Controlling superstructural ordering in the clathrate-I Ba8M16P30 (M = Cu, Zn) through the formation of metal-metal bonds.

    Science.gov (United States)

    Dolyniuk, J; Whitfield, P S; Lee, K; Lebedev, O I; Kovnir, K

    2017-05-01

    Order-disorder-order phase transitions in the clathrate-I Ba8Cu16P30 were induced and controlled by aliovalent substitutions of Zn into the framework. Unaltered Ba8Cu16P30 crystallizes in an ordered orthorhombic (Pbcn) clathrate-I superstructure that maintains complete segregation of metal and phosphorus atoms over 23 different crystallographic positions in the clathrate framework. The driving force for the formation of this Pbcn superstructure is the avoidance of Cu-Cu bonds. This superstructure is preserved upon aliovalent substitution of Zn for Cu in Ba8Cu16-x Zn x P30 with 0 Cu-Zn bonds in the framework, leading to a collapse of the orthorhombic superstructure into the more common cubic subcell of clathrate-I (Pm3n). In the resulting cubic phases, each clathrate framework position is jointly occupied by three different elements: Cu, Zn, and P. Detailed structural characterization of the Ba-Cu-Zn-P clathrates-I via single crystal X-ray diffraction, joint synchrotron X-ray and neutron powder diffractions, pair distribution function analysis, electron diffraction and high-resolution electron microscopy, along with elemental analysis, indicates that local ordering is present in the cubic clathrate framework, suggesting the evolution of Cu-Zn bonds. For the compounds with the highest Zn content, a disorder-order transformation is detected due to the formation of another superstructure with trigonal symmetry and Cu-Zn bonds in the clathrate-I framework. It is shown that small changes in the composition, synthesis, and crystal structure have significant impacts on the structural and transport properties of Zn-substituted Ba8Cu16P30.

  5. An Investigation of SiC/SiC Woven Composite Under Monotonic and Cyclic Loading

    Science.gov (United States)

    Lang, J.; Sankar, J.; Kelkar, A. D.; Bhatt, R. T.; Singh, M.; Lua, J.

    1997-01-01

    The desirable properties in ceramic matrix composites (CMCs), such as high temperature strength, corrosion resistance, high toughness, low density, or good creep resistance have led to increased use of CMCs in high-speed engine structural components and structures that operate in extreme temperature and hostile aero-thermo-chemical environments. Ceramic matrix composites have been chosen for turbine material in the design of 21 st-century civil propulsion systems to achieve high fuel economy, improved reliability, extended life, and reduced cost. Most commercial CMCs are manufactured using a chemical vapor infiltration (CVI) process. However, a lower cost fabrication known as melt-infiltration process is also providing CMCs marked for use in hot sections of high-speed civil transports. The scope of this paper is to report on the material and mechanical characterization of the CMCs subjected to this process and to predict the behavior through an analytical model. An investigation of the SiC/SiC 8-harness woven composite is ongoing and its tensile strength and fatigue behavior is being characterized for room and elevated temperatures. The investigation is being conducted at below and above the matrix cracking stress once these parameters are identified. Fractography and light microscopy results are being studied to characterize the failure modes resulting from pure uniaxial loading. A numerical model is also being developed to predict the laminate properties by using the constituent material properties and tow undulation.

  6. SiC/SiC Leading Edge Turbine Airfoil Tested Under Simulated Gas Turbine Conditions

    Science.gov (United States)

    Robinson, R. Craig; Hatton, Kenneth S.

    1999-01-01

    Silicon-based ceramics have been proposed as component materials for use in gas turbine engine hot-sections. A high pressure burner rig was used to expose both a baseline metal airfoil and ceramic matrix composite leading edge airfoil to typical gas turbine conditions to comparatively evaluate the material response at high temperatures. To eliminate many of the concerns related to an entirely ceramic, rotating airfoil, this study has focused on equipping a stationary metal airfoil with a ceramic leading edge insert to demonstrate the feasibility and benefits of such a configuration. Here, the idea was to allow the SiC/SiC composite to be integrated as the airfoil's leading edge, operating in a "free-floating" or unrestrained manner. and provide temperature relief to the metal blade underneath. The test included cycling the airfoils between simulated idle, lift, and cruise flight conditions. In addition, the airfoils were air-cooled, uniquely instrumented, and exposed to the same internal and external conditions, which included gas temperatures in excess of 1370 C (2500 F). Results show the leading edge insert remained structurally intact after 200 simulated flight cycles with only a slightly oxidized surface. The instrumentation clearly suggested a significant reduction (approximately 600 F) in internal metal temperatures as a result of the ceramic leading edge. The object of this testing was to validate the design and analysis done by Materials Research and Design of Rosemont, PA and to determine the feasibility of this design for the intended application.

  7. 3C-SiC microdisk mechanical resonators with multimode resonances at radio frequencies

    Science.gov (United States)

    Lee, Jaesung; Zamani, Hamidrera; Rajgopal, Srihari; Zorman, Christian A.; X-L Feng, Philip

    2017-07-01

    We report on the design, modeling, fabrication and measurement of single-crystal 3C-silicon carbide (SiC) microdisk mechanical resonators with multimode resonances operating at radio frequencies (RF). These microdisk resonators (center-clamped on a vertical stem pedestal) offer multiple flexural-mode resonances with frequencies dependent on both disk and anchor dimensions. The resonators are made using a novel fabrication method comprised of focused ion beam nanomachining and hydroflouic : nitric : acetic (HNA) acid etching. Resonance peaks (in the frequency spectrum) are detected through laser-interferometry measurements. Resonators with different dimensions are tested, and multimode resonances, mode splitting, energy dissipation (in the form of quality factor measurement) are investigated. Further, we demonstrate a feedback oscillator based on a passive 3C-SiC resonator. This investigation provides important guidelines for microdisk resonator development, ranging from an analytical prediction of frequency scaling law to fabrication, suggesting RF microdisk resonators can be good candidates for future sensing applications in harsh environments.

  8. Development of Design Analysis Methods for C/SiC Composite Structures

    Science.gov (United States)

    Sullivan, Roy M.; Mital, Subodh K.; Murthy, Pappu L. N.; Palko, Joseph L.; Cueno, Jacques C.; Koenig, John R.

    2006-01-01

    The stress-strain behavior at room temperature and at 1100 C (2000 F) was measured for two carbon-fiber-reinforced silicon carbide (C/SiC) composite materials: a two-dimensional plain-weave quasi-isotropic laminate and a three-dimensional angle-interlock woven composite. Micromechanics-based material models were developed for predicting the response properties of these two materials. The micromechanics based material models were calibrated by correlating the predicted material property values with the measured values. Four-point beam bending sub-element specimens were fabricated with these two fiber architectures and four-point bending tests were performed at room temperature and at 1100 C. Displacements and strains were measured at various locations along the beam and recorded as a function of load magnitude. The calibrated material models were used in concert with a nonlinear finite element solution to simulate the structural response of these two materials in the four-point beam bending tests. The structural response predicted by the nonlinear analysis method compares favorably with the measured response for both materials and for both test temperatures. Results show that the material models scale up fairly well from coupon to subcomponent level.

  9. Issues on Fabrication and Evaluation of SiC/SiC Tubes With Various Fiber Architectures

    Science.gov (United States)

    Yun, H. M.; DiCarlo, J. A.; Fox, D. S.

    2004-01-01

    SiC/SiC engine components, high-modulus Sylramic-iBN SiC fiber tows were used to form nine different tubular architectural preforms with 13 mm (0.5 in.) inner diameter and lengths of approx. 75 and 230 mm (approx. 3 and approx, 9 in.). The thin-walled preforms were then coated with a BN interphase and densified with a hybrid SiC matrix using nearly the same process steps previously established for slurry-cast melt-infiltrated Sylramic-iBN/BN/SiC flat panels. The as-fabricated CMC tubes were microstructurally evaluated and tested for tensile hoop and flexural behavior, and some of the tubes were also tested in a low-pressure burner rig test with a high thru-thickness thermal gradient. To date, four general tube scale-up issues have been identified: greater CVI deposits on outer wall than inner wall; increased ply thickness and reduced fiber fraction; poor test standards for accurately determining the hoop strength of a small-diameter tube; and poor hoop strength for architectures with seams or ply ends. The underlying mechanisms and possible methods for their minimization are discussed.

  10. Optimization of self-interstitial clusters in 3C-SiC with genetic algorithm

    Science.gov (United States)

    Ko, Hyunseok; Kaczmarowski, Amy; Szlufarska, Izabela; Morgan, Dane

    2017-08-01

    Under irradiation, SiC develops damage commonly referred to as black spot defects, which are speculated to be self-interstitial atom clusters. To understand the evolution of these defect clusters and their impacts (e.g., through radiation induced swelling) on the performance of SiC in nuclear applications, it is important to identify the cluster composition, structure, and shape. In this work the genetic algorithm code StructOpt was utilized to identify groundstate cluster structures in 3C-SiC. The genetic algorithm was used to explore clusters of up to ∼30 interstitials of C-only, Si-only, and Si-C mixtures embedded in the SiC lattice. We performed the structure search using Hamiltonians from both density functional theory and empirical potentials. The thermodynamic stability of clusters was investigated in terms of their composition (with a focus on Si-only, C-only, and stoichiometric) and shape (spherical vs. planar), as a function of the cluster size (n). Our results suggest that large Si-only clusters are likely unstable, and clusters are predominantly C-only for n ≤ 10 and stoichiometric for n > 10. The results imply that there is an evolution of the shape of the most stable clusters, where small clusters are stable in more spherical geometries while larger clusters are stable in more planar configurations. We also provide an estimated energy vs. size relationship, E(n), for use in future analysis.

  11. Long term stability of c-Si surface passivation using corona charged SiO2

    Science.gov (United States)

    Bonilla, Ruy S.; Reichel, Christian; Hermle, Martin; Hamer, Phillip; Wilshaw, Peter R.

    2017-08-01

    Recombination at the semiconductor surface continues to be a major limit to optoelectronic device performance, in particular for solar cells. Passivation films reduce surface recombination by a combination of chemical and electric field effect components. Dielectric films used for this purpose, however, must also accomplish optical functions at the cell surface. In this paper, corona charge is seen as a potential method to enhance the passivation properties of a dielectric film while maintaining its optical characteristics. It is observed that corona charge can produce extreme reductions in surface recombination via field effect, in the best case leading to lifetimes exceeding 5 ms at an injection of 1015 cm-3. For a 200 μm n-type 1 Ω cm c-Si wafer, this equates to surface recombination velocities below 0.65 cm/s and J0e values of 0.92 fA/cm2. The average improvement in passivation after corona charging gave lifetimes of 1-3 ms. This was stabilised for a period of 3 years by chemically treating the films to prevent water absorption. Surface recombination was kept below 7 cm/s, and J0e power in the cell (the loss in power output) when the passivation is kept better than 16 fA/cm2, and as high as 10% if front recombination is worse than 100 fA/cm2.

  12. Characterization of C/SiC Ceramic Matrix Composites (CMCs) with Novel Interface Fiber Coatings

    Science.gov (United States)

    Petko, Jeanne F.; Kiser, J. Douglas; Gray, Hugh R. (Technical Monitor)

    2002-01-01

    Ceramic Matrix Composites (CMCs) are attractive candidate aerospace materials due to their high specific strength, low density and high temperature capabilities. The National Aeronautics and Space Administration (NASA) is pursuing the use of CMC components in advanced Reusable Launch Vehicle (RLV) propulsion applications. Carbon fiber-reinforced silicon carbide (C/SiC) is the primary material of interest for a variety of RLV propulsion applications. These composites consist of high-strength carbon fibers and a high modulus, oxidation resistant matrix. For RLV propulsion applications, environmental durability will be critical. Two types of carbon fibers were processed with both standard (pyrolytic carbon) and novel (multilayer and pseudoporous) types of interface coatings as part of a study investigating various combinations of constituents. The benefit of protecting the composites with a surface sealant was also investigated. The strengths, durability in oxidizing environments, and microstructures of these developmental composite materials are presented. The novel interface coatings and the surface sealant show promise for protecting the carbon fibers from the oxidizing environment.

  13. Modelling on c-Si/a-Si:H wire solar cells: some key parameters to optimize the photovoltaic performance

    Directory of Open Access Journals (Sweden)

    Alvarez J.

    2012-07-01

    Full Text Available Solar cells based on silicon nano- or micro-wires have attracted much attention as a promising path for low cost photovoltaic technology. The key point of this structure is the decoupling of the light absorption from the carriers collection. In order to predict and optimize the performance potential of p- (or n- doped c-Si/ n-(or p- doped a-Si:H nanowire-based solar cells, we have used the Silvaco-Atlas software to model a single-wire device. In particular, we have noticed a drastic decrease of the open-circuit voltage (Voc when increasing the doping density of the silicon core beyond an optimum value. We present here a detailed study of the parameters that can alter the Voc of c-Si(p/a-Si:H (n wires according to the doping density in c-Si. A comparison with simulation results obtained on planar c-Si/a-Si:H heterojunctions shows that the drop in Voc, linked to an increase of the dark current in both structures, is more pronounced for radial junctions due to geometric criteria. These numerical modelling results have lead to a better understanding of transport phenomena within the wire.

  14. Modelling on c-Si/a-Si:H wire solar cells: some key parameters to optimize the photovoltaic performance

    Science.gov (United States)

    Ngo, I.; Gueunier-Farret, M. E.; Alvarez, J.; Kleider, J. P.

    2012-07-01

    Solar cells based on silicon nano- or micro-wires have attracted much attention as a promising path for low cost photovoltaic technology. The key point of this structure is the decoupling of the light absorption from the carriers collection. In order to predict and optimize the performance potential of p- (or n-) doped c-Si/ n-(or p-) doped a-Si:H nanowire-based solar cells, we have used the Silvaco-Atlas software to model a single-wire device. In particular, we have noticed a drastic decrease of the open-circuit voltage (Voc) when increasing the doping density of the silicon core beyond an optimum value. We present here a detailed study of the parameters that can alter the Voc of c-Si(p)/a-Si:H (n) wires according to the doping density in c-Si. A comparison with simulation results obtained on planar c-Si/a-Si:H heterojunctions shows that the drop in Voc, linked to an increase of the dark current in both structures, is more pronounced for radial junctions due to geometric criteria. These numerical modelling results have lead to a better understanding of transport phenomena within the wire.

  15. Electrical analysis of c-Si/CGSe monolithic tandem solar cells by using a cell-selective light absorption scheme.

    Science.gov (United States)

    Jeong, Ah Reum; Choi, Sung Bin; Kim, Won Mok; Park, Jong-Keuk; Choi, Jihye; Kim, Inho; Jeong, Jeung-Hyun

    2017-11-16

    A monolithic tandem solar cell consisting of crystalline Si (c-Si)/indium tin oxide (ITO)/CuGaSe 2 (CGSe) was demonstrated by stacking a CGSe solar cell on a c-Si/ITO solar cell to obtain a photovoltaic conversion efficiency of about 10%. Electrical analyses based on cell-selective light absorption were applied to individually characterize the photovoltaic performances of the top and bottom subcells. Illumination at a frequency that could be absorbed only by a targeted top or bottom subcell permitted measurement of the open-circuit voltage of the target subcell and the shunt resistance of the non-target subcell. The cell parameters measured from each subcell were very similar to those of the corresponding single cell, confirming the validity of the suggested method. In addition, separating the light absorption intensities at the top and bottom subcells made us measure the bias-dependent photocurrent for each subcell. The series resistance of a c-Si/ITO/CGSe cell subjected to bottom-cell limiting conditions was slightly large, implying that the tunnel junction was a little resistive or slightly beyond ohmic. This analysis demonstrated that aside from producing a slightly resistive tunnel junction, our fabrication processes were successful in monolithically integrating a CGSe cell onto a c-Si/ITO cell without degrading the performances of both cells.

  16. The effect of grain size and phosphorous-doping of polycrystalline 3C-SiC on infrared reflectance spectra

    Energy Technology Data Exchange (ETDEWEB)

    Rooyen, I.J. van, E-mail: Isabella.vanRooyen@inl.gov [Fuel Performance and Design Department, Idaho National Laboratory, Idaho Falls, ID 83415-6188 (United States); Department of Physics, Nelson Mandela Metropolitan University, Port Elizabeth (South Africa); Engelbrecht, J.A.A. [Department of Physics, Nelson Mandela Metropolitan University, Port Elizabeth (South Africa); Henry, A.; Janzen, E. [Department of Physics, Chemistry and Biology, Semiconductor Materials, Linkoeping University, Linkoeping 58183 (Sweden); Neethling, J.H. [Department of Physics, Nelson Mandela Metropolitan University, Port Elizabeth (South Africa); Rooyen, P.M. van [Philip M van Rooyen Network Consultants, Midlands Estates (South Africa)

    2012-03-15

    Highlights: Black-Right-Pointing-Pointer IR is investigated as a technique to measure grain size and P-doping of polycrystalline SiC. Black-Right-Pointing-Pointer Infrared plasma minima can be used to determine doping levels in 3C-SiC for doping levels greater than 5 Multiplication-Sign 10{sup 17} cm{sup -3}. Black-Right-Pointing-Pointer A linear relationship is found between FWHM and the inverse of grain size of 3C-SiC irrespective of P-doping level. Black-Right-Pointing-Pointer It is further found that {omega}{sub p} is not influenced by the grain size. Black-Right-Pointing-Pointer P-doping level has no significant effect on the linear relationship between grain size and surface roughness. - Abstract: The effect of P-doping and grain size of polycrystalline 3C-SiC on the infrared reflectance spectra is reported. The relationship between grain size and full width at half maximum (FWHM) suggest that the behavior of the 3C-SiC with the highest phosphorous doping level (of 1.2 Multiplication-Sign 10{sup 19} at. cm{sup -3}) is different from those with lower doping levels (<6.6 Multiplication-Sign 10{sup 18} at. cm{sup -3}). It is also further demonstrated that the plasma resonance frequency ({omega}{sub p}) is not influenced by the grain size.

  17. Formation of cyclobutanones by the photolytic reaction of (CO)/sub 5/Cr/double bond/C(OMe)Me with electron-rich olefins

    Energy Technology Data Exchange (ETDEWEB)

    Sierra, M.A.; Hegedus, L.S.

    1989-03-15

    Recent research has centered on the development of useful organic synthetic methodology based on the photolytic reactions of chromium Fischer carbene complexes, particularly in regards to the development of new /beta/-lactam syntheses. In the course of these studies it became evident that photolysis of chromium-carbene complexes resulted in the reversible production of chromium-ketene complexes, by a photochemically driven CO insertion into the chromium-carbene carbon double bond and that this unstable intermediate was responsible for /beta/-lactam formation.

  18. The new C-C bond formation in the reaction of o-amidophenolate indium(III) complex with alkyl iodides.

    Science.gov (United States)

    Piskunov, Alexandr V; Meshcheryakova, Irina N; Fukin, Georgy K; Shavyrin, Andrei S; Cherkasov, Vladimir K; Abakumov, Gleb A

    2013-08-07

    The reaction of bis(4,6-di-tert-butyl-N-(2,6-di-iso-propylphenyl)-o-amidophenolato)indium(III) anion with alkyl iodides is reported. This process includes oxidative addition of two RI (R = Me, Et) molecules to the non-transition metal complex and results in an alkyl transfer to ring carbon atoms with the formation of two new C-C bonds. The interaction proceeds at mild conditions and gives new indium(III) derivatives containing iminocyclohexa-1,4-dienolate type ligands.

  19. The Stereoselective Formation of Bicyclic Enamines with Bridgehead Unsaturation via Tandem C-H Bond Activation/Alkenylation/Electrocyclization

    Energy Technology Data Exchange (ETDEWEB)

    Ellman, Jonathan A.; Yotphan, Sirilata; Bergman, Robert

    2007-12-10

    Rhodium-catalyzed intermolecular C-H activation of {alpha}, {beta}-unsaturated imines in the presence of alkynes leads to a tandem process in which coupling to the alkyne occurs at the {beta}-C-H bond of the imine, followed by electrocyclization of the resulting azatriene intermediates to give dihydropyridines (eq 1). Consideration of the intramolecular version of this overall transformation (Scheme 1) raises interesting regiochemical issues. For example in a compound such as 1, where the nitrogen and alkyne are connected by a 4-carbon tether, the presumed first-formed hydrido(vinyl)rhodium function can add to the triple bond in a 1,2-fashion, producing complex 2 with a new endocyclic double bond. Alternatively, addition might occur in a 2,1-fashion, leading to product 4 with an exocyclic double bond. We now wish to report that this intramolecular cyclization occurs smoothly at 100 C, and the exocyclic double bond route is exclusively followed. Remarkably, products such as 4 do not resist further cyclization. Even though both the transition state for this process and the resulting product are presumably strained, the overall transformation leads to good yields of unusual bridgehead doubly-bonded enamines such as 5. The unique chemistry of conjugated enamine 5 is consistent with the increased strain of this molecule as well as with inhibited conjugation between the nitrogen lone pair and the adjacent double bond (vida infra). We began our investigation into the C-H activation/cyclization of alkyne-tethered imine 1 by extensive screening of transition metal catalysts for this process. Rhodium-based catalysts were found to be the most efficient (Table 1), leading exclusively to the bridgehead dienamine; none of the catalysts that were employed in the screening led to quinolizidine 3 or to the product of intramolecular Diels-Alder reaction. The optimized reaction conditions employ the electron-rich monophosphine ligand (p-NMe{sub 2})PhPEt{sub 2} in 1:1 ratio relative

  20. Grafting of diazonium salts on oxides surface: formation of aryl-O bonds on iron oxide nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Brymora, Katarzyna [LUNAM Université du Maine, IMMM UMR CNRS 6283 (France); Fouineau, Jonathan; Eddarir, Asma; Chau, François [Université Paris Diderot, Sorbonne Paris Cité, ITODYS CNRS UMR 7086 (France); Yaacoub, Nader; Grenèche, Jean-Marc [LUNAM Université du Maine, IMMM UMR CNRS 6283 (France); Pinson, Jean; Ammar, Souad [Université Paris Diderot, Sorbonne Paris Cité, ITODYS CNRS UMR 7086 (France); Calvayrac, Florent, E-mail: florent.calvayrac@univ-lemans.fr [LUNAM Université du Maine, IMMM UMR CNRS 6283 (France)

    2015-11-15

    Combining ab initio modeling and {sup 57}Fe Mössbauer spectrometry, we characterized the nature of the chemical linkage of aminoalkyl arenediazonium salt on the surface of iron oxide nanoparticles. We established that it is built through a metal–oxygen–carbon bonding and not a metal–carbon one, as usually suggested and commonly observed in previously studied metal- or carbon-based surfaces.

  1. Reactivity of damaged pyrimidines: formation of a Schiff base intermediate at the glycosidic bond of saturated dihydrouridine.

    Science.gov (United States)

    Jian, Yajun; Lin, Gengjie; Chomicz, Lidia; Li, Lei

    2015-03-11

    DNA glycosylases catalyze the first step of the base excision repair (BER) pathway. The chemistry used by these enzymes for deglycosylation has been largely considered as the chemistry of the oxocarbenium ion, e.g., direct rupture of the C1'-N1 bond resulting in an oxocarbenium ion intermediate. Here we present mechanistic studies revealing the 2'-deoxyribose isomerization and subsequent deglycosylation processes in two pyrimidine lesions: 5,6-dihydro-2'-deoxyuridine (dHdU) and 5,6-dihydrothymidine (dHT), formed via ionizing radiation damage to 2'-deoxycytidine and thymidine, respectively, under anoxic conditions. Acid or heat treatment of these two lesions leads to the production of two pairs of C1' epimers containing a pyranose and a furanose, respectively, indicating that both lesions favor the rupture of the C1'-O4' bond, resulting in a Schiff base intermediate at the N-glycosidic bond. Such a Schiff base intermediate was trapped and characterized by either Pd-catalyzed hydrogenation or thiol-mediated addition reaction. In contrast, in undamaged 2'-deoxyuridine and thymidine, reactions at elevated temperatures lead to the release of nucleobases most likely via the traditional oxocarbenium ion pathway. DFT calculations further support the experimental findings, suggesting that the oxocarbenium ion intermediate is responsible for the deglycosylation process if the integrity of the pyrimidine ring is maintained, while the Schiff base intermediate is preferred if the C5═C6 bond is saturated. Currently, the oxocarbenium ion pathway is indicated to be solely responsible for the deglycosylation in BER enzymes, however our results suggest an alternative Schiff base mechanism which may be responsible for the repair of saturated pyrimidine damages.

  2. Strong stacking between FH--N hydrogen-bonded foldamers and fullerenes: formation of supramolecular nano networks.

    Science.gov (United States)

    Li, Chuang; Zhu, Yuan-Yuan; Yi, Hui-Ping; Li, Chang-Zhi; Jiang, Xi-Kui; Li, Zhan-Ting; Yu, Yi-Hua

    2007-01-01

    The stacking interactions between FH--N hydrogen-bonded foldamers 1-3, bis-foldamer 4, and tris-foldamer 5 and C(60) and C(70) are described. Compound 4 contains two folded units, which are connected by an isophthalamide linker, whereas 5 has a C(3)-symmetrical discotic structure, in which three folded units are connected by a benzene-1,3,5-tricarboxamide unit. UV/Vis, fluorescence, and NMR experiments have revealed that the foldamers or folded units strongly stack with fullerenes in chloroform. The (apparent) association constants of the respective complexes have been determined by a fluorescence titration method. The strong association is tentatively attributed to intermolecular cooperative fluorophenylpi and solvophobic interactions. A similar but weaker interaction has also been observed between an MeOH--N hydrogen-bonded foldamer and fullerenes. AFM studies have revealed that the surfaces of 3 and 4 show fibrous networks, while the surface of 5 shows particles. In sharp contrast, mixtures of 3 and 4 with C(60) have been shown to generate thinner separated fibrils, whereas a mixture of 5 and C(60) produces honeycomb-like nano networks, for which a columnar cooperative stacking pattern is proposed. The results demonstrate the usefulness of FH--N hydrogen-bonded folded structures in the construction of nanoscaled materials.

  3. The Molybdenum Active Site of Formate Dehydrogenase Is Capable of Catalyzing C-H Bond Cleavage and Oxygen Atom Transfer Reactions.

    Science.gov (United States)

    Hartmann, Tobias; Schrapers, Peer; Utesch, Tillmann; Nimtz, Manfred; Rippers, Yvonne; Dau, Holger; Mroginski, Maria Andrea; Haumann, Michael; Leimkühler, Silke

    2016-04-26

    Formate dehydrogenases (FDHs) are capable of performing the reversible oxidation of formate and are enzymes of great interest for fuel cell applications and for the production of reduced carbon compounds as energy sources from CO2. Metal-containing FDHs in general contain a highly conserved active site, comprising a molybdenum (or tungsten) center coordinated by two molybdopterin guanine dinucleotide molecules, a sulfido and a (seleno-)cysteine ligand, in addition to a histidine and arginine residue in the second coordination sphere. So far, the role of these amino acids in catalysis has not been studied in detail, because of the lack of suitable expression systems and the lability or oxygen sensitivity of the enzymes. Here, the roles of these active site residues is revealed using the Mo-containing FDH from Rhodobacter capsulatus. Our results show that the cysteine ligand at the Mo ion is displaced by the formate substrate during the reaction, the arginine has a direct role in substrate binding and stabilization, and the histidine elevates the pKa of the active site cysteine. We further found that in addition to reversible formate oxidation, the enzyme is further capable of reducing nitrate to nitrite. We propose a mechanistic scheme that combines both functionalities and provides important insights into the distinct mechanisms of C-H bond cleavage and oxygen atom transfer catalyzed by formate dehydrogenase.

  4. Intelligent MONitoring System for antiviral pharmacotherapy in patients with chronic hepatitis C (SiMON-VC

    Directory of Open Access Journals (Sweden)

    Luis Margusino-Framiñán

    2017-01-01

    Full Text Available Two out of six strategic axes of pharmaceutical care in our hospital are quality and safety of care, and the incorporation of information technologies. Based on this, an information system was developed in the outpatient setting for pharmaceutical care of patients with chronic hepatitis C, SiMON-VC, which would improve the quality and safety of their pharmacotherapy. The objective of this paper is to describe requirements, structure and features of Si- MON-VC. Requirements demanded were that the information system would enter automatically all critical data from electronic clinical records at each of the visits to the Outpatient Pharmacy Unit, allowing the generation of events and alerts, documenting the pharmaceutical care provided, and allowing the use of data for research purposes. In order to meet these requirements, 5 sections were structured for each patient in SiMON-VC: Main Record, Events, Notes, Monitoring Graphs and Tables, and Follow-up. Each section presents a number of tabs with those coded data needed to monitor patients in the outpatient unit. The system automatically generates alerts for assisted prescription validation, efficacy and safety of using antivirals for the treatment of this disease. It features a completely versatile Indicator Control Panel, where temporary monitoring standards and alerts can be set. It allows the generation of reports, and their export to the electronic clinical record. It also allows data to be exported to the usual operating systems, through Big Data and Business Intelligence. Summing up, we can state that SiMON-VC improves the quality of pharmaceutical care provided in the outpatient pharmacy unit to patients with chronic hepatitis C, increasing the safety of antiviral therapy.

  5. Dielectric passivation schemes for high efficiency n-type c-si solar cells

    Energy Technology Data Exchange (ETDEWEB)

    Saynova, D.S.; Romijn, I.G.; Cesar, I.; Lamers, M.W.P.E.; Gutjahr, A. [ECN Solar Energy, P.O. Box 1, NL-1755 ZG Petten (Netherlands); Dingemans, G. [ASM, Kapeldreef 75, B-3001 Leuven (Belgium); Knoops, H.C.M.; Van de Loo, B.W.H.; Kessels, W.M.M. [Eindhoven University of Technology, Department of Appl. Physics, P.O. Box 513, 5600 MB Eindhoven (Netherlands); Siarheyeva, O.; Granneman, E. [Levitech BV, Versterkerstraat 10, 1322AP Almere (Netherlands); Venema, P.R.; Vlooswijk, A.H.G. [Tempress Systems BV, Radeweg 31, 8171 Vaassen (Netherlands); Gautero, L.; Borsa, D.M.

    2013-10-15

    We investigate the impact of different dielectric layers and stacks on the passivation properties of boron doped p{sup ++}-emitters and phosphorous doped n{sup +}-BSFs which are relevant for competitive n-type cell conversion efficiencies. The applied passivation schemes are associated with specific properties at c-Si/dielectric interface and functional mechanisms. In this way we aim to gain a deeper understanding of the passivation mechanism of the differently doped fields within the n-type cells and identify options to further improve the efficiency. The deposition technologies in our study comprise industrial PECVD systems and/or ALD both in industrial and lab scale configurations. In case of p{sup ++}-emitters the best results were achieved by combining field effect and chemical passivation using stacks of low temperature wet chemical oxide and thin ALD-AlOx capped with PECVD-SiNx. The corresponding Implied Voc values were of about (673{+-}2) mV and J{sub 0} of (68{+-}2) fA/cm{sup 2}. For the n{sup +}-BSF passivation the passivation scheme based on SiOx with or without additional AlOx film deposited by a lab scale temporal ALD processes and capped with PECVD-SiNx layer yielded a comparable Implied Voc of (673{+-}2) mV, but then corresponding to J{sub 0} value of (80{+-}15) fA/cm{sup 2}. This passivation scheme is mainly based on the chemical passivation and was also suitable for p{sup ++} surface. This means that we have demonstrated that for n-Pasha cells both the emitter and BSF can be passivated with the same type of passivation that should lead to > 20% cell efficiency. This offers the possibility for transfer this passivation scheme to advanced cell architectures, such as IBC.

  6. Electroluminescence of a-Si/c-Si heterojunction solar cells after high energy irradiation

    Energy Technology Data Exchange (ETDEWEB)

    Ferrara, Manuela

    2009-11-24

    The crystalline silicon as absorber material will certainly continue to dominate the market for space applications of solar cells. In the contribution under consideration the applicability of a-Si:H/c-Si heterojunction solar cells in space has been tested by the investigation of the cell modification by high energy protons and comparing the results to the degradation of homojunction crystalline silicon reference cells. The investigated solar cells have been irradiated with protons of different energies and doses. For all investigated solar cells the maximum damage happens for an energy of about 1.7 MeV and is mainly due to the decrease of the effective minority carrier diffusion length in the crystalline silicon absorber. Simulations carried out by AFORS-HET, a heterojunction simulation program, also confirmed this result. The main degradation mechanism for all types of devices is the monotonically decreasing charge carrier diffusion length in the p-type monocrystalline silicon absorber layer. For the heterojunction solar cell an enhancement of the photocurrent in the blue wavelength region has been observed but only in the case of heterojunction solar cell with intrinsic a-Si:H buffer layer. Additionally to the traditional characterization techniques the electroluminescence technique used for monitoring the modifications of the heteroluminescence technique used for monitoring the modifications of the heterointerface between amorphous silicon and crystalline silicon in solar cells after proton irradiation. A direct relation between minority carrier diffusion length and electroluminescence quantum efficiency has been observed but also details of the interface modification could be monitored by this technique.

  7. Effect of curing modes of dual-curing core systems on microtensile bond strength to dentin and formation of an acid-base resistant zone.

    Science.gov (United States)

    Li, Na; Takagaki, Tomohiro; Sadr, Alireza; Waidyasekera, Kanchana; Ikeda, Masaomi; Chen, Jihua; Nikaido, Toru; Tagami, Junji

    2011-12-01

    To evaluate the microtensile bond strength (μTBS) and acid-base resistant zone (ABRZ) of two dualcuring core systems to dentin using four curing modes. Sixty-four caries-free human molars were randomly divided into two groups according to two dual-curing resin core systems: (1) Clearfil DC Core Automix; (2) Estelite Core Quick. For each core system, four different curing modes were applied to the adhesive and core resin: (1) dual-cured and dual-cured (DD); (2) chemically cured and dual-cured (CD); (3) dual-cured and chemically cured (DC); (4) chemically cured and chemically cured (CC). The specimens were sectioned into sticks (n = 20 for each group) for the microtensile bond test. μTBS data were analyzed using two-way ANOVA and the Dunnett T3 test. Failure patterns were examined with scanning electron microscopy (SEM) to determine the proportion of each mode. Dentin sandwiches were produced and subjected to an acid-base challenge. After argon-ion etching, the ultrastructure of ABRZ was observed using SEM. For Clearfil DC Core Automix, the μTBS values in MPa were as follows: DD: 29.1 ± 5.4, CD: 21.6 ± 5.6, DC: 17.9 ± 2.8, CC: 11.5 ± 3.2. For Estelite Core Quick, they were: DD: 48.9 ±5.7, CD: 20.5 ± 4.7, DC: 41.4 ± 8.3, CC: 19.1 ± 6.0. The bond strength was affected by both material and curing mode, and the interaction of the two factors was significant (p core systems affects bond strength to dentin, but has no significant effect on the formation of ABRZ.

  8. Pendeo-epitaxy of stress-free AlN layer on a profiled SiC/Si substrate

    Energy Technology Data Exchange (ETDEWEB)

    Bessolov, V.N. [Ioffe Physical Technical Institute, Russian Academy of Sciences, Politekhnicheskaya 26, St. Petersburg, 194021 (Russian Federation); Institute of Problems of Mechanical Engineering, Russian Academy of Sciences, V.O., Bolshoj pr., 61, St. Petersburg, 199178 (Russian Federation); Karpov, D.V. [St. Petersburg Academic University - Nanotechnology Research and Education Centre of the Russian Academy of Sciences (Academic University), Khlopina 8/3, St Petersburg, 194021 (Russian Federation); University of Eastern Finland, P.O. Box 111, Joensuu, 80101 (Finland); Konenkova, E.V. [Ioffe Physical Technical Institute, Russian Academy of Sciences, Politekhnicheskaya 26, St. Petersburg, 194021 (Russian Federation); Institute of Problems of Mechanical Engineering, Russian Academy of Sciences, V.O., Bolshoj pr., 61, St. Petersburg, 199178 (Russian Federation); Lipovskii, A.A. [St. Petersburg Academic University - Nanotechnology Research and Education Centre of the Russian Academy of Sciences (Academic University), Khlopina 8/3, St Petersburg, 194021 (Russian Federation); Peter the Great St. Petersburg Polytechnic University, Politekhnicheskaya 29, St. Petersburg, 195251 (Russian Federation); Osipov, A.V. [Institute of Problems of Mechanical Engineering, Russian Academy of Sciences, V.O., Bolshoj pr., 61, St. Petersburg, 199178 (Russian Federation); St. Petersburg National Research University of Information Technologies, Mechanics and Optics, Kronverkskii pr. 49, St. Petersburg, 197101 (Russian Federation); Redkov, A.V. [Institute of Problems of Mechanical Engineering, Russian Academy of Sciences, V.O., Bolshoj pr., 61, St. Petersburg, 199178 (Russian Federation); St. Petersburg Academic University - Nanotechnology Research and Education Centre of the Russian Academy of Sciences (Academic University), Khlopina 8/3, St Petersburg, 194021 (Russian Federation); Peter the Great St. Petersburg Polytechnic University, Politekhnicheskaya 29, St. Petersburg, 195251 (Russian Federation); and others

    2016-05-01

    A new approach to the pendeo-epitaxy of elastically-unstrained AlN films is developed. The AlN films are grown using chloride-hydride vapor phase epitaxy (HVPE) on a silicon substrate with specially synthesized and shaped buffer layer of nano-SiC (NSiC). This NSiC epitaxial layer is grown using a new technique based on the substitution of a part of silicon atoms by carbon ones in a 100–110 nm thick subsurface layer of the silicon substrate. The 2D array of ~ 200 nm in diameter wells with the depth of ~ 70 nm that is less than the NSiC layer thickness is formed on the NSiC surface using electron beam lithography followed by reactive ion etching, the period of the array is of 400 nm. In a single HVPE process we grew ~ 20 μm thick AlN film both on the shaped and smooth regions of the prepared substrate. The AlN films are examined with reflection high energy electron diffraction, X-ray diffractometry, Raman spectroscopy and scanning electron microscopy. We use the results of these measurements to compare residual elastic stresses in the AlN film grown on the shaped and smooth regions of the substrate. The film on the shaped part of the substrate is elastically-unstrained contrary to the smooth part where elastic stresses result in the formation of a textured AlN layer. The model of the AlN growth on shaped SiC/Si substrates prepared using the atomic substitution technique is proposed. - Highlights: • A new method for chloride-hydride vapor phase pendeo-epitaxy of AlN is proposed • Unstrained AlN layer is grown on a Si substrate with a nanoprofiled SiC buffer • SiC made by substitution of atoms is well suited for the growth of AlN • Dissolution of pores in silicon beneath the nano-SiC is revealed.

  9. Admittance spectroscopy investigations of the a-Si:H/c-Si heterojunction with a view to applications in photovoltaic energy conversion; Admittanzspektroskopische Untersuchungen des a-Si:H/c-Si-Heteroueberganges im Hinblick auf photovoltaische Anwendungen

    Energy Technology Data Exchange (ETDEWEB)

    Gall, S.

    1997-12-31

    a-Si:H/c-Si heterojunctions in solar cells were investigated by admittance spectroscopy, which is able to observe defects at the a-Si:H/c-Si interface. The reasons for the investigation are stated in chapter 2. Chapter 3 describes the main characteristics of the materials involved, while chapter 4 discusses the heterojunction between the materials. Chapter 5 describes Schottky contacts on a-Si:H that were used in this investigation for investigating the heterojunction. Chapter 6 describes the preparation of specimens and chapter 7 their characterisation. Chapter 8 describes the investigations by admittance spectroscopy. Apart from the results of the measurements and simulations, also the method of measurement, the measuring set-up and the fundamentals are presented. Photovoltaic characteristics of the junctions are presented in chapter 9. The report ends with a summary. (orig.)

  10. Vibrational mode-selected differential scattering of NH3+ methanol (d1, d3, d4): Control of product branching by hydrogen-bonded complex formation

    Science.gov (United States)

    Fu, Hungshin; Qian, Jun; Green, Richard J.; Anderson, Scott L.

    1998-02-01

    We report a study of vibrational mode effects and differential scattering in reaction of NH3+ with CD3OD, CD3OH, and CH3OD over the collision energy range from 0.1 to 5 eV. At low collision energies, abstraction of both methyl and hydroxyl D atoms is observed with roughly equal probability, even though methyl D-abstraction should be favored on both energetic and statistical grounds. Branching between the two abstraction reactions is controlled by two different hydrogen-bonded complexes. Formation of these complexes is enhanced by NH3+ umbrella bending, unaffected by the NH3+ symmetric stretch, and inhibited by collision energy. Endoergic proton transfer is mediated at low energies by a third hydrogen-bonded complex, formation of which is enhanced by both umbrella bending and the symmetric stretch. Charge transfer (CT) has a significant cross section only when the NH3+ umbrella bend excitation exceeds the endoergicity. Collision energy and symmetric stretching appear to have no effect on CT. At high collision energies all reactions become direct, with near spectator stripping dynamics. In this energy range product branching appears to be controlled by collision geometry and there are no significant vibrational effects.

  11. Large Scale Solid Phase Synthesis of Peptide Drugs: Use of Commercial Anion Exchange Resin as Quenching Agent for Removal of Iodine during Disulphide Bond Formation

    Directory of Open Access Journals (Sweden)

    K. M. Bhaskara Reddy

    2012-01-01

    Full Text Available The S-acetamidomethyl (Acm or trityl (Trt protecting groups are widely used in the chemical synthesis of peptides that contain one or more disulfide bonds. Treatment of peptides containing S-Acm protecting group with iodine results in simultaneous removal of the sulfhydryl protecting group and disulfide formation. However, the excess iodine needs to be quenched or adsorbed as quickly as possible after completion of the disulfide bond formation in order to minimize side reactions that are often associated with the iodination step. We report here a simple method for simultaneous quenching and removal of iodine and isolation of disulphide bridge peptides. The use of excess inexpensive anion exchange resin to the oxidized peptide from the aqueous acetic acid/methanol solution affords quantitative removal of iodine and other color impurities. This improves the resin life time of expensive chromatography media that is used in preparative HPLC column during the purification of peptide using preparative HPLC. Further, it is very useful for the conversion of TFA salt to acetate in situ. It was successfully applied commercially, to the large scale synthesis of various peptides including Desmopressin, Oxytocin, and Octreotide. This new approach offers significant advantages such as more simple utility, minimal side reactions, large scale synthesis of peptide drugs, and greater cost effectiveness.

  12. Large Scale Solid Phase Synthesis of Peptide Drugs: Use of Commercial Anion Exchange Resin as Quenching Agent for Removal of Iodine during Disulphide Bond Formation.

    Science.gov (United States)

    Reddy, K M Bhaskara; Kumari, Y Bharathi; Mallikharjunasarma, Dokka; Bulliraju, Kamana; Sreelatha, Vanjivaka; Ananda, Kuppanna

    2012-01-01

    The S-acetamidomethyl (Acm) or trityl (Trt) protecting groups are widely used in the chemical synthesis of peptides that contain one or more disulfide bonds. Treatment of peptides containing S-Acm protecting group with iodine results in simultaneous removal of the sulfhydryl protecting group and disulfide formation. However, the excess iodine needs to be quenched or adsorbed as quickly as possible after completion of the disulfide bond formation in order to minimize side reactions that are often associated with the iodination step. We report here a simple method for simultaneous quenching and removal of iodine and isolation of disulphide bridge peptides. The use of excess inexpensive anion exchange resin to the oxidized peptide from the aqueous acetic acid/methanol solution affords quantitative removal of iodine and other color impurities. This improves the resin life time of expensive chromatography media that is used in preparative HPLC column during the purification of peptide using preparative HPLC. Further, it is very useful for the conversion of TFA salt to acetate in situ. It was successfully applied commercially, to the large scale synthesis of various peptides including Desmopressin, Oxytocin, and Octreotide. This new approach offers significant advantages such as more simple utility, minimal side reactions, large scale synthesis of peptide drugs, and greater cost effectiveness.

  13. Effect of oxygen impurity on the efficiency of the formation of complexes with H-bond and aggregation of color centers in lithium fluoride

    Science.gov (United States)

    Nebogin, S. A.; Bryukvina, L. I.; Ivanov, N. A.; Glazunov, D. S.

    2017-06-01

    The effect of impurities on the efficiency of the formation of color centers and hydrogen-bonded molecular complexes upon exposure to various radiations in lithium fluoride crystals grown in air is studied. The results of experiments for measuring optical properties, IR vibrational spectra, luminescence, and thermally stimulated luminescence are presented. The fact that the band in the range of 1800-2300 cm-1 corresponds to stretching vibrations of a complex with strong hydrogen bond is proved based on the Fermi-resonance perturbation in the region of 2080 cm-1, shaped as the Evans hole and bands A, B, and C. It is shown that the composition of these complexes includes an OH- ion and an HF molecule. The crucial role of O2‒ V a + oxygen dipoles in the aggregation efficiency and gradient distribution of color centers and radiation resistance of hydroxyl ions is revealed. It is shown that products of radiation decomposition of OH- ions stimulate, while decay of O2‒ V a + dipoles suppress, the formation of positively charged color centers.

  14. Effect of water vapor treatment on apatite formation on precalcified titanium and bond strength of coatings to substrates.

    Science.gov (United States)

    Feng, B; Chen, Y; Zhang, X D

    2002-01-01

    In previous investigations, a simple method, precalcification, was developed for bioactivating titanium. After a titanium sample was precalcified in a boiling saturated Ca(OH)(2) solution and then immersed in a calcium phosphate supersaturated solution, an apatite coating rapidly precipitated onto its surface. In the present study, heat-treatment in water vapor was carried out prior to precalcification. Heat-treatment in water vapor stimulated the chemical reaction between titanium, calcium, and phosphate. Coating properties were improved, and the bond strength of the coating to substrate was enhanced. Copyright 2001 John Wiley & Sons, Inc.

  15. When friendship formation goes down the toilet: design features of shared accommodation influence interpersonal bonds and well-being.

    Science.gov (United States)

    Easterbrook, Matthew J; Vignoles, Vivian L

    2015-03-01

    Despite its omnipresence, the influence of the built environment on human psychology is not well understood. In a five-wave longitudinal study, we investigated whether physical design features within shared student accommodation predicted the frequency of coincidental meetings between new flatmates, and whether these meetings predicted the strength of their interpersonal bonds and psychological well-being. Multilevel latent growth modelling on responses from 462 new university residents supported our hypotheses: Respondents living in flats with design features that encouraged the use of communal areas--a shared common area and an absence of ensuite toilets--reported unintentionally meeting their flatmates more frequently within their flats. This in turn predicted the initial strength of their interpersonal bonds with their flatmates, which in turn positively predicted their well-being. These effects were maintained throughout the 10-week study. Our findings provide an empirical basis for the development of shared housing designed to foster positive relationships and well-being among residents. © 2014 The British Psychological Society.

  16. Impedance spectroscopy of heterojunction solar cell a-SiC/c-Si with ITO antireflection film investigated at different temperatures

    Science.gov (United States)

    Šály, V.; Perný, M.; Janíček, F.; Huran, J.; Mikolášek, M.; Packa, J.

    2017-04-01

    Progressive smart photovoltaic technologies including heterostructures a-SiC/c-Si with ITO antireflection film are one of the prospective replacements of conventional photovoltaic silicon technology. Our paper is focused on the investigation of heterostructures a-SiC/c-Si provided with a layer of ITO (indium oxide/tin oxide 90/10 wt.%) which acts as a passivating and antireflection coating. Prepared photovoltaic cell structure was investigated at various temperatures and the influence of temperature on its operation was searched. The investigation of the dynamic properties of heterojunction PV cells was carried out using impedance spectroscopy. The equivalent AC circuit which approximates the measured impedance data was proposed. Assessment of the influence of the temperature on the operation of prepared heterostructure was carried out by analysis of the temperature dependence of AC equivalent circuit elements.

  17. Effect of simultaneous ion irradiation on microstructural change of SiC/SiC composites at high temperature

    Science.gov (United States)

    Taguchi, T.; Wakai, E.; Igawa, N.; Nogami, S.; Snead, L. L.; Hasegawa, A.; Jitsukawa, S.

    2002-12-01

    The effect of simultaneous triple ion irradiation of He, H and Si on microstructural evolution of two kinds of SiC/SiC composites (HNS composite (using Hi-Nicalon type S SiC fiber) and TSA composite (using Tyranno SA SiC fiber)) at 1000 °C has been investigated. The microstructure observations of SiC/SiC composites irradiated to 10 dpa were examined by transmission electron microscopy. He bubbles were hardly formed in matrix of TSA composite, but many helium bubbles and some cracks were observed at grain boundaries of matrix of HNS composite. He bubbles and cracks were not, on the other hand, observed in the both fiber fabrics of HNS and TSA composites. Debonding between fiber and carbon layer following irradiation region was not observed in the both composites. Under these irradiation conditions, TSA composite showed the better microstructural stability against ion beams irradiation than one of HNS composite.

  18. Optical properties of hybrid T3Pyr/SiO2/3C-SiC nanowires.

    Science.gov (United States)

    Fabbri, Filippo; Rossi, Francesca; Melucci, Manuela; Manet, Ilse; Attolini, Giovanni; Favaretto, Laura; Zambianchi, Massimo; Salviati, Giancarlo

    2012-12-17

    A new class of nanostructured hybrid materials is developed by direct grafting of a model thiophene-based organic dye on the surface of 3C-SiC/SiO2 core/shell nanowires. TEM-EDX analysis reveals that the carbon distribution is more spread than it would be, considering only the SiC core size, suggesting a main contribution from C of the oligothiophene framework. Further, the sulfur signal found along the treated wires is not detected in the as-grown samples. In addition, the fluorescent spectra are similar for the functionalized nanostructures and T3Pyr in solution, confirming homogeneous molecule grafting on the nanowire surface. Chemical and luminescence characterizations confirm a homogeneous functionalization of the nanowires. In particular, the fluorophore retains its optical properties after functionalization.

  19. Thermal Conductivity Degradation and Microstructural Damage Characterization in Low-Dose Ion Beam-Irradiated 3C-SiC

    Science.gov (United States)

    Chauhan, Vinay S.; Riyad, M. Faisal; Du, Xinpeng; Wei, Changdong; Tyburska-Püschel, Beata; Zhao, Ji-Cheng; Khafizov, Marat

    2017-12-01

    This study assesses the impact of low-dose and low-temperature irradiation on the properties of cubic silicon carbide (3C-SiC). 3C-SiC was irradiated with Kr ions to different fluences at 420 K (147 °C). Raman spectroscopy was used to investigate the impact of irradiation-induced defects on vibrational modes and time-domain thermoreflectance (TDTR) was used to measure thermal conductivity. We observe a noticeable reduction in thermal conductivity with increasing fluence. Analysis of Raman spectra reveals the longitudinal optical (LO) and transverse optical (TO) modes with noticeable peak broadening of LO mode with increasing dosage. We also notice a decrease of ratio of peak intensities of LO and TO modes in irradiated samples. We observe a correlation between the thermal conductivity reduction and the decrease in the peak intensity ratio and attribute this to the accumulation of charged vacancy defects.

  20. SiC/SiC Composites: The Effect of Fiber Type and Fiber Architecture on Mechanical Properties

    Science.gov (United States)

    Morscher, Gregory N.

    2008-01-01

    Woven SiC/SiC composites represent a broad family of composites with a broad range of properties which are of interest for many energy-based and aero-based applications. Two important features of SiC/SiC composites which one must consider are the reinforcing fibers themselves and the fiber-architecture they are formed into. The range of choices for these two features can result in a wide range of elastic, mechanical, thermal, and electrical properties. In this presentation, it will be demonstrated how the effect of fiber-type and fiber architecture effects the important property of "matrix cracking stress" for slurry-cast melt-infiltrated SiC matrix composites, which is often considered to be a critical design parameter for this system of composites.

  1. Nanoindentation, microscratch, friction and wear studies of carbon-fibre reinforced SiC-Si matrix composite

    Energy Technology Data Exchange (ETDEWEB)

    Fouquet, S.; Jouannigot, S.; Pailler, R.; Bourrat, X.; Guette, A.; Naslain, R. [Lab. des Composites Thermostructuraux (Univ. Bordeaux 1), Pessac (France); Alexis, J. [Lab. Genie de Production (Ecole Nationale d' Ingenieurs de Tarbes), Tarbes (France)

    2004-07-01

    This paper describes some tribological properties of a carbon / silicon carbide - silicon composite (C/SiC-Si). Friction and wear tests were conducted at room temperature under various relative humidity rates using a pin-on-disc test apparatus. Further study aimed at assessing the extent of the damage induced by indentation / scratch through the different parts of the composite. The mechanisms involved were discussed after examining the morphology of the worn surfaces and debris by scanning electron microscopy. For the different friction conditions, rather polished surfaces were generated but the morphology of the debris varied according to the relative humidity of the atmosphere. The indentation / scratch study revealed that damage occurred mostly as fragmentation of the carbon fibres, cracking of the silicon carbide matrix, ductile deformation and to a less extent cracking of the silicon matrix. (orig.)

  2. Formation of a Three-Electron Sulfur-Sulfur Bond as a Probe for Interaction between Side Chains of Methionine Residues.

    Science.gov (United States)

    Filipiak, Piotr; Bobrowski, Krzysztof; Hug, Gordon L; Pogocki, Dariusz; Schöneich, Christian; Marciniak, Bronislaw

    2016-09-15

    The mechanism of oxidation processes of l-Met-(Pro)n-l-Met peptides that contain two Met residues located on the N- and C-terminal and separated by a defined number (n = 0-4) of proline residues was investigated in aqueous solutions using pulse radiolysis. The use of such peptides allowed for distance control between the sulfur atoms located in the side chains of the Met residues. The formation of a contact between the side chains of the Met residues was probed by the observation of transients with σ*-type 2c-3e S∴S and S∴O bonds as well as of α-(alkylthio)alkyl radicals (αS). This approach enabled the monitoring, in real time, of the efficiency and kinetics of interactions between methionine side chains. Such knowledge is important, inter alia, for long-distance electron transfer processes because methionine side chains can serve as relay stations and also for many aspects of protein folding when the formation of a contact between two amino acid residues in an unfolded polypeptide chain plays a central role in protein-folding mechanisms. The yields of these transients (measured as G-values) were found to be dependent on the number of Pro residues; however, they were not dependent in a simple way on the average distance ⟨rS-S⟩ between the sulfur atoms in Met residues. A decrease in the yield of the (S∴S)(+) species with an increase in the number of Pro residues in the bridge occurred at the expense of an increase in the yields of the intramolecular three-electron-bonded (S∴O)(+) radical cations and αS radicals. A detailed understanding of these trends in the chemical yields was developed by modeling the underlying chemical kinetics with Langevin dynamical simulations of the various oligoproline peptide chains and combining them with a simple statistical mechanical theory on the end-to-end contact rates for polymer chains. This analysis showed that the formation of a contact between terminal Met residues in the peptides with 0-2 Pro residues was

  3. T300HoneySiC: a new near-zero CTE molded C/SiC material

    Science.gov (United States)

    Goodman, William A.; Ghasemi Nejhad, Mehrdad N.; Wright, Stan; Welson, Darren

    2015-09-01

    Using an Additive Manufacturing process, Trex Enterprises and teammates were successful in producing a 12-inch by 12-inch by 0.5-inch vented, lightweight, Honeycomb C/SiC ceramic matrix composite (CMC) panel which had a density relative to bulk silicon carbide of 11% (89% lightweighting). The so-called T300HoneySiC™ panel and facesheet stock material were fabricated into ASTM standard coupons and tested at Southern Research Institute to obtain basic materials properties data. The material properties data showed that we had made a near-zero coefficient of thermal expansion (CTE= -0.22 ppm/°C from -196°C to +24°C) CMC C/SiC material with good strength. This material will be ideal for space opto-mechanical structures and optical benches due to its near-zero CTE and light weight. The material is initially molded and then converted to a C/SiC ceramic matrix composite, thus the fabrication time can be less than 3 weeks from start to finish, resulting in low cost.

  4. Study on the effect of atmospheric plasma processing using gas mixture on 3C-SiC

    Science.gov (United States)

    Abdullah, Zulaika; Zaaba, S. K.; Nasir, N. F. Mohd; Mustaffa, M. T.; Arcena, Mayvinne; Zakaria, A.

    2017-03-01

    Atmospheric plasma processing are widely used for improving surfaces properties. Cubic silicon carbide (3C-SiC) is one of the material used as biosensor for their biocompatibility properties. In this work, we present the results of atmospheric plasma processing treatments using gas mixture on 3C-SiC surface. The 3C-SiC samples were treated at different duration and flow rate. Helium/Nitrogen and Argon/Nitrogen gas mixtures were used as plasma treatments and its effect on the surface was investigated. A significant increment of surface wettability were observed after plasma exposition. Investigation by surface morphological measurements was performed by using Atomic Force Microscopy (AFM) and Scanning Electron Microscopy (SEM). Contact angle measurement results showed a decreased in contact angle with increasing of treatment time and flow rate, and Argon/Nitrogen mixture promote more wettability compared to Helium/Nitrogen mixture. At the request of all authors of the paper, and with the agreement of the Proceedings Editor, an updated version of this article was published on 24 May 2017.

  5. Fabrication Technology and Characteristics of a Magnetic Sensitive Transistor with nc-Si:H/c-Si Heterojunction

    Directory of Open Access Journals (Sweden)

    Xiaofeng Zhao

    2017-01-01

    Full Text Available This paper presents a magnetically sensitive transistor using a nc-Si:H/c-Si heterojunction as an emitter junction. By adopting micro electro-mechanical systems (MEMS technology and chemical vapor deposition (CVD method, the nc-Si:H/c-Si heterojunction silicon magnetically sensitive transistor (HSMST chips were designed and fabricated on a p-type <100> orientation double-side polished silicon wafer with high resistivity. In addition, a collector load resistor ( R L was integrated on the chip, and the resistor converted the collector current ( I C to a collector output voltage ( V out . When I B = 8.0 mA, V DD = 10.0 V, and R L = 4.1 kΩ, the magnetic sensitivity ( S V at room temperature and temperature coefficient ( α C of the collector current for HSMST were 181 mV/T and −0.11%/°C, respectively. The experimental results show that the magnetic sensitivity and temperature characteristics of the proposed transistor can be obviously improved by the use of a nc-Si:H/c-Si heterojunction as an emitter junction.

  6. Multi-scale Model of Residual Strength of 2D Plain Weave C/SiC Composites in Oxidation Atmosphere

    Science.gov (United States)

    Chen, Xihui; Sun, Zhigang; Sun, Jianfen; Song, Yingdong

    2017-02-01

    Multi-scale models play an important role in capturing the nonlinear response of woven carbon fiber reinforced ceramic matrix composites. In plain weave carbon fiber/silicon carbon (C/SiC) composites, the carbon fibers and interphases will be oxidized at elevated temperature and the strength of the composite will be degraded when oxygen enters micro-cracks formed in the as-produced parts due to the mismatch in thermal properties between constituents. As a result of the oxidation on fiber surface, fiber shows a notch-like morphology. In this paper, the change rule of fiber notch depth is fitted by circular function. And a multi-scale model based upon the change rule of fiber notch depth is developed to simulate the residual strength and post-oxidation stress-strain curves of the composite. The multi-scale model is able to accurately predict the residual strength and post-oxidation stress-strain curves of the composite. Besides, the simulated residual strength and post-oxidation stress-strain curves of 2D plain weave C/SiC composites in oxidation atmosphere show good agreements with experimental results. Furthermore, the oxidation time and temperature of the composite are investigated to show their influences upon the residual strength and post-oxidation stress-strain curves of plain weave C/SiC composites.

  7. Fabrication Technology and Characteristics of a Magnetic Sensitive Transistor with nc-Si:H/c-Si Heterojunction.

    Science.gov (United States)

    Zhao, Xiaofeng; Li, Baozeng; Wen, Dianzhong

    2017-01-22

    This paper presents a magnetically sensitive transistor using a nc-Si:H/c-Si heterojunction as an emitter junction. By adopting micro electro-mechanical systems (MEMS) technology and chemical vapor deposition (CVD) method, the nc-Si:H/c-Si heterojunction silicon magnetically sensitive transistor (HSMST) chips were designed and fabricated on a p-type orientation double-side polished silicon wafer with high resistivity. In addition, a collector load resistor ( R L ) was integrated on the chip, and the resistor converted the collector current ( I C ) to a collector output voltage ( V out ). When I B = 8.0 mA, V DD = 10.0 V, and R L = 4.1 kΩ, the magnetic sensitivity ( S V ) at room temperature and temperature coefficient ( α C ) of the collector current for HSMST were 181 mV/T and -0.11%/°C, respectively. The experimental results show that the magnetic sensitivity and temperature characteristics of the proposed transistor can be obviously improved by the use of a nc-Si:H/c-Si heterojunction as an emitter junction.

  8. Formation of Bonded Exciplex in the Excited States of Dicyanoanthracene-Pyridine System : Time Dependent Density Functional Theory Study

    NARCIS (Netherlands)

    Setiawan, D.; Sethio, D.; Martoprawiro, M.A.; Filatov, M.; Gaol, FL; Nguyen, QV

    2012-01-01

    Strong quenching of fluorescence was recently observed in pyridine solutions of 9,10-dicyanoanthracene chromophore. It was hypothesized that quenching may be attributed to the formation of bound charge transfer complexes in the excited states of the molecules. In this work, using time-dependent

  9. Processing and Structural Advantages of the Sylramic-iBN SiC Fiber for SiC/SiC Components

    Science.gov (United States)

    Yun, H. M.; Dicarlo, J. A.; Bhatt, R. T.; Hurst, J. B.

    2008-01-01

    The successful high-temperature application of complex-shaped SiC/SiC components will depend on achieving as high a fraction of the as-produced fiber strength as possible during component fabrication and service. Key issues center on a variety of component architecture, processing, and service-related factors that can reduce fiber strength, such as fiber-fiber abrasion during architecture shaping, surface chemical attack during interphase deposition and service, and intrinsic flaw growth during high-temperature matrix formation and composite creep. The objective of this paper is to show that the NASA-developed Sylramic-iBN SiC fiber minimizes many of these issues for state-of-the-art melt-infiltrated (MI) SiC/BN/SiC composites. To accomplish this, data from various mechanical tests are presented that compare how different high performance SiC fiber types retain strength during formation of complex architectures, during processing of BN interphases and MI matrices, and during simulated composite service at high temperatures.

  10. Oligomerization reactions of deoxyribonucleotides on montmorillonite clay - The effect of mononucleotide structure, phosphate activation and montmorillonite composition on phosphodiester bond formation

    Science.gov (United States)

    Ferris, James P.; KAMALUDDIN; Ertem, Gozen

    1990-01-01

    The 2(prime)-d-5(prime)-GMP and 2(prime)-d-5(prime)-AMP bind 2 times more strongly to montmorillonite 22A than do 2(prime)-d-5(prime)-CMP and 5(prime)-TMP. The dinucleotide d(pG)2 forms in 9.2 percent yield and the cyclic dinucleotide c(dpG)2 in 5.4 percent yield in the reaction of 2(prime)-d-5(prime)-GMP with EDAC in the presence of montmorillonite 22A. The yield of dimers which contain the phosphodiester bond decreases as the reaction medium is changed from 0.2 M NaCl to a mixture of 0.2 M NaCl and 0.075 M MgCl2. A low yield of d(pA)2 was observed in the condensation reaction of 5(prime)-ImdpA on montmorillonite 22A. The yield of d(pA)2 obtained when EDAC is used as the condensing agent increases with increasing iron content of the Na(+)-montmorillonite used as catalyst. Evidence is presented which shows that the acidity of the Na(+)-montmorillonite is a necessary but not sufficient factor for the montmorillonite catalysis of phosphodiester bond formation.

  11. A Novel Strategy for Biomass Upgrade: Cascade Approach to the Synthesis of Useful Compounds via C-C Bond Formation Using Biomass-Derived Sugars as Carbon Nucleophiles

    Directory of Open Access Journals (Sweden)

    Sho Yamaguchi

    2016-07-01

    Full Text Available Due to the depletion of fossil fuels, biomass-derived sugars have attracted increasing attention in recent years as an alternative carbon source. Although significant advances have been reported in the development of catalysts for the conversion of carbohydrates into key chemicals (e.g., degradation approaches based on the dehydration of hydroxyl groups or cleavage of C-C bonds via retro-aldol reactions, only a limited range of products can be obtained through such processes. Thus, the development of a novel and efficient strategy targeted towards the preparation of a range of compounds from biomass-derived sugars is required. We herein describe the highly-selective cascade syntheses of a range of useful compounds using biomass-derived sugars as carbon nucleophiles. We focus on the upgrade of C2 and C3 oxygenates generated from glucose to yield useful compounds via C-C bond formation. The establishment of this novel synthetic methodology to generate valuable chemical products from monosaccharides and their decomposed oxygenated materials renders carbohydrates a potential alternative carbon resource to fossil fuels.

  12. Hydrogen Bonding-Mediated Microphase Separation during the Formation of Mesoporous Novolac-Type Phenolic Resin Templated by the Triblock Copolymer, PEO-b-PPO-b-PEO.

    Science.gov (United States)

    Chu, Wei-Cheng; Chiang, Shih-Fan; Li, Jheng-Guang; Kuo, Shiao-Wei

    2013-11-07

    After blending the triblock copolymer, poly(ethylene oxide-b-propylene oxide-b-ethylene oxide) (PEO-b-PPO-b-PEO) with novolac-type phenolic resin, Fourier transform infrared spectroscopy revealed that the ether groups of the PEO block were stronger hydrogen bond acceptors for the OH groups of phenolic resin than were the ether groups of the PPO block. Thermal curing with hexamethylenetetramine as the curing agent resulted in the triblock copolymer being incorporated into the phenolic resin, forming a nanostructure through a mechanism involving reaction-induced microphase separation. Mild pyrolysis conditions led to the removal of the PEO-b-PPO-b-PEO triblock copolymer and formation of mesoporous phenolic resin. This approach provided a variety of composition-dependent nanostructures, including disordered wormlike, body-centered-cubic spherical and disorder micelles. The regular mesoporous novolac-type phenolic resin was formed only at a phenolic content of 40-60 wt %, the result of an intriguing balance of hydrogen bonding interactions among the phenolic resin and the PEO and PPO segments of the triblock copolymer.

  13. Formation of intersubunit disulfide bonds and properties of the single histidine and cysteine residues in each subunit relative to the decameric structure of cyanase.

    Science.gov (United States)

    Anderson, P M; Korte, J J; Holcomb, T A; Cho, Y G; Son, C M; Sung, Y C

    1994-05-27

    Reaction of the single cysteine residue in each subunit of cyanase with certain SH reagents gives an active decameric derivative that dissociates reversibly to an inactive dimer derivative (Anderson, P. M., Johnson, W. V., Korte, J. J., Xiong, X., Sung, Y.-c., and Fuchs, J. A. (1988) J. Biol. Chem. 263, 5674-5680). Reaction of mixed disulfide dimer derivatives of cyanase with dithiothreitol at 0 degree C results in formation of a disulfide bond between the subunits in the dimer. The disulfide dimer was inactive and did not associate to a decamer; the intersubunit disulfide bond could not be formed when the dimers were associated as a decamer. The two SH groups apparently are in close proximity to each other in the dissociated dimer but not when the dimer is associated to a decamer. Substitution of glycine for the cysteine residue or of tyrosine, asparagine, glycine, valine, or leucine for the single histidine residue in each subunit gave mutant enzymes that were active. However, H113N, H113Y, and C83G were unstable at low temperature and/or ionic strength, dissociating reversibly to an inactive dimer. Efficient reassociation required the presence of bicarbonate or cyanate analog. The results are consistent with a proposed single site per subunit model explaining apparent half-site binding of substrates and the requirement of decameric structure for activity.

  14. Hydrogen Bonding-Mediated Microphase Separation during the Formation of Mesoporous Novolac-Type Phenolic Resin Templated by the Triblock Copolymer, PEO-b-PPO-b-PEO

    Directory of Open Access Journals (Sweden)

    Wei-Cheng Chu

    2013-11-01

    Full Text Available After blending the triblock copolymer, poly(ethylene oxide-b-propylene oxide-b-ethylene oxide (PEO-b-PPO-b-PEO with novolac-type phenolic resin, Fourier transform infrared spectroscopy revealed that the ether groups of the PEO block were stronger hydrogen bond acceptors for the OH groups of phenolic resin than were the ether groups of the PPO block. Thermal curing with hexamethylenetetramine as the curing agent resulted in the triblock copolymer being incorporated into the phenolic resin, forming a nanostructure through a mechanism involving reaction-induced microphase separation. Mild pyrolysis conditions led to the removal of the PEO-b-PPO-b-PEO triblock copolymer and formation of mesoporous phenolic resin. This approach provided a variety of composition-dependent nanostructures, including disordered wormlike, body-centered-cubic spherical and disorder micelles. The regular mesoporous novolac-type phenolic resin was formed only at a phenolic content of 40–60 wt %, the result of an intriguing balance of hydrogen bonding interactions among the phenolic resin and the PEO and PPO segments of the triblock copolymer.

  15. Roles of Intramolecular and Intermolecular Hydrogen Bonding in a Three-Water-Assisted Mechanism of Succinimide Formation from Aspartic Acid Residues

    Directory of Open Access Journals (Sweden)

    Ohgi Takahashi

    2014-08-01

    Full Text Available Aspartic acid (Asp residues in peptides and proteins are prone to isomerization to the β-form and racemization via a five-membered succinimide intermediate. These nonenzymatic reactions have relevance to aging and age-related diseases. In this paper, we report a three water molecule-assisted, six-step mechanism for the formation of succinimide from Asp residues found by density functional theory calculations. The first two steps constitute a stepwise iminolization of the C-terminal amide group. This iminolization involves a quintuple proton transfer along intramolecular and intermolecular hydrogen bonds formed by the C-terminal amide group, the side-chain carboxyl group, and the three water molecules. After a conformational change (which breaks the intramolecular hydrogen bond involving the iminol nitrogen and a reorganization of water molecules, the iminol nitrogen nucleophilically attacks the carboxyl carbon of the Asp side chain to form a five-membered ring. This cyclization is accompanied by a triple proton transfer involving two water molecules, so that a gem-diol tetrahedral intermediate is formed. The last step is dehydration of the gem-diol group catalyzed by one water molecule, and this is the rate-determining step. The calculated overall activation barrier (26.7 kcal mol−1 agrees well with an experimental activation energy.

  16. A Novel Strategy for Biomass Upgrade: Cascade Approach to the Synthesis of Useful Compounds via C-C Bond Formation Using Biomass-Derived Sugars as Carbon Nucleophiles.

    Science.gov (United States)

    Yamaguchi, Sho; Baba, Toshihide

    2016-07-20

    Due to the depletion of fossil fuels, biomass-derived sugars have attracted increasing attention in recent years as an alternative carbon source. Although significant advances have been reported in the development of catalysts for the conversion of carbohydrates into key chemicals (e.g., degradation approaches based on the dehydration of hydroxyl groups or cleavage of C-C bonds via retro-aldol reactions), only a limited range of products can be obtained through such processes. Thus, the development of a novel and efficient strategy targeted towards the preparation of a range of compounds from biomass-derived sugars is required. We herein describe the highly-selective cascade syntheses of a range of useful compounds using biomass-derived sugars as carbon nucleophiles. We focus on the upgrade of C2 and C3 oxygenates generated from glucose to yield useful compounds via C-C bond formation. The establishment of this novel synthetic methodology to generate valuable chemical products from monosaccharides and their decomposed oxygenated materials renders carbohydrates a potential alternative carbon resource to fossil fuels.

  17. Alcohol and Group Formation: A Multimodal Investigation of the Effects of Alcohol on Emotion and Social Bonding

    OpenAIRE

    Sayette, Michael A.; Creswell, Kasey G.; Dimoff, John D.; Fairbairn, Catharine E.; Cohn, Jeffrey F.; Heckman, Bryan W.; Kirchner, Thomas R.; Levine, John M.; Moreland, Richard L.

    2012-01-01

    We integrated research on emotion and on small groups to address a fundamental and enduring question facing alcohol researchers: What are the specific mechanisms that underlie the reinforcing effects of drinking? In one of the largest alcohol-administration studies yet conducted, we employed a novel group-formation paradigm to evaluate the socioemotional effects of alcohol. Seven hundred twenty social drinkers (360 male, 360 female) were assembled into groups of 3 unacquainted persons each an...

  18. Synthesis of Bioactive 2-(Arylaminothiazolo[5,4-f]-quinazolin-9-ones via the Hügershoff Reaction or Cu- Catalyzed Intramolecular C-S Bond Formation

    Directory of Open Access Journals (Sweden)

    Damien Hédou

    2016-06-01

    Full Text Available A library of thirty eight novel thiazolo[5,4-f]quinazolin-9(8H-one derivatives (series 8, 10, 14 and 17 was prepared via the Hügershoff reaction and a Cu catalyzed intramolecular C-S bond formation, helped by microwave-assisted technology when required. The efficient multistep synthesis of the key 6-amino-3-cyclopropylquinazolin-4(3H-one (3 has been reinvestigated and performed on a multigram scale from the starting 5-nitroanthranilic acid. The inhibitory potency of the final products was evaluated against five kinases involved in Alzheimer’s disease and showed that some molecules of the 17 series described in this paper are particularly promising for the development of novel multi-target inhibitors of kinases.

  19. Tailored synthesis of various nanomaterials by using a graphene-oxide-based gel as a nanoreactor and nanohybrid-catalyzed C-C bond formation.

    Science.gov (United States)

    Biswas, Abhijit; Banerjee, Arindam

    2014-12-01

    New graphene oxide (GO)-based hydrogels that contain vitamin B2/B12 and vitamin C (ascorbic acid) have been synthesized in water (at neutral pH value). These gel-based soft materials have been used to synthesize various metal nanoparticles, including Au, Ag, and Pd nanoparticles, as well as nanoparticle-containing reduced graphene oxide (RGO)-based nanohybrid systems. This result indicates that GO-based gels can be used as versatile reactors for the synthesis of different nanomaterials and hybrid systems on the nanoscale. Moreover, the RGO-based nanohybrid hydrogel with Pd nanoparticles was used as an efficient catalyst for C-C bond-formation reactions with good yields and showed high recyclability in Suzuki-Miyaura coupling reactions. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Identification of coevolving residues and coevolution potentials emphasizing structure, bond formation and catalytic coordination in protein evolution.

    Directory of Open Access Journals (Sweden)

    Daniel Y Little

    Full Text Available The structure and function of a protein is dependent on coordinated interactions between its residues. The selective pressures associated with a mutation at one site should therefore depend on the amino acid identity of interacting sites. Mutual information has previously been applied to multiple sequence alignments as a means of detecting coevolutionary interactions. Here, we introduce a refinement of the mutual information method that: 1 removes a significant, non-coevolutionary bias and 2 accounts for heteroscedasticity. Using a large, non-overlapping database of protein alignments, we demonstrate that predicted coevolving residue-pairs tend to lie in close physical proximity. We introduce coevolution potentials as a novel measure of the propensity for the 20 amino acids to pair amongst predicted coevolutionary interactions. Ionic, hydrogen, and disulfide bond-forming pairs exhibited the highest potentials. Finally, we demonstrate that pairs of catalytic residues have a significantly increased likelihood to be identified as coevolving. These correlations to distinct protein features verify the accuracy of our algorithm and are consistent with a model of coevolution in which selective pressures towards preserving residue interactions act to shape the mutational landscape of a protein by restricting the set of admissible neutral mutations.

  1. Atomic state and characterization of nitrogen at the SiC/SiO2 interface

    Science.gov (United States)

    Xu, Y.; Zhu, X.; Lee, H. D.; Xu, C.; Shubeita, S. M.; Ahyi, A. C.; Sharma, Y.; Williams, J. R.; Lu, W.; Ceesay, S.; Tuttle, B. R.; Wan, A.; Pantelides, S. T.; Gustafsson, T.; Garfunkel, E. L.; Feldman, L. C.

    2014-01-01

    We report on the concentration, chemical bonding, and etching behavior of N at the SiC(0001)/SiO2 interface using photoemission, ion scattering, and computational modeling. For standard NO processing of a SiC MOSFET, a sub-monolayer of nitrogen is found in a thin inter-layer between the substrate and the gate oxide (SiO2). Photoemission shows one main nitrogen related core-level peak with two broad, higher energy satellites. Comparison to theory indicates that the main peak is assigned to nitrogen bound with three silicon neighbors, with second nearest neighbors including carbon, nitrogen, and oxygen atoms. Surprisingly, N remains at the surface after the oxide was completely etched by a buffered HF solution. This is in striking contrast to the behavior of Si(100) undergoing the same etching process. We conclude that N is bound directly to the substrate SiC, or incorporated within the first layers of SiC, as opposed to bonding within the oxide network. These observations provide insights into the chemistry and function of N as an interface passivating additive in SiC MOSFETs.

  2. Synthesis of the proteinase inhibitor LEKTI domain 6 by the fragment condensation method and regioselective disulfide bond formation.

    Science.gov (United States)

    Vasileiou, Zoe; Barlos, Kostas K; Gatos, Dimitrios; Adermann, Knut; Deraison, Celine; Barlos, Kleomenis

    2010-01-01

    Proteinase inhibitors are of high pharmaceutical interest and are drug candidates for a variety of indications. Specific kallikrein inhibitors are important for their antitumor activity and their potential application to the treatment of skin diseases. In this study we describe the synthesis of domain 6 of the kallikrein inhibitor Lympho-Epithilial Kazal-Type Inhibitor (LEKTI) by the fragment condensation method and site-directed cystine bridge formation. To obtain the linear LEKTI precursor, the condensation was best performed in solution, coupling the protected fragment 1-22 to 23-68. This method yielded LEKTI domain 6 of high purity and equipotent to the recombinantly produced peptide. (c) 2010 Wiley Periodicals, Inc.

  3. Mechanistic elucidation of the stepwise formation of a tetranuclear manganese pinned butterfly cluster via N-N bond cleavage, hydrogen atom transfer, and cluster rearrangement.

    Science.gov (United States)

    Hamilton, Clifton R; Gau, Michael R; Baglia, Regina A; McWilliams, Sean F; Zdilla, Michael J

    2014-12-31

    A mechanistic pathway for the formation of the structurally characterized manganese-amide-hydrazide pinned butterfly complex, Mn4(μ3-PhN-NPh-κ(3)N,N')2(μ-PhN-NPh-κ(2)-N,N')(μ-NHPh)2L4 (L = THF, py), is proposed and supported by the use of labeling studies, kinetic measurements, kinetic competition experiments, kinetic isotope effects, and hydrogen atom transfer reagent substitution, and via the isolation and characterization of intermediates using X-ray diffraction and electron paramagnetic resonance spectroscopy. The data support a formation mechanism whereby bis[bis(trimethylsilyl)amido]manganese(II) (Mn(NR2)2, where R = SiMe3) reacts with N,N'-diphenylhydrazine (PhNHNHPh) via initial proton transfer, followed by reductive N-N bond cleavage to form a long-lived Mn(IV) imido multinuclear complex. Coordinating solvents activate this cluster for abstraction of hydrogen atoms from an additional equivalent of PhNHNHPh resulting in a Mn(II)phenylamido dimer, Mn2(μ-NHPh)2(NR2)2L2. This dimeric complex further assembles in fast steps with two additional equivalents of PhNHNHPh replacing the terminal silylamido ligands with η(1)-hydrazine ligands to give a dimeric Mn2(μ-NHPh)2(PhN-NHPh)2L4 intermediate, and finally, the addition of two additional equivalents of Mn(NR2)2 and PhNHNHPh gives the pinned butterfly cluster.

  4. Acetaldehyde partial oxidation on the Au(111) model catalyst surface: C-C bond activation and formation of methyl acetate as an oxidative coupling product

    Science.gov (United States)

    Karatok, Mustafa; Vovk, Evgeny I.; Shah, Asad A.; Turksoy, Abdurrahman; Ozensoy, Emrah

    2015-11-01

    Partial oxidation of acetaldehyde (CH3CHO) on the oxygen pre-covered Au(111) single crystal model catalyst was investigated via Temperature Programmed Desorption (TPD) and Temperature Programmed Reaction Spectroscopy (TPRS) techniques, where ozone (O3) was utilized as the oxygen delivery agent providing atomic oxygen to the reacting surface. We show that for low exposures of O3 and small surface oxygen coverages, two partial oxidation products namely, methyl acetate (CH3COOCH3) and acetic acid (CH3COOH) can be generated without the formation of significant quantities of carbon dioxide. The formation of methyl acetate as the oxidative coupling reaction product implies that oxygen pre-covered Au(111) single crystal model catalyst surface can activate C-C bonds. In addition to the generation of these products; indications of the polymerization of acetaldehyde on the gold surface were also observed as an additional reaction route competing with the partial and total oxidation pathways. The interplay between the partial oxidation, total oxidation and polymerization pathways reveals the complex catalytic chemistry associated with the interaction between the acetaldehyde and atomic oxygen on catalytic gold surfaces.

  5. An optically controlled SiC lateral power transistor based on SiC/SiCGe super junction structure

    Energy Technology Data Exchange (ETDEWEB)

    Pu Hongbin; Cao Lin; Ren Jie; Chen Zhiming; Nan Yagong, E-mail: puhongbin@xaut.edu.c [Xi' an University of Technology, Xi' an 710048 (China)

    2010-04-15

    An optically controlled SiC/SiCGe lateral power transistor based on superjunction structure has been proposed, in which n-SiCGe/p-SiC superjunction structure is employed to improve device figure of merit. Performance of the novel optically controlled power transistor was simulated using Silvaco Atlas tools, which has shown that the device has a very good response to the visible light and the near infrared light. The optoelectronic responsivities of the device at 0.5 {mu}m and 0.7 {mu}m are 330 mA/W and 76.2 mA/W at 2 V based voltage, respectively. (semiconductor devices)

  6. Effect of initial porosity on mechanical properties of C/SiC composites fabricated by silicon melt infiltration process

    Energy Technology Data Exchange (ETDEWEB)

    Bae, D.S.; Son, D.Y. [Dept. of Materials and Metallurgical Eng., Dong-Eui Univ., Busan (Korea); Lee, S.P. [Dept. of Mechanical Eng., Dong-Eui Univ., Busan (Korea); Park, H.S.; Kim, K.S. [Dreaming and Challenging Co., Changwon (Korea); Jeon, J.H. [Korea Inst. of Machinery and Materials, Changwon (Korea)

    2004-07-01

    Four kinds of raw C/C composites with a density between 1.25{proportional_to}1.66 g/cm{sup 3} were used in order to investigate the effect of the initial porosity of C/C composites on mechanical properties of liquid silicon infiltrated C/SiC composites. The microstructure observation, image analysis and flexural strength test of the composites were performed. The density and microstructural changes with the variation of the initial porosity was discussed in the terms of the infiltration behavior of liquid silicon and the reaction between liquid silicon and matrix carbon. (orig.)

  7. Behavior of insoluble particles during parabolic flight solidification processing of Fe-C-Si and Fe-C-V alloys

    Science.gov (United States)

    Stefanescu, D. M.; Fiske, M. R.; Curreri, P. A.

    1986-01-01

    In a high-g rapid solidification environment, Fe-base alloy insoluble particles at the solidification interface may be pushed ahead of the interface or may be trapped in the solid, depending on the correlation of various interface energies, the solidification rates, and the Stokes force; particle agglomeration due to buoyancy-driven convection further complicates the problem. Attention is presently given to results obtained for directionally solidified Fe-C-Si and Fe-C-V alloys during parabolic low-g flight and ground experiments. In these systems, graphite and vanadium carbide can be considered to be the insoluble particles.

  8. THE INFLUENCE OF NEUTRON-IRRADIATION AT LOW TEMPERATURES ON THE DIELECTRIC PARAMETERS OF 3C-SiC

    Energy Technology Data Exchange (ETDEWEB)

    J.A.A. Engelbrecht; G. Deyzel; E. Minnaar; W.E. Goosen; I. J. van Rooyen

    2014-04-01

    3C-SiC wafers were irradiated with neutrons of various fluences and at low (200 - 400 ?C) irradiation temperatures. Fourier Transform infrared (FTIR) reflectance spectra were obtained for the samples, and the spectra used to extract the dielectric parameters for each specimen, using statistical curve-fitting procedures. Analysis of all data revealed trends in reflectance peak heights as well as in the dielectric parameters. The surface roughness of the irradiated samples was measured by atomic force spectroscopy (AFM) and certain trends could be ascribed to surface roughness.

  9. The influence of neutron-irradiation at low temperatures on the dielectric parameters of 3C-SiC

    Energy Technology Data Exchange (ETDEWEB)

    Engelbrecht, J.A.A., E-mail: Japie.Engelbrecht@nmmu.ac.za [Physics Department, Nelson Mandela Metropolitan University, P.O. Box 77000, Port Elizabeth 6031 (South Africa); Deyzel, G.; Minnaar, E.G.; Goosen, W.E. [Physics Department, Nelson Mandela Metropolitan University, P.O. Box 77000, Port Elizabeth 6031 (South Africa); Rooyen, I.J. van [Fuel Performance and Design Department, Idaho National Laboratory, P.O. Box 1625, Idaho Falls, ID 83415-6188 (United States)

    2014-04-15

    3C-SiC wafers were irradiated with neutrons of various fluences and at low (200–400 °C) irradiation temperatures. Fourier transform infrared (FTIR) reflectance spectra were obtained for the samples, and the spectra used to extract the dielectric parameters for each specimen, using statistical curve-fitting procedures. Analysis of all data revealed trends in reflectance peak heights as well as in the dielectric parameters. The surface roughness of the irradiated samples was measured by atomic force spectroscopy (AFM) and certain trends could be ascribed to surface roughness.

  10. Surface passivation of c-Si for silicon heterojunction solar cells using high-pressure hydrogen diluted plasmas

    Directory of Open Access Journals (Sweden)

    Dimitrios Deligiannis

    2015-09-01

    Full Text Available In this work we demonstrate excellent c-Si surface passivation by depositing a-Si:H in the high-pressure and high hydrogen dilution regime. By using high hydrogen dilution of the precursor gases during deposition the hydrogen content of the layers is sufficiently increased, while the void fraction is reduced, resulting in dense material. Results show a strong dependence of the lifetime on the substrate temperature and a weaker dependence on the hydrogen dilution. After applying a post-deposition annealing step on the samples equilibration of the lifetime occurs independent of the initial nanostructure.

  11. a-Si:H/c-Si heterojunction front- and back contacts for silicon solar cells with p-type base

    Energy Technology Data Exchange (ETDEWEB)

    Rostan, Philipp Johannes

    2010-07-01

    This thesis reports on low temperature amorphous silicon back and front contacts for high-efficiency crystalline silicon solar cells with a p-type base. The back contact uses a sequence of intrinsic amorphous (i-a-Si:H) and boron doped microcrystalline (p-{mu}c-Si:H) silicon layers fabricated by Plasma Enhanced Chemical Vapor Deposition (PECVD) and a magnetron sputtered ZnO:Al layer. The back contact is finished by evaporating Al onto the ZnO:Al and altogether prepared at a maximum temperature of 220 C. Analysis of the electronic transport of mobile charge carriers at the back contact shows that the two high-efficiency requirements low back contact series resistance and high quality c-Si surface passivation are in strong contradiction to each other, thus difficult to achieve at the same time. The preparation of resistance- and effective lifetime samples allows one to investigate both requirements independently. Analysis of the majority charge carrier transport on complete Al/ZnO:Al/a-Si:H/c-Si back contact structures derives the resistive properties. Measurements of the effective minority carrier lifetime on a-Si:H coated wafers determines the back contact surface passivation quality. Both high-efficiency solar cell requirements together are analyzed in complete photovoltaic devices where the back contact series resistance mainly affects the fill factor and the back contact passivation quality mainly affects the open circuit voltage. The best cell equipped with a diffused emitter with random texture and a full-area a-Si:H/c-Si back contact has an independently confirmed efficiency {eta} = 21.0 % with an open circuit voltage V{sub oc} = 681 mV and a fill factor FF = 78.7 % on an area of 1 cm{sup 2}. An alternative concept that uses a simplified a-Si:H layer sequence combined with Al-point contacts yields a confirmed efficiency {eta} = 19.3 % with an open circuit voltage V{sub oc} = 655 mV and a fill factor FF = 79.5 % on an area of 2 cm{sup 2}. Analysis of the

  12. Spectrofluorimetric determination of total free thiols based on formation of complexes of Ce(III) with disulfide bonds

    Energy Technology Data Exchange (ETDEWEB)

    Han Guocheng; Peng Yong; Hao Yuanqiang [College of Chemistry and Chemical Engineering, Central South University, Changsha, Hunan 410083 (China); Liu Younian, E-mail: liuyoun@mail.csu.edu.cn [College of Chemistry and Chemical Engineering, Central South University, Changsha, Hunan 410083 (China); Zhou Feimeng, E-mail: fzhou@exchange.calstatela.edu [College of Chemistry and Chemical Engineering, Central South University, Changsha, Hunan 410083 (China); Department of Chemistry and Biochemistry, California State University, Los Angeles, Los Angeles, CA 90032 (United States)

    2010-02-05

    A simple, rapid, and sensitive determination of total free thiol groups in biological samples using cerium (IV) as a fluorescence probe is reported. The protocol is based on the oxidation of thiols by Ce(IV) and the formation the Ce(III) disulfide complex, which gives a fluorescence enhancement of Ce(III) at 352 nm. Using glutathione (GSH) and cysteine as model compounds, incubation with Ce(IV) at 25 {sup o}C for 6 min results in fluorescence, whose intensity is proportional to the thiol concentration in the range of 1.00-160 nM. The detection limits for GSH and cysteine are 0.05 and 0.08 nM, respectively. Other common metal ions and amino acids have little interference to the thiol detection. Cu(II) was used as a fluorescence quencher to eliminate potential interference from tryptophan. The method has been successfully applied to assays of free thiol contents in pig liver tissue samples, with a RSD lower than 2.5% and recovery between 100.6% and 102.3%.

  13. High Improvement in Conversion Efficiency of μc-SiGe Thin-Film Solar Cells with Field-Enhancement Layers

    Directory of Open Access Journals (Sweden)

    Shu-Hung Yu

    2012-01-01

    Full Text Available The improved performance for hydrogenated microcrystalline silicon-germanium (μc-Si1−xGex:H, x~0.1 p-i-n single solar cells with hydrogenated microcrystalline silicon (μc-Si:H field-enhancement layers (FELs is demonstrated for the first time. The fill factor (FF and conversion efficiency (η increase by about 19% and 28% when the thickness of the μc-Si FEL is increased from 0 to 200 nm, it is attributed to the longer hole life-time and enhanced electric field in the μc-Si0.9Ge0.1:H layer. Therefore, we can successfully manufacture high-performance μc-SiGe:H solar cells with the thickness of absorbers smaller than 1 μm by conducting FELs. Moreover, the simulation tool is used to simulate the current-voltage (J-V curve, thus we can investigate the carrier transport in the absorber of μc-Si0.9Ge0.1:H solar cells with different EFLs.

  14. Communications: Photoinitiated bond dissociation of bromoiodomethane in solution: Comparison of one-photon and two-photon excitations and the formation of iso-CH2Br-I and iso-CH2I-Br

    Science.gov (United States)

    Tang, Kuo-Chun; Peng, Jian; Spears, Kenneth G.; Sension, Roseanne J.

    2010-04-01

    Broadband UV-visible femtosecond transient absorption spectroscopy was used to monitor the excited state photochemistry of CH2BrI following one-photon excitation at 266 or 271 nm and two-photon excitation at 395 or 405 nm in 2-butanol. The results for one-photon excitation agree with earlier studies in acetonitrile, showing clear formation of iso-CH2Br-I following cleavage of the C-I bond. In contrast, two-photon excitation at 395 nm results in the appearance of a blueshifted photoproduct absorption band assigned to formation of iso-CH2I-Br following cleavage of the C-Br bond. The results are discussed in the context of prior experimental and theoretical work and the prospects for optical control of bond cleavage.

  15. Multi-scale thermodynamic analysis method for 2D SiC/SiC composite turbine guide vanes

    Directory of Open Access Journals (Sweden)

    Xin LIU

    2018-01-01

    Full Text Available Ceramic Matrix Composite (CMC turbine guide vanes possess multi-scale stress and strain with inhomogeneity at the microscopic scale. Given that the macroscopic distribution cannot reflect the microscopic stress fluctuation, the macroscopic method fails to meet the requirements of stress and strain analysis of CMC turbine guide vanes. Furthermore, the complete thermodynamic properties of 2D woven SiC/SiC-CMC cannot be obtained through experimentation. Accordingly, a method to calculate the thermodynamic properties of CMC and analyze multi-scale stress and strain of the turbine guide vanes should be established. In this study, the multi-scale thermodynamic analysis is investigated. The thermodynamic properties of Chemical Vapor Infiltration (CVI processed SiC/SiC-CMC are predicted by a Representative Volume Element (RVE model with porosity, leading to the result that the relative error between the calculated in-plane tensile modulus and the experimental value is 4.2%. The macroscopic response of a guide vane under given conditions is predicted. The relative error between the predicted strain on the trailing edge and the experimental value is 9.7%. The calculation of the stress distribution of micro-scale RVE shows that the maximum value of microscopic stress, which is located in the interlayer matrix, is more than 1.5 times that of macroscopic stress in the same direction and the microscopic stress distribution of the interlayer matrix is related to the pore distribution of the composite.

  16. Study of optical sensors of the form Al/a-SiC:H/c-Si(n with high sensitivity.

    Directory of Open Access Journals (Sweden)

    L. Magafas

    2008-06-01

    Full Text Available In the present work optical sensors of the form Al/a-SiC:H/c-Si(n, for different thickness of a-SiC:H thin films are stud-ied. More specifically, a-SiC:H thin films were deposited by rf sputtering technique on c-Si(n substrates for different thickness of the amorphous semiconductor and, subsequently, the samples were annealed in the temperature range from 300oC up to 675 oC. Experimental measurements of the optical response of these sensors showed that for thicknesses of a-SiC:H greater than a critical value, which depends on annealing temperature, a mechanism of losses is appeared in the region of wavelengths from 525nm up to 625nm. This behaviour is attributed to the recombination of photo-generated electrons-hole pairs in the neutral region of a-SiC:H, when this exceeds the diffusion length of minority carries, Lp. Also, the value of the reverse bias voltage appears to influence considerably the optical response of these sensors when d > Lp in the case where the a-SiC: H thin films were annealed at 600oC.

  17. Electrical Resistance as a NDE Technique to Monitor Processing and Damage Accumulation in SiC/SiC Composites

    Science.gov (United States)

    Smith, Craig; Morscher, Gregory N.; Xia, Zhenhai

    2008-01-01

    Ceramic matrix composites are suitable for high temperature structural applications such as turbine airfoils and hypersonic thermal protection systems. The employment of these materials in such applications is limited by the ability to process components reliable and to accurately monitor and predict damage evolution that leads to failure under stressed-oxidation conditions. Current nondestructive methods such as ultrasound, x-ray, and thermal imaging are limited in their ability to quantify small scale, transverse, in-plane, matrix cracks developed over long-time creep and fatigue conditions. Electrical resistance of SiC/SiC composites is one technique that shows special promise towards this end. Since both the matrix and the fibers are conductive, changes in matrix or fiber properties should relate to changes in electrical conductivity along the length of a specimen or part. Initial efforts to quantify the electrical resistance of different fiber and different matrix SiC/SiC composites will be presented. Also, the effect of matrix cracking on electrical resistivity for several composite systems will be presented. The implications towards electrical resistance as a technique applied to composite processing, damage detection, and life-modeling will be discussed.

  18. Atomic probe microscopy of 3C SiC films grown on 6H SiC substrates

    Science.gov (United States)

    Steckl, A. J.; Roth, M. D.; Powell, J. A.; Larkin, D. J.

    1993-01-01

    The surface of 3C SiC films grown on 6H SiC substrates has been studied by atomic probe microscopy in air. Atomic-scale images of the 3C SiC surface have been obtained by STM which confirm the 111 line type orientation of the cubic 3C layer grown on the 0001 plane type surface of the hexagonal 6H substrate. The nearest-neighbor atomic spacing for the 3C layer has been measured to be 3.29 +/- 0.2 A, which is within 7 percent of the bulk value. Shallow terraces in the 3C layer have been observed by STM to separate regions of very smooth growth in the vicinity of the 3C nucleation point from considerably rougher 3C surface regions. These terraces are oriented at right angles to the growth direction. Atomic force microscopy has been used to study etch pits present on the 6H substrate due to high temperature HCl cleaning prior to CVD growth of the 3C layer. The etch pits have hexagonal symmetry and vary in depth from 50 nm to 1 micron.

  19. On the c-Si/SiO2 interface recombination parameters from photo-conductance decay measurements

    Science.gov (United States)

    Bonilla, Ruy S.; Wilshaw, Peter R.

    2017-04-01

    The recombination of electric charge carriers at semiconductor surfaces continues to be a limiting factor in achieving high performance optoelectronic devices, including solar cells, laser diodes, and photodetectors. The theoretical model and a solution algorithm for surface recombination have been previously reported. However, their successful application to experimental data for a wide range of both minority excess carrier concentrations and dielectric fixed charge densities has not previously been shown. Here, a parametrisation for the semiconductor-dielectric interface charge Q i t is used in a Shockley-Read-Hall extended formalism to describe recombination at the c-Si/SiO2 interface, and estimate the physical parameters relating to the interface trap density D i t , and the electron and hole capture cross-sections σ n and σ p . This approach gives an excellent description of the experimental data without the need to invoke a surface damage region in the c-Si/SiO2 system. Band-gap tail states have been observed to limit strongly the effectiveness of field effect passivation. This approach provides a methodology to determine interface recombination parameters in any semiconductor-insulator system using macro scale measuring techniques.

  20. Formation of hydrogen-bonded chains through inter- and intra-molecular hydrogen bonds by a strong base of guanidine-like character and 2,2‧-biphenols

    Science.gov (United States)

    Brzezinski, B.; Wojciechowski, G.; Bartl, F.; Zundel, G.

    2000-11-01

    2,2‧-Biphenol mixtures with 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene (MTBD) were studied by FTIR spectroscopy. In chloroform, a proton transfer from 2,2‧-biphenol to MTBD occurs. In this solution the protonated MTBD molecules are hydrogen-bonded to the 2,2‧-biphenol-2,2‧-biphenolate chains. In acetonitrile, after the proton transfer, the complexes dissociate and hence protonated MTBD molecules and hydrogen-bonded 2,2‧-biphenol-2,2‧-biphenolate chains are present. The hydrogen bonds and the hydrogen-bonded chains show large proton polarizability. In the systems intra- as well as inter-molecular hydrogen bonds are formed.

  1. Formats

    Directory of Open Access Journals (Sweden)

    Gehmann, Ulrich

    2012-03-01

    Full Text Available In the following, a new conceptual framework for investigating nowadays’ “technical” phenomena shall be introduced, that of formats. The thesis is that processes of formatting account for our recent conditions of life, and will do so in the very next future. It are processes whose foundations have been laid in modernity and which will further unfold for the time being. These processes are embedded in the format of the value chain, a circumstance making them resilient to change. In addition, they are resilient in themselves since forming interconnected systems of reciprocal causal circuits.Which leads to an overall situation that our entire “Lebenswelt” became formatted to an extent we don’t fully realize, even influencing our very percep-tion of it.

  2. Thermal shock performance of carbon-bonded carbon fiber composite and ceramic matrix composite joints for thermal protection re-entry applications

    OpenAIRE

    Triantou, K.I.; Mergia, K.; Perez, B.; Florez, S.; Stefan, A.; Ban, C.; Pelin, G.; Ionescu, G.; Zuber, C.; Fischer, W.P.P.; Barcena, J.

    2017-01-01

    Hybrid thermal protection systems for aerospace applications based on carbon-bonded carbon fiber composite (CALCARB®) and ceramic matrix composites have been investigated. Two types of ceramic composite materials were considered, Cf/SiC (SiCARBON™) and C/C-SiC. The ablative material and the ceramic matrix composite were joined using alumina, graphite and zirconia-zirconium silicate based commercial high temperature adhesives and their performance on thermal shock tests was evaluated. Microstr...

  3. Copper wire bonding

    CERN Document Server

    Chauhan, Preeti S; Zhong, ZhaoWei; Pecht, Michael G

    2014-01-01

    This critical volume provides an in-depth presentation of copper wire bonding technologies, processes and equipment, along with the economic benefits and risks.  Due to the increasing cost of materials used to make electronic components, the electronics industry has been rapidly moving from high cost gold to significantly lower cost copper as a wire bonding material.  However, copper wire bonding has several process and reliability concerns due to its material properties.  Copper Wire Bonding book lays out the challenges involved in replacing gold with copper as a wire bond material, and includes the bonding process changes—bond force, electric flame off, current and ultrasonic energy optimization, and bonding tools and equipment changes for first and second bond formation.  In addition, the bond–pad metallurgies and the use of bare and palladium-coated copper wires on aluminum are presented, and gold, nickel and palladium surface finishes are discussed.  The book also discusses best practices and re...

  4. An Electron-Poor C64 Nanographene by Palladium-Catalyzed Cascade C-C Bond Formation: One-Pot Synthesis and Single-Crystal Structure Analysis.

    Science.gov (United States)

    Seifert, Sabine; Shoyama, Kazutaka; Schmidt, David; Würthner, Frank

    2016-05-23

    Herein, we report the one-pot synthesis of an electron-poor nanographene containing dicarboximide groups at the corners. We efficiently combined palladium-catalyzed Suzuki-Miyaura cross-coupling and dehydrohalogenation to synthesize an extended two-dimensional π-scaffold of defined size in a single chemical operation starting from N-(2,6-diisopropylphenyl)-4,5-dibromo-1,8-naphthalimide and a tetrasubstituted pyrene boronic acid ester as readily accessible starting materials. The reaction of these precursors under the conditions commonly used for Suzuki-Miyaura cross-coupling afforded a C64 nanographene through the formation of ten C-C bonds in a one-pot process. Single-crystal X-ray analysis unequivocally confirmed the structure of this unique extended aromatic molecule with a planar geometry. The optical and electrochemical properties of this largest ever synthesized planar electron-poor nanographene skeleton were also analyzed. © 2016 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

  5. Stacked base-pair structures of adenine nucleosides stabilized by the formation of hydrogen-bonding network involving the two sugar groups

    Energy Technology Data Exchange (ETDEWEB)

    Asami, Hiroya [Graduate School of Bio- and Nanosystem Sciences, Yokohama City University, Yokohama 236-0027 (Japan); Yagi, Kiyoshi [Department of Chemistry, School of Chemical Sciences, University of Illinois at Urbana-Champaign, Urbana, IL 61801 (United States); Ohba, Masashi [Yokohama College of Pharmacy, Yokohama 245-0066 (Japan); Urashima, Shu-hei [Graduate School of Bio- and Nanosystem Sciences, Yokohama City University, Yokohama 236-0027 (Japan); Saigusa, Hiroyuki, E-mail: saigusa@yokohama-cu.ac.jp [Graduate School of Bio- and Nanosystem Sciences, Yokohama City University, Yokohama 236-0027 (Japan)

    2013-06-20

    Highlights: ► A combination of laser desorption and supersonic jet-cooling is used to produce base pairs of adenine nucleosides. ► Stacked base-pair structure of N6,N6-dimethyladnosine is identified by IR vibrational spectroscopy. ► Anharmonic vibrational calculation is employed to analyze the vibrational mode coupling in the stacked base pair. - Abstract: We have employed a laser desorption technique combined with supersonic-jet cooling for producing base pairs of adenine nucleosides, adenosine (Ado) and N6,N6-dimethyladenosine (DMAdo) under low-temperature conditions. The resulting base pairs are then ionized through resonant two-photon ionization (R2PI) and analyzed by time-of-flight mass spectrometry. It is found that dimers of these adenine nucleosides are stable, especially in the case of DMAdo, with respect to those of the corresponding bases, i.e., adenine and N6,N6-dimethyladenine. Structural analysis of the DMAdo dimer is performed based on the IR–UV double resonance measurements and theoretical calculations. The result demonstrates that the dimer possesses a stacked structure being stabilized by the formation of hydrogen-bonding network involving the two sugar groups. The occurrence of the frequency shift and broadening is explained satisfactorily based on the anharmonic coupling of the OH stretching modes with specific bending modes and low-frequency modes of base and sugar moieties.

  6. Phylogeny of the Vitamin K 2,3-Epoxide Reductase (VKOR) Family and Evolutionary Relationship to the Disulfide Bond Formation Protein B (DsbB) Family.

    Science.gov (United States)

    Bevans, Carville G; Krettler, Christoph; Reinhart, Christoph; Watzka, Matthias; Oldenburg, Johannes

    2015-07-29

    In humans and other vertebrate animals, vitamin K 2,3-epoxide reductase (VKOR) family enzymes are the gatekeepers between nutritionally acquired K vitamins and the vitamin K cycle responsible for posttranslational modifications that confer biological activity upon vitamin K-dependent proteins with crucial roles in hemostasis, bone development and homeostasis, hormonal carbohydrate regulation and fertility. We report a phylogenetic analysis of the VKOR family that identifies five major clades. Combined phylogenetic and site-specific conservation analyses point to clade-specific similarities and differences in structure and function. We discovered a single-site determinant uniquely identifying VKOR homologs belonging to human pathogenic, obligate intracellular prokaryotes and protists. Building on previous work by Sevier et al. (Protein Science 14:1630), we analyzed structural data from both VKOR and prokaryotic disulfide bond formation protein B (DsbB) families and hypothesize an ancient evolutionary relationship between the two families where one family arose from the other through a gene duplication/deletion event. This has resulted in circular permutation of primary sequence threading through the four-helical bundle protein folds of both families. This is the first report of circular permutation relating distant a-helical membrane protein sequences and folds. In conclusion, we suggest a chronology for the evolution of the five extant VKOR clades.

  7. Use of a temporary "solubilizing" peptide tag for the Fmoc solid-phase synthesis of human insulin glargine via use of regioselective disulfide bond formation.

    Science.gov (United States)

    Hossain, Mohammed Akhter; Belgi, Alessia; Lin, Feng; Zhang, Suode; Shabanpoor, Fazel; Chan, Linda; Belyea, Chris; Truong, Hue-Trung; Blair, Amy R; Andrikopoulos, Sof; Tregear, Geoffrey W; Wade, John D

    2009-07-01

    Solid-phase peptide synthesis has been refined to a stage where efficient preparation of long and complex peptides is now achievable. However, the postsynthesis handling of poorly soluble peptides often remains a significant hindrance to their purification and further use. Several synthetic schemes have been developed for the preparation of such peptides containing modifications to aid their solubility. However, these require the use of complex chemistry or yield non-native sequences. We describe a simple approach based on the use of penta-lysine "tags" that are linked to the C-terminus of the peptide of interest via a base-labile linker. After ready purification of the now freely solubilized peptide, the "tag" is removed by simple, brief base treatment giving the native sequence in much higher overall yield. The applicability of the method was demonstrated by the novel preparation of insulin glargine via solid-phase synthesis of each of the two chains--including the notoriously poorly soluble A-chain--followed by their combination in solution via regioselective disulfide bond formation. At the conclusion of the chain combination, the solubilizing peptide tag was removed from the A-chain to provide synthetic human glargine in nearly 10% overall yield. This approach should facilitate the development of new insulin analogues as well as be widely applicable to the improved purification and acquisition of otherwise poorly soluble synthetic peptides.

  8. Phylogeny of the Vitamin K 2,3-Epoxide Reductase (VKOR Family and Evolutionary Relationship to the Disulfide Bond Formation Protein B (DsbB Family

    Directory of Open Access Journals (Sweden)

    Carville G. Bevans

    2015-07-01

    Full Text Available In humans and other vertebrate animals, vitamin K 2,3-epoxide reductase (VKOR family enzymes are the gatekeepers between nutritionally acquired K vitamins and the vitamin K cycle responsible for posttranslational modifications that confer biological activity upon vitamin K-dependent proteins with crucial roles in hemostasis, bone development and homeostasis, hormonal carbohydrate regulation and fertility. We report a phylogenetic analysis of the VKOR family that identifies five major clades. Combined phylogenetic and site-specific conservation analyses point to clade-specific similarities and differences in structure and function. We discovered a single-site determinant uniquely identifying VKOR homologs belonging to human pathogenic, obligate intracellular prokaryotes and protists. Building on previous work by Sevier et al. (Protein Science 14:1630, we analyzed structural data from both VKOR and prokaryotic disulfide bond formation protein B (DsbB families and hypothesize an ancient evolutionary relationship between the two families where one family arose from the other through a gene duplication/deletion event. This has resulted in circular permutation of primary sequence threading through the four-helical bundle protein folds of both families. This is the first report of circular permutation relating distant a-helical membrane protein sequences and folds. In conclusion, we suggest a chronology for the evolution of the five extant VKOR clades.

  9. Quality of Metal Deposited Flux Cored Wire With the System Fe-C-Si-Mn-Cr-Mo-Ni-V-Co

    Science.gov (United States)

    Gusev, Aleksander I.; Kozyrev, Nikolay A.; Osetkovskiy, Ivan V.; Kryukov, Roman E.; Kozyreva, Olga A.

    2017-10-01

    Studied the effect of the introduction of vanadium and cobalt into the charge powder fused wire system Fe-C-Si-Mn-Cr-Ni-Mo-V, used in cladding assemblies and equipment parts and mechanisms operating under abrasive and abrasive shock loads. the cored wires samples were manufactured in the laboratory conditions and using appropriate powder materials and as a carbonfluoride contained material were used the dust from gas purification of aluminum production, with the following components composition, %: Al2O3 = 21-46.23; F = 18-27; Na2O = 8-15; K2O = 0.4-6; CaO = 0.7-2.3; Si2O = 0.5-2.48; Fe2O3 = 2.1-3.27; C = 12.5-30.2; MnO = 0.07-0.9; MgO = 0.06-0.9; S = 0.09-0.19; P = 0.1-0.18. Surfacing was produced on the St3 metal plates in 6 layers under the AN-26C flux by welding truck ASAW-1250. Cutting and preparation of samples for research had been implemented. The chemical composition and the hydrogen content of the weld metal were determined by modern methods. The hardness and abrasion rate of weld metal had been measured. Conducted metallographic studies of weld metal: estimated microstructure, grain size, contamination of oxide non-metallic inclusions. Metallographic studies showed that the microstructure of the surfaced layer by cored wire system Fe-C-Si-Mn-Cr-Mo-Ni-V-Co is uniform, thin dendrite branches are observed. The microstructure consists of martensite, which is formed inside the borders of the former austenite grain retained austenite present in small amounts in the form of separate islands, and thin layers of δ-ferrite, which is located on the borders of the former austenite grains. Carried out an assessment the effect of the chemical composition of the deposited metal on the hardness and wear and hydrogen content. In consequence of multivariate correlation analysis, it was determined dependence to the hardness of the deposited layer and the wear resistance of the mass fraction of the elements included in the flux-cored wires of the system Fe-C-Si

  10. Rapid formation of Ni3Sn4 joints for die attachment of SiC-based high temperature power devices using ultrasound-induced transient liquid phase bonding process.

    Science.gov (United States)

    Li, Z L; Dong, H J; Song, X G; Zhao, H Y; Feng, J C; Liu, J H; Tian, H; Wang, S J

    2017-05-01

    High melting point Ni3Sn4 joints for the die attachment of SiC-based high temperature power devices was successfully achieved using an ultrasound-induced transient liquid phase (TLP) bonding process within a remarkably short bonding time of 8s. The formed intermetallic joints, which are completely composed of the refined equiaxial Ni3Sn4 grains with the average diameter of 2μm, perform the average shear strength of 26.7MPa. The sonochemical effects of ultrasonic waves dominate the mechanism and kinetics of the rapid formation of Ni3Sn4 joints. Copyright © 2016 Elsevier B.V. All rights reserved.

  11. LETTER TO THE EDITOR: First-principles study on the lonsdaleite phases of C, Si and Ge

    Science.gov (United States)

    Wang, S. Q.; Ye, H. Q.

    2003-04-01

    Crystalline C, Si and Ge in a lonsdaleite (hexagonal diamond) structure are studied by plane-wave pseudopotential calculations in the scheme of density-functional theory and the local density approximation. The same calculations with generalized gradient corrections and also for the cubic diamond phases of these elements are also performed for comparison. Our results show that the bulk moduli are quite similar between the diamond and lonsdaleite polytypes of these elements. The theoretical bulk modulus of lonsdaleite C is 0.2-0.3% higher than diamond. It is expected to replace diamond as the hardest material in the world. The LDA result shows lonsdaleite Ge as a semimetal for its zero band gap at its Gamma point. Considering the exchange-correlation energy correction, it is estimated that lonsdaleite Ge is a semiconductor with a small direct band gap.

  12. Graphene synthesis on cubic SiC/Si wafers. perspectives for mass production of graphene-based electronic devices.

    Science.gov (United States)

    Aristov, Victor Yu; Urbanik, Grzegorz; Kummer, Kurt; Vyalikh, Denis V; Molodtsova, Olga V; Preobrajenski, Alexei B; Zakharov, Alexei A; Hess, Christian; Hänke, Torben; Büchner, Bernd; Vobornik, Ivana; Fujii, Jun; Panaccione, Giancarlo; Ossipyan, Yuri A; Knupfer, Martin

    2010-03-10

    The outstanding properties of graphene, a single graphite layer, render it a top candidate for substituting silicon in future electronic devices. The so far exploited synthesis approaches, however, require conditions typically achieved in specialized laboratories and result in graphene sheets whose electronic properties are often altered by interactions with substrate materials. The development of graphene-based technologies requires an economical fabrication method compatible with mass production. Here we demonstrate for the fist time the feasibility of graphene synthesis on commercially available cubic SiC/Si substrates of >300 mm in diameter, which result in graphene flakes electronically decoupled from the substrate. After optimization of the preparation procedure, the proposed synthesis method can represent a further big step toward graphene-based electronic technologies.

  13. Effect of Fabric Preform Structure on Mechanical Properties of SiCf/PyC/SiBCN Composites

    Directory of Open Access Journals (Sweden)

    TAN Xi

    2017-08-01

    Full Text Available Three continuous silicon carbide fiber reinforced SiBCN composites (SiCf/PyC/SiBCN distinguished by different weaving methods of fibers (including two dimensional woven, 2.5 dimensional woven with the fiber tow through the thickness and three dimensional five directional braiding were fabricated by resin transfer molding (RTM, polymer impregnation and pyrolysis (PIP technology. In order to study the impact of waving methods, the microstructures of fabricated composites were observed and the mechanical properties such as tensile, compression strength and bending strength of the composites were tested. The results show that different distributions of fibers on different directions lead to anisotropy of mechanical properties for each composite, and fabric preform structure has a significant influence on the mechanical properties of the composites.

  14. Tandem Solar Cells Based on Cu2O and c-Si Subcells in Parallel Configuration: Numerical Simulation

    Directory of Open Access Journals (Sweden)

    Mihai Răzvan Mitroi

    2017-01-01

    Full Text Available A tandem solar cell consisting of a bottom c-Si high-efficiency subcell and a top low-cost Cu2O subcell in parallel configuration is evaluated for the first time by a use of an electrical model. A numerical simulation based on the single-diode model of the solar cell is performed. The numerical method determines both the model parameters and the parameters of the subcells and tandem from the maximization of output power. The simulations indicate a theoretical limit value of the tandem power conversion efficiency of 31.23% at 298 K. The influence of temperature on the maximum output power is analyzed. This tandem configuration allows a great potential for the development of a new generation of low-cost high-efficiency solar cells.

  15. LAMMPS Framework for Directional Dynamic Bonding

    DEFF Research Database (Denmark)

    2012-01-01

    We have extended the Large-scale Atomic/Molecular Massively Parallel Simulator (LAMMPS) to support directional bonds and dynamic bonding. The framework supports stochastic formation of new bonds, breakage of existing bonds, and conversion between bond types. Bond formation can be controlled...... and bond types. When breaking bonds, all angular and dihedral interactions involving broken bonds are removed. The framework allows chemical reactions to be modeled, and use it to simulate a simplistic, coarse-grained DNA model. The resulting DNA dynamics illustrates the power of the present framework....... to limit the maximal functionality of a bead with respect to various bond types. Concomitant with the bond dynamics, angular and dihedral interactions are dynamically introduced between newly connected triplets and quartets of beads, where the interaction type is determined from the local pattern of bead...

  16. Effect of Specimen Thickness on Mechanical Behavior of SiC/SiC Composites

    Science.gov (United States)

    Morscher, Gregory N.; Singh, Mrityunjay; Freedman, Marc

    2004-01-01

    Potential composite applications in aerospace and transportation application systems have different thickness requirements. For example, space applications such as nozzle ramps or heat exchangers use very thin (less than 1 mm) structures whereas turbine blades need very thick parts greater than or equal to cm). There has been little investigation into the effect of thickness on stress-strain behavior or elevated temperature tensile properties controlled by oxidation. In this study, composites consisting of woven Hi-NicalonTM fibers, a carbon interphase, and CVI Sic matrix were fabricated with different numbers of plies to provide variable thickness. The composites ranged from a single ply (approximately 0.4 mm) to thirty-six plies (approximately 1 cm). Tensile tests were performed at room temperature with acoustic emission used to monitor matrix crack behavior. Elevated temperature tensile stress-rupture tests were performed in air. Considerably different room and elevated temperature tensile behavior was observed that will be discussed with respect to the effect of thickness on matrix crack formation, matrix crack growth and oxidation diffusion kinetics.

  17. Formation of hydrogen-bonded chains through inter- and intra-molecular hydrogen bonds by a strong base of guanidine-like character and 5,5'-dibromo-2,2'-biphenols

    Science.gov (United States)

    Wojciechowski, G.; Brzezinski, B.

    2002-04-01

    5,5'-dibromo-2,2'-biphenol mixtures with 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene (MTBD) were studied by FTIR as well as 1H NMR spectroscopy. In chloroform, a proton transfer from DBBPh to MTBD occurs and the protonated MTBD molecule is hydrogen-bonded to the chain formed between 5,5'-dibromo-2,2'-biphenol and 5,5'-dibromo-2,2'-biphenolate molecule. In acetonitrile, the complex dissociates and hence protonated MTBD molecules and hydrogen-bonded chains formed between 5,5'-dibromo-2,2'-biphenol and 5,5'-dibromo-2,2'-biphenolate are present. The hydrogen bonds of these chains show large proton polarizability.

  18. Formation of hydrogen-bonded chains through inter- and intra-molecular hydrogen bonds by 5,5'-dinitro-2,2'-biphenol with a strong base of guanidine-like character and triethylamine

    Science.gov (United States)

    Wojciechowski, Grzegorz; Brzezinski, Bogumil

    2002-04-01

    The complexes of 5,5'-dinitro-2,2'-biphenol (DNBPh) with 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene (MTBD) and triethylamine (TEA) were studied by FTIR and 1H NMR spectroscopy. In chloroform and in acetonitrile a proton transfer from DNBPh to N-bases (MTBD, TEA) occurs. In chloroform solution the protonated N-base molecules are hydrogen-bonded to the deprotonated DNBPh molecules whereas in acetonitrile the complexes dissociate and hence protonated N-base molecules and hydrogen-bonded chains formed between DNBPh and 5,5'-dinitro-2,2'-biphenolate are present. The intra- as well as inter-molecular hydrogen bonds within the chains show large proton polarizability.

  19. Comparison of Multiscale Method of Cells-Based Models for Predicting Elastic Properties of Filament Wound C/C-SiC

    Science.gov (United States)

    Pineda, Evan J.; Fassin, Marek; Bednarcyk, Brett A.; Reese, Stefanie; Simon, Jaan-Willem

    2017-01-01

    Three different multiscale models, based on the method of cells (generalized and high fidelity) micromechanics models were developed and used to predict the elastic properties of C/C-SiC composites. In particular, the following multiscale modeling strategies were employed: Concurrent multiscale modeling of all phases using the generalized method of cells, synergistic (two-way coupling in space) multiscale modeling with the generalized method of cells, and hierarchical (one-way coupling in space) multiscale modeling with the high fidelity generalized method of cells. The three models are validated against data from a hierarchical multiscale finite element model in the literature for a repeating unit cell of C/C-SiC. Furthermore, the multiscale models are used in conjunction with classical lamination theory to predict the stiffness of C/C-SiC plates manufactured via a wet filament winding and liquid silicon infiltration process recently developed by the German Aerospace Institute.

  20. IMPACT OF DIELECTRIC PARAMETERS ON THE REFLECTIVITY OF 3C-SiC WAFERS WITH A ROUGH SURFACE MORPHOLOGY IN THE RESTSTRAHLEN REGION

    Energy Technology Data Exchange (ETDEWEB)

    J.A.A. Engelbrecht; E. Janzén; A. Henry; I.J. van Rooyen

    2014-04-01

    A layer-on-substrate model is used to obtain the infrared reflectance for 3C-SiC with a rough surface morphology. The effect of varying dielectric parameters of the “damaged layer” on the observed reflectivity of the 3C-SiC in the reststrahlen region is assessed. Different simulated reflectance spectra are obtained to those if the dielectric parameters of the “substrate” were varied. Most notable changes in the shape of the simulated reststrahlen peak are observed for changes in the high frequency dielectric constant, the phonon damping constant, the phonon frequencies and “thickness” of damaged surface layer.

  1. CORRIGENDUM: The mechanism of defect creation and passivation at the SiC/SiO2 interface

    Science.gov (United States)

    Deák, Peter; Knaup, Jan; Thill, Christoph; Frauenheim, Thomas; Hornos, Tamás; Gali, Adam

    2008-02-01

    In a recent rewiew article we have reported—among other things—on preliminary computational studies regarding the effect of nitridation on the SiC/SiO2 interface, in case of n-type doping. We have since discovered a few numerical errors in the paper, which also influence some of our statements. Here we present the correct results and their consequences. 1. Introduction In our review we reported energies of reactions occurring at the SiC/SiO2 interface upon nitridation. Our computational approach was to calculate the energy of incoming and outgoing molecules in a bulk supercell of SiO2, and that of interface defects before or after the reaction in a slab model of the 4H-SiC/SiO2 interface. Incoming molecules in bulk SiO2 were assumed to be neutral, but the interface was coupled to a reservoir of electrons with energy corresponding to the Fermi level of the semiconductor. The latter was determined by the temperature of nitridation (~1100 °C) and the usual doping of the channel region (1015-1016 cm-3) of a MOS (metal-oxide-semiconductor) transistor with an n-type channel, to be 1.9-2.2 eV, with respect to the valence band edge of SiC. Using the calculated total energies, energies of exchange reactions between the models have been calculated, adding a band off-set correction for each electron transfer between the models (to account for the error introduced by using the pseudopotential approximation in two different models). Unfortunately, some of the results were erroneously given. Here we present the correct values, and briefly state the consequences. 2. Corrected results (A) The energy gain on reaction (1) of the original paper is equal to 3EF - 2.7 eV, which gives 3.0-3.9 eV in the Fermi-energy range considered (not, as erroneously reported 1.0-1.3 eV). As a consequence, this reaction is, in fact, dominating over reaction (2) of the original paper with an energy gain of EF + 0.7 eV, i.e., 2.6-2.9 eV in the chosen Fermi-level range. Therefore, nitrogen insertion

  2. Effects of bainitic transformation temperature on microstructure and tensile properties of 0.6C-Si-Mn steel; 0.6C-Si-Mn ko no bisai soshiki to hippari tokusei ni oyobosu benaito hentai ondo no eikyo

    Energy Technology Data Exchange (ETDEWEB)

    Tomita, Y. [University of Osaka Prefecture, Osaka (Japan). Faculty of Engineering

    1995-06-15

    To acquire excellent mechanical properties of Si-Mn steel by using an austempering treatment to have the steel undergo a bainitic transformation, it is important to identify the effect of its transformation temperature. This paper describes a transformation of 0.6% C-Si-Mn steel at temperatures ranging from 593 K to 673 K, and discussions on the effect of the transformation temperature on the microstructure and tensile properties. The following results were obtained: bainitic ferrite containing very little carbon is produced in layers at any transformation temperature, but a trend was shown that the bainitic ferrite is produced with its width grown larger and denser as the transformation temperature rises; the {gamma}R amount increases remarkably with increasing transformation temperature, and at the same time massive {gamma}R begins to remain in addition to thin film {gamma}R that exists between individual bainitic ferrites; and the result of this experiment revealed that when the transformation temperature is sufficiently high, the fracture elongation increases notably because of the transformation induced plasticity (TRIP) effect of the {gamma}R that occurs effectively during the transformation. 12 refs., 7 figs., 4 tabs.

  3. Possible interstellar formation of glycine through a concerted mechanism: a computational study on the reaction of CH2[double bond, length as m-dash]NH, CO2 and H2.

    Science.gov (United States)

    Nhlabatsi, Zanele P; Bhasi, Priya; Sitha, Sanyasi

    2016-07-27

    Glycine being the simplest amino acid and also having significant astrobiological implications, has meant that intensive investigations have been carried out in the past, starting from its detection in the interstellar medium (ISM) to analysis of meteorites and cometary samples and laboratory synthesis, as well as computational studies on the possible reaction paths. In this present work quantum chemical calculations have been performed to investigate the possible interstellar formation of glycine via two different paths; (1) in a two-step process via a dihydroxy carbene intermediate and (2) through a one-step concerted mechanism, starting from reactants like CH2[double bond, length as m-dash]NH, CO, CO2, H2O and H2. For the two reactions representing the carbene route, it was observed that the formation of dihydroxy carbene from either CO + H2O or CO2 + H2 is highly endothermic with large barrier heights, whereas the subsequent step of interaction of this carbene with CH2[double bond, length as m-dash]NH to give glycine is exothermic and the barrier is below the reactants. Based on this observation it is suggested that the formation of glycine via the carbene route is a least favourable or even unfavourable path. On the other hand, the two reactions CH2[double bond, length as m-dash]NH + CO + H2O and CH2[double bond, length as m-dash]NH + CO2 + H2 representing the concerted paths were found to be favourable in leading to the formation of glycine. After an extensive study on the first concerted reaction in our previous work (Phys. Chem. Chem. Phys., 2016, 18, 375-381), in this work a detailed investigation has been carried out for the second concerted reaction, CH2[double bond, length as m-dash]NH + CO2 + H2, which can possibly lead to the interstellar formation of glycine. It was observed that this reaction proceeds through a large barrier and at the same time the transition state shows prominent hydrogen dynamics, indicating a tunnelling possibility for this

  4. Vanadium-Catalyzed Oxidative C(CO)-C(CO) Bond Cleavage for C-N Bond Formation: One-Pot Domino Transformation of 1,2-Diketones and Amidines into Imides and Amides.

    Science.gov (United States)

    Digwal, Chander Singh; Yadav, Upasana; Ramya, P V Sri; Sana, Sravani; Swain, Baijayantimala; Kamal, Ahmed

    2017-07-21

    A novel vanadium-catalyzed one-pot domino reaction of 1,2-diketones with amidines has been identified that enables their transformation into imides and amides. The reaction proceeds by dual acylation of amidines via oxidative C(CO)-C(CO) bond cleavage of 1,2-diketones to afford N,N'-diaroyl-N-arylbenzamidine intermediates. In the reaction, these intermediates are easily hydrolyzed into imides and amides through vanadium catalysis. This method provides a practical, simple, and mild synthetic approach to access a variety of imides as well as amides in high yields. Moreover, one-step construction of imide and amide bonds with a long-chain alkyl group is an attractive feature of this protocol.

  5. Damage characteristics and constitutive modeling of the 2D C/SiC composite: Part I – Experiment and analysis

    Directory of Open Access Journals (Sweden)

    Li Jun

    2014-12-01

    Full Text Available This paper reports an experimental investigation on the macroscopic mechanical behaviors and damage mechanisms of the plain-woven (2D C/SiC composite under in-plane on- and off-axis loading conditions. Specimens with 15°, 30°, and 45° off-axis angles were prepared and tested under monotonic and incremental cyclic tension and compression loads. The obtained results were compared with those of uniaxial tension, compression, and shear specimens. The relationships between the damage modes and the stress state were analyzed based on scanning electronic microscopy (SEM observations and acoustic emission (AE data. The test results reveal the remarkable axial anisotropy and unilateral behavior of the material. The off-axis tension test results show that the material is fiber-dominant and the evolution rate of damage and inelastic strain is accelerated under the corresponding combined biaxial tension and shear loads. Due to the damage impediment effect of compression stress, compression specimens show higher mechanical properties and lower damage evolution rates than tension specimens with the same off-axis angle. Under cyclic tension–compression loadings, both on-axis and off-axis specimens exhibit progressive damage deactivation behaviors in the compression range, but with different deactivation rates.

  6. Novel Fe@C-TiO2 and Fe@C-SiO2 water-dispersible magnetic nanocomposites

    Science.gov (United States)

    Fleaca, Claudiu Teodor; Dumitrache, Florian; Morjan, Ion; Alexandrescu, Rodica; Luculescu, Catalin; Niculescu, Ana; Vasile, Eugeniu; Kuncser, Victor

    2013-08-01

    We report the synthesis of novel nanocomposites based on Fe@C nanoparticles obtained from Fe(CO)5 and C2H4/H2 by laser pyrolysis technique using a three nozzles injector. The αFe-FexCy@C particles (below 24 nm diameter) were first functionalized with hydrophilic groups using Na carboxymethylcellulose. Oxidic precursors (Si(OC2H5)4 or Ti(OC2H5)4) dissolved in ethanol were mixed with ethanolic suspensions of hydrophilized Fe@C nanoparticles using strong ultrasonication, then with water (at different pH values) and finally the Fe-containing composites were recovered by magnetic separation. The SiO2 and TiO2-coated powders were characterized by XRD, FT-IR and TEM techniques and their magnetic hysteresis curves were recorded at different temperatures. Both composites contain submicron aggregates of Fe@C nanoparticles embedded in/surrounded by a disordered porous oxidic matrix/shell. Near superparamagnetic behavior and room temperature and 26 A m2/kg (for Fe@C/SiO2) or 57 A m2/kg (for Fe@C/TiO2) saturation magnetization values were recorded and a blocking temperature around 500 K was extrapolated.

  7. Delamination Mechanisms of Thermal and Environmental Barrier Coatings on SiC/SiC Ceramic Matrix Composites

    Science.gov (United States)

    Zhu, Dongming; Choi, Sung R.; Lee, Kang N.; Miller, Robert A.

    2003-01-01

    Advanced ceramic thermal harrier coatings will play an increasingly important role In future gas turbine engines because of their ability to effectively protect the engine components and further raise engine temperatures. However, the coating durability issue remains a major concern with the ever-increasing temperature requirements. In this paper, thermal cyclic response and delamination failure modes of a ZrO2-8wt%Y2O3 and mullite/BSAS thermaVenvironmenta1 barrier coating system on SiC/SiC ceramic matrix composites were investigated using a laser high-heat-flux technique. The coating degradation and delamination processes were monitored in real time by measuring coating apparent conductivity changes during the cyclic tests under realistic engine temperature and stress gradients, utilizing the fact that delamination cracking causes an apparent decrease in the measured thermal conductivity. The ceramic coating crack initiation and propagation driving forces under the cyclic thermal loads, in conjunction with the mechanical testing results, will be discussed.

  8. Time-dependent bridging and life prediction of SiC/SiC in a hypothetical fusion environment

    Energy Technology Data Exchange (ETDEWEB)

    Henager, C.H. Jr.; Lewinsohn, C.A.; Windisch, C.F. Jr.; Jones, R.H. [Pacific Northwest National Lab., Richland, WA (United States)

    1996-10-01

    Growth of subcritical cracks in SiC/SiC composites of CG-Nicalon fibers with a {approximately}1 {mu}m C-interphase has been measured on a related Basic Energy Sciences program using environments of purified argon and mixtures of argon and oxygen at 1073K to 1373K. Companion thermo-gravimetric (TGA) testing measured mass loss in identical environments. The TGA mass loss was from C-interphase oxidation to CO and CO{sub 2}, which was undetectable in argon and linear with oxygen concentration in argon-oxygen mixtures, and was converted into an interphase linear recession rate. Crack growth in pure argon indicated that fiber creep was causing time-dependent crack bridging to occur, while crack growth in argon-oxygen mixtures indicated that time-dependent C-interphase recession was also causing time-dependent bridging with different kinetics. A model of time-dependent bridging was used to compute crack growth rates in argon and in argon-oxygen mixtures and gave an estimate of useable life of about 230 days at 1073K in a He + 1.01 Pa O{sub 2} (10 ppm) environment.

  9. Chemical Vapor Deposition of TaC/SiC on Graphite Tube and Its Ablation and Microstructure Studies

    Directory of Open Access Journals (Sweden)

    Suresh Kumar

    2017-07-01

    Full Text Available Tantalum carbide (TaC and silicon carbide (SiC layers were deposited on a graphite tube using a chemical vapor deposition process. Tantalum chloride (TaCl5 was synthesized in situ by reacting tantalum chips with chlorine at 550 °C. TaC was deposited by reacting TaCl5 with CH4 in the presence of H2 at 1050–1150 °C and 50–100 mbar. SiC was deposited at 1000 °C using methyl-tri-chloro-silane as a precursor at 50 mbar. At 1150 °C; the coating thickness was found to be about 600 μm, while at 1050 °C it was about 400 μm for the cumulative deposition time of 10 h. X-ray diffraction (XRD and X-ray Photo-Electron Spectroscopy (XPS studies confirmed the deposition of TaC and SiC and their phases. Ablation studies of the coated specimens were carried out under oxyacetylene flame up to 120 s. The coating was found to be intact without surface cracks and with negligible erosion. The oxide phase of TaC (TaO2 and Ta2O5 and the oxide phase of SiC (SiO2 were also found on the surface, which may have protected the substrate underneath from further oxidation.

  10. Effect of TCO/μc-Si:H Interface Modification on Hydrogenated Microcrystalline Silicon Thin-Film Solar Cells

    Directory of Open Access Journals (Sweden)

    Shin-Wei Liang

    2013-01-01

    Full Text Available The effects of H2 plasma exposure on optical, electrical, and structural properties of fluorine-doped tin oxide (FTO and AZO/FTO substrates have been investigated. With increasing the time of H2-plasma exposure, the hydrogen radical and ions penetrated through the FTO surface to form more suboxides such as SnO and metallic Sn, which was confirmed by the XPS analysis. The Sn reduction on the FTO surface can be effectively eliminated by capping the FTO with a very thin layer of sputtered aluminum-doped zinc oxide (AZO, as confirmed by the XPS analysis. By using the AZO/FTO as front TCO with the subsequent annealing, the p-i-n μc-Si:H cell exhibited a significantly enhanced JSC from 15.97 to 19.40 mA/cm2 and an increased conversion efficiency from 5.69% to 7.09%. This significant enhancement was ascribed to the effective elimination of the Sn reduction on the FTO surface by the thin AZO layer during the Si-based thin-film deposition with hydrogen-rich plasma exposure. Moreover, the subsequent annealing of the sputtered AZO could lead to less defects as well as a better interface of AZO/FTO.

  11. Development of ASTM Standard for SiC-SiC Joint Testing Final Scientific/Technical Report

    Energy Technology Data Exchange (ETDEWEB)

    Jacobsen, George [General Atomics, San Diego, CA (United States); Back, Christina [General Atomics, San Diego, CA (United States)

    2015-10-30

    As the nuclear industry moves to advanced ceramic based materials for cladding and core structural materials for a variety of advanced reactors, new standards and test methods are required for material development and licensing purposes. For example, General Atomics (GA) is actively developing silicon carbide (SiC) based composite cladding (SiC-SiC) for its Energy Multiplier Module (EM2), a high efficiency gas cooled fast reactor. Through DOE funding via the advanced reactor concept program, GA developed a new test method for the nominal joint strength of an endplug sealed to advanced ceramic tubes, Fig. 1-1, at ambient and elevated temperatures called the endplug pushout (EPPO) test. This test utilizes widely available universal mechanical testers coupled with clam shell heaters, and specimen size is relatively small, making it a viable post irradiation test method. The culmination of this effort was a draft of an ASTM test standard that will be submitted for approval to the ASTM C28 ceramic committee. Once the standard has been vetted by the ceramics test community, an industry wide standard methodology to test joined tubular ceramic components will be available for the entire nuclear materials community.

  12. Boron-doped hydrogenated microcrystalline silicon oxide (μc-SiOx:H) for application in thin-film silicon solar cells

    NARCIS (Netherlands)

    Lambertz, A.|info:eu-repo/dai/nl/411290983; Finger, F.; Holländer, B.; Rath, J.K.|info:eu-repo/dai/nl/304830585; Schropp, R.E.I.|info:eu-repo/dai/nl/072502584

    2011-01-01

    We report on the development of p-type μc-SiOx:H material, in particular the relationship between the deposition parameters and the material properties like band gap, electrical conductivity, and crystalline volume fraction. The material was deposited from gas mixtures of silane, carbon dioxide and

  13. Variation in the Optical Properties of the SiC-SiO2 Composite Antireflection Layer in Crystalline Silicon Solar Cells by Annealing

    Science.gov (United States)

    Jannat, Azmira; Li, Zhen Yu; Akhter, M. Shaheer; Yang, O.-Bong

    2017-11-01

    This study showed the effects of annealing on a sol-gel-derived SiC-SiO2 composite antireflection (AR) layer and investigated the optical and photovoltaic properties of crystalline silicon (Si) solar cells. The SiC-SiO2 composite AR coating showed a considerable decrease in reflectance from 7.18% to 3.23% at varying annealing temperatures of 450-800°C. The refractive indices of the SiC-SiO2 composite AR layer were tuned from 2.06 to 2.45 with the increase in annealing temperature. The analysis of the current density-voltage characteristics indicated that the energy conversion efficiencies of the fabricated Si solar cells gradually increased from 16.99% to 17.73% with increasing annealing temperatures of 450-800°C. The annealing of the SiC-SiO2 composite AR layer in Si solar cells was crucial to improving the optical, morphological, and photovoltaic properties.

  14. Synthesis and optical characterization of C-SiO2 and C-NiO sol-gel composite films for use as selective solar absorbers

    CSIR Research Space (South Africa)

    Makiwa, G

    2008-08-01

    Full Text Available The authors present a cheaper and environmentally friendly method to fabricate efficient spectrally selective solar absorber materials. The sol-gel technique was used to fabricate carbon-silica (C-SiO2) and carbon-nickel oxide (C-NiO) composite...

  15. Creep/Stress Rupture Behavior and Failure Mechanisms of Full CVI and Full PIP SiC/SiC Composites at Elevated Temperatures in Air

    Science.gov (United States)

    Bhatt, R. T.; Kiser, J. D.

    2017-01-01

    SiC/SiC composites fabricated by melt infiltration are being considered as potential candidate materials for next generation turbine components. However these materials are limited to 2400 F application because of the presence of residual silicon in the SiC matrix. Currently there is an increasing interest in developing and using silicon free SiC/SiC composites for structural aerospace applications above 2400 F. Full PIP or full CVI or CVI + PIP hybrid SiC/SiC composites can be fabricated without excess silicon, but the upper temperature stress capabilities of these materials are not fully known. In this study, the on-axis creep and rupture properties of the state-of-the-art full CVI and full PIP SiC/SiC composites with Sylramic-iBN fibers were measured at temperatures to 2700 F in air and their failure modes examined. In this presentation creep rupture properties, failure mechanisms and upper temperature capabilities of these two systems will be discussed and compared with the literature data.

  16. Correlation between Macro-Mechanical Behavior and Microstructure Characteristics in SiC/SiC Composites; A Micro-Raman Spectroscopy Study (Preprint)

    Science.gov (United States)

    2017-04-19

    mechanical performance and mechanical constants of SiC/SiC CMCs are very sensitive to processing. This is especially true for properties such as the elastic...to processing. This is especially true for properties such as the elastic modulus, tensile strength and strain to failure. In this paper, micro

  17. Formation of hydrogen-bonded complexes of 3,3',5,5'-tetrabromo-2,2'-biphenol with MTBD and triethylamine

    Science.gov (United States)

    Wojciechowski, Grzegorz; Brzezinski, Bogumil

    2002-10-01

    The complexes of 3,3',5,5'-tetrabromo-2,2'-biphenol (TBBPh) with 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene (MTBD) and triethylamine (TEA) were studied by FTIR spectroscopy. In chloroform and in acetonitrile a proton transfer from TBBPh to N-bases (MTBD, TEA) occurs. In chloroform solution the protonated N-base molecules are hydrogen-bonded to the deprotonated TBBPh molecules, whereas in acetonitrile the complexes dissociate. The intra- as well as intermolecular hydrogen bonds within the chains show large proton polarizability.

  18. M3FT-16OR020202112 - Report on viability of hydrothermal corrosion resistant SiC/SiC Joint development

    Energy Technology Data Exchange (ETDEWEB)

    Katoh, Yutai [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Koyanagi, Takaaki [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Kiggans Jr, James O. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Terrani, Kurt A. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

    2016-06-30

    Hydrothermal corrosion of four types of the silicon carbide (SiC) to SiC plate joints were investigated under PWR and BWR relevant chemical conditions without irradiation. The joints were formed by metal diffusion bonding using molybdenum or titanium interlayer, reaction sintering using Ti-Si-C system, and SiC nanopowder sintering. Most of the formed joints withstood the corrosion tests for five weeks. The recession of the SiC substrates was limited. Based on the recession rate of the bonding layers, it was concluded that all the joints except for the molybdenum diffusion bond are promising under the reducing activity environments. The SiC nanopowder sintered joint was the most corrosion tolerant under the oxidizing activity environment among the four joints.

  19. Hydrogen bonded supramolecular materials

    CERN Document Server

    Li, Zhan-Ting

    2015-01-01

    This book is an up-to-date text covering topics in utilizing hydrogen bonding for constructing functional architectures and supramolecular materials. The first chapter addresses the control of photo-induced electron and energy transfer. The second chapter summarizes the formation of nano-porous materials. The following two chapters introduce self-assembled gels, many of which exhibit unique functions. Other chapters cover the advances in supramolecular liquid crystals and the versatility of hydrogen bonding in tuning/improving the properties and performance of materials. This book is designed

  20. Isopeptide bonds of the major pilin protein BcpA influence pilus structure and bundle formation on the surface of Bacillus cereus

    Energy Technology Data Exchange (ETDEWEB)

    Hendrickx, Antoni P.A.; Poor, Catherine B.; Jureller, Justin E.; Budzik, Jonathan M.; He, Chuan; Schneewind, Olaf (UC)

    2012-09-05

    Bacillus cereus strains elaborate pili on their surface using a mechanism of sortase-mediated cross-linking of major and minor pilus components. Here we used a combination of electron microscopy and atomic force microscopy to visualize these structures. Pili occur as single, double or higher order assemblies of filaments formed from monomers of the major pilin, BcpA, capped by the minor pilin, BcpB. Previous studies demonstrated that within assembled pili, four domains of BcpA -- CNA{sub 1}, CNA{sub 2}, XNA and CNA{sub 3} -- each acquire intramolecular lysine-asparagine isopeptide bonds formed via catalytic glutamic acid or aspartic acid residues. Here we showed that mutants unable to form the intramolecular isopeptide bonds in the CNA2 or CNA3 domains retain the ability to form pilus bundles. A mutant lacking the CNA{sub 1} isopeptide bond assembled deformed pilin subunits that failed to associate as bundles. X-ray crystallography revealed that the BcpA variant Asp{sup 312}Ala, lacking an aspartyl catalyst, did not generate the isopeptide bond within the jelly-roll structure of XNA. The Asp{sup 312}Ala mutant was also unable to form bundles and promoted the assembly of deformed pili. Thus, structural integrity of the CNA{sub 1} and XNA domains are determinants for the association of pili into higher order bundle structures and determine native pilus structure.

  1. SOCIAL BONDING: REGULATION BY NEUROPEPTIDES

    Directory of Open Access Journals (Sweden)

    Claudia eLieberwirth

    2014-06-01

    Full Text Available Affiliative social relationships (e.g., among spouses, family members, and friends play an essential role in human society. These relationships affect psychological, physiological, and behavioral functions. As positive and enduring bonds are critical for the overall well-being of humans, it is not surprising that considerable effort has been made to study the neurobiological mechanisms that underlie social bonding behaviors. The present review details the involvement of the nonapeptides, oxytocin (OT and arginine vasopressin (AVP, in the regulation of social bonding in mammals including humans. In particular, we will discuss the role of OT and AVP in the formation of social bonds between partners of a mating pair as well as between parents and their offspring. Furthermore, the role of OT and AVP in the formation of interpersonal bonding involving trust is also discussed.

  2. Reductive benzylation of singly bonded 1,2,4,15-C60 dimers with an oxazoline or imidazoline heterocycle: unexpected formation of 1,2,3,16-C60 adducts and insights into the reactivity of singly bonded C60 dimers.

    Science.gov (United States)

    Li, Zong-Jun; Li, Shu-Hui; Sun, Tao; Hou, Hui-Lei; Gao, Xiang

    2015-04-03

    Upon reduction, singly bonded 1,2,4,15-C60 dimers with an oxazoline or imidazoline heterocycle dissociate into monoanionic 1,2,4-C60 intermediates, which surprisingly leads to the formation of 1,2,3,16-C60 rather than 1,2,4,15-C60 adducts of the original configuration by further benzylation, even though the analogue of dibenzylated C60 oxazoline with a 1,2,4,15-configuration is stable and has been obtained. These results are corroborated by computational calculations, which rationalize the reaction and clarify the structure of the 1,2,3,16-C60 adducts, providing new insights into the intrinsic reactivity of singly bonded C60 dimers.

  3. Improvement of μc-Si:H n–i–p cell efficiency with an i-layer made by hot-wire CVD by reverse H2-profiling

    NARCIS (Netherlands)

    Li, H. B. T.; Franken, R.H.; Stolk, R.L.; van der Werf, C.H.M.; Rath, J.K.; Schropp, R.E.I.

    2008-01-01

    The technique of maintaining a proper crystalline ratio in microcrystalline silicon (μc-Si:H) layers along the thickness direction by decreasing the H2 dilution ratio during deposition (H2 profiling) was introduced by several laboratories while optimizing either n–i–p or p–i–n μc-Si:H cells made by

  4. A Model for the Chemical Bond

    Science.gov (United States)

    Magnasco, Valerio

    2004-01-01

    Bond stereochemistry in polyatomic hydrides is explained in terms of the principle of bond energies maximization, which yields X-H straight bonds and suggests the formation of appropriate sp hybrids on the central atom. An introduction to the electron charge distribution in molecules is given, and atomic, overlap, gross and formal charges are…

  5. The thermodynamics and kinetics of phosphoester bond formation, use, and dissociation in biology, with the example of polyphosphate in platelet activation, trasience, and mineralization.

    Science.gov (United States)

    Omelon, S. J.

    2014-12-01

    Mitochondria condense orthophosphates (Pi), forming phosphoester bonds for ATP production that is important to life. This represents an exchange of energy from dissociated carbohydrate bonds to phosophoester bonds. These bonds are available to phosphorylate organic compounds or hydrolyze to Pi, driving many biochemical processes. The benthic bacteria T. namibiensis 1 and Beggiatoa 2 condense Pi into phosphate polymers in oxygenated environments. These polyphosphates (polyPs) are stored until the environment becomes anoxic, when these bacteria retrieve the energy from polyP dissociation into Pi3. Dissociated Pi is released outside of the bacteria, where it precipitates as apatite.The Gibbs free energy of polyP phosphoester bond hydrolysis is negative, however, the kinetics are slow4. Diatoms contain a polyP pool that is stable until after death, after which the polyPs hydrolyze and form apatite5. The roles of polyP in eukaryotic organism biochemistry continue to be discovered. PolyPs have a range of biochemical roles, such as bioavailable P-storage, stress adaptation, and blood clotting6. PolyP-containing granules are released from anuclear platelets to activate factor V7 and factor XII in the blood clotting process due to their polyanionic charge8. Platelets have a lifespan of approximately 8 days, after which they undergo apoptosis9. Data will be presented that demonstrate the bioactive, thermodynamically unstable polyP pool within older platelets in vitro can spontaneously hydrolyze and form phosphate minerals. This process is likely avoided by platelet digestion in the spleen and liver, possibly recycling platelet polyPs with their phosphoester bond energy for other biochemical roles. 1 Schulz HN et al. Science (2005) 307: 416-4182 Brüchert V et al. Geochim Cosmochim Acta (2003) 67: 4505-45183 Goldhammer T et al. Nat Geosci (2010) 3: 557-5614 de Jager H-J et al. J Phys Chem A (1988) 102: 2838-28415 Diaz, J et al. Science (2008) 320: 652-6556 Mason KD et al

  6. DsbA2 (27-kDa Com1-Like Protein) of Legionella pneumophila Catalyses Extracytoplasmic Disulfide-Bond Formation in Proteins Including the Dot/Icm Type IV Secretion System

    OpenAIRE

    Jameson-Lee, Max; Rafael A Garduno; Hoffman, Paul S.

    2011-01-01

    In Gram negative bacteria, thiol oxidoreductases catalyze the formation of disulfide bonds (DSB) in extracytoplasmic proteins. In this study, we sought to identify DSB-forming proteins required for assembly of macromolecular structures in Legionella pneumophila. Here we describe two DSB forming proteins, one annotated as dsbA1 and the other annotated as a 27-kDa outer membrane protein similar to Com1 of Coxiella burnetii, which we designate as dsbA2. Both proteins are predicted to be periplas...

  7. Investigation of the agglomeration and amorphous transformation effects of neutron irradiation on the nanocrystalline silicon carbide (3C-SiC) using TEM and SEM methods

    Energy Technology Data Exchange (ETDEWEB)

    Huseynov, Elchin M., E-mail: elchin.h@yahoo.com [Department of Nanotechnology and Radiation Material Science, National Nuclear Research Center, Inshaatchilar pr. 4, AZ 1073 Baku (Azerbaijan); Institute of Radiation Problems of Azerbaijan National Academy of Sciences, B.Vahabzade 9, AZ 1143 Baku (Azerbaijan)

    2017-04-01

    Nanocrystalline 3C-SiC particles irradiated by neutron flux during 20 h in TRIGA Mark II light water pool type research reactor. Silicon carbide nanoparticles were analyzed by Scanning Electron Microscope (SEM) and Transmission Electron Microscopy (TEM) devices before and after neutron irradiation. The agglomeration of nanoparticles was studied comparatively before and after neutron irradiation. After neutron irradiation the amorphous layer surrounding the nanoparticles was analyzed in TEM device. Neutron irradiation defects in the 3C-SiC nanoparticles and other effects investigated by TEM device. The effect of irradiation on the crystal structure of the nanomaterial was studied by selected area electron diffraction (SAED) and electron diffraction patterns (EDP) analysis.

  8. Electronic structure and magnetic properties of (Cu, N)-codoped 3C-SiC studied by first-principles calculations

    Science.gov (United States)

    Pan, Feng-chun; Chen, Zhi-peng; Lin, Xue-ling; Zheng, Fu; Wang, Xu-ming; Chen, Huan-ming

    2016-09-01

    The electronic structures and magnetic properties of the Cu and N codoped 3C-SiC system have been investigated by the first-principles calculation. The results show that the Cu doped SiC system prefers the anti-ferromagnetic (AFM) state. Compared to the Cu doped system, the ionicities of C-Cu and C-Si in Cu and N codoped SiC are respectively enhanced and weakened. Especially, the Cu and N codoped SiC systems favor the ferromagnetic (FM) coupling. The FM interactions can be explained by virtual hopping. However, higher N concentration will weaken the ferromagnetism. In order to keep the FM interaction, the N concentration should be restricted within 9.3% according to our analysis. Project supported by the Higher School Science Research Outstanding Youth Fund Project of Ningxia, China (Grant No. NGY2015049).

  9. Mechanical Properties and Real-Time Damage Evaluations of Environmental Barrier Coated SiC/SiC CMCs Subjected to Tensile Loading Under Thermal Gradients

    Science.gov (United States)

    Appleby, Matthew; Zhu, Dongming; Morscher, Gregory

    2015-01-01

    SiC/SiC ceramic matrix composites (CMCs) require new state-of-the art environmental barrier coatings (EBCs) to withstand increased temperature requirements and high velocity combustion corrosive combustion gasses. The present work compares the response of coated and uncoated SiC/SiC CMC substrates subjected to simulated engine environments followed by high temperature mechanical testing to asses retained properties and damage mechanisms. Our focus is to explore the capabilities of electrical resistance (ER) measurements as an NDE technique for testing of retained properties under combined high heat-flux and mechanical loading conditions. Furthermore, Acoustic Emission (AE) measurements and Digital Image Correlation (DIC) were performed to determine material damage onset and accumulation.

  10. Elastic and inelastic properties of SiC/Si biomorphic composites and biomorphic SiC based on oak and eucalyptus

    Science.gov (United States)

    Kardashev, B. K.; Nefagin, A. S.; Smirnov, B. I.; de Arellano-Lopez, A. R.; Martinez-Fernandez, J.; Sepulveda, R.

    2006-09-01

    This paper reports on the results of a comparative investigation into the elastic and microplastic properties of biomorphic SiC/Si composites and biomorphic SiC prepared by pyrolysis of oak and eucalyptus with subsequent infiltration of molten silicon into a carbon matrix and additional chemical treatment to remove excess silicon. The acoustic studies were performed by the composite oscillator technique using resonant longitudinal vibrations at frequencies of about 100 kHz. It is shown that, in biomorphic SiC (as in biomorphic SiC/Si) at small-amplitude strains ɛ, adsorption and desorption of the environmental (air) molecules determine to a considerable extent the Young’s modulus E and the internal friction (decrement of acoustic vibrations δ) and that the changes in E and δ at these amplitudes are irreversible. The stress-microplastic strain curves are constructed from the acoustic data for the materials under study at temperatures of 100 and 290 K.

  11. Development of Advanced Environmental Barrier Coatings for SiC/SiC Ceramic Matrix Composites: Path Toward 2700 F Temperature Capability and Beyond

    Science.gov (United States)

    Zhu, Dongming; Harder, Bryan; Hurst, Janet B.; Good, Brian; Costa, Gustavo; Bhatt, Ramakrishna T.; Fox, Dennis S.

    2017-01-01

    Advanced environmental barrier coating systems for SiC-SiC Ceramic Matrix Composite (CMC) turbine and combustor hot section components are currently being developed to meet future turbine engine emission and performance goals. One of the significant coating development challenges is to achieve prime-reliant environmental barrier coating systems to meet the future 2700F EBC-CMC temperature stability and environmental durability requirements. This presentation will emphasize recent NASA environmental barrier coating system testing and down-selects, particularly the development path and properties towards 2700-3000F durability goals by using NASA hafnium-hafnia-rare earth-silicon-silicate composition EBC systems for the SiC-SiC CMC turbine component applications. Advanced hafnium-based compositions for enabling next generation EBC and CMCs capabilities towards ultra-high temperature ceramic coating systems will also be briefly mentioned.

  12. A frequent, GxxxG-mediated, transmembrane association motif is optimized for the formation of interhelical Cα–H hydrogen bonds

    OpenAIRE

    Mueller, Benjamin K.; Subramaniam, Sabareesh; Senes, Alessandro

    2014-01-01

    The transmembrane helices of single-span membrane proteins are commonly engaged in oligomeric interactions that are essential for structure and function. These interactions often occur in the form of recurrent structural motifs. Here we present an analysis of one of the most important motifs (GASright), showing that its geometry is optimized to form carbon hydrogen bonds at the helix−helix interface. The analysis reveals the structural basis for its characteristic GxxxG sequence signature. We...

  13. Properties of the major non-specific endonuclease from the strict anaerobe Fibrobacter succinogenes and evidence for disulfide bond formation in vivo.

    Science.gov (United States)

    MacLellan, S R; Forsberg, C W

    2001-02-01

    DNase A is a non-specific endonuclease of Fibrobacter succinogenes. The enzyme was purified to homogeneity and its properties studied both in vitro and in vivo. Magnesium but not calcium was essential for nucleolytic activity. Manganese ions substituted for magnesium but were less stimulatory. DNase A activity was markedly inhibited by either NaCl or KCl at concentrations greater than 75 mM. The enzyme had a temperature optimum of 25 degrees C and a pH optimum of about 7.0. Values for K:(m) and K:(cat) were determined to be 61 microM and 330 s(-1) respectively, with a catalytic efficiency approximately threefold greater than bovine pancreatic DNase I, but 10-fold less than the Serratia marcescens NucA. DNase A was localized to the periplasm and probably exists as a monomeric species. The enzyme possessed one or more disulfide bonds. In the reduced form it had an apparent mass of 33 kDa, while in the oxidized form it was 29 kDa as estimated by SDS-PAGE. Reduction of the disulfide bonds by dithiothreitol with or without subsequent alkylation by iodoacetamide strongly inactivated the enzyme. DNase A accumulated in vivo had an apparent mass of 29 kDa, indicating that it was in an oxidized form. This is the first indication in a strict anaerobe of a functional periplasmic disulfide bond forming system, phenotypically similar to Dsb systems in facultative and aerobic bacteria.

  14. Investigation of chemical bonding states at interface of Zn/organic materials for analysis of early stage of inorganic/organic hybrid multi-layer formation

    Energy Technology Data Exchange (ETDEWEB)

    Cho, Ken, E-mail: k_cho@jwri.osaka-u.ac.jp [Joining and Welding Research Institute, Osaka University, 11-1 Mihogaoka, Ibaraki, Osaka 567-0047 (Japan); Japan Science and Technology Agency, CREST (Japan); Takenaka, Kosuke; Setsuhara, Yuichi [Joining and Welding Research Institute, Osaka University, 11-1 Mihogaoka, Ibaraki, Osaka 567-0047 (Japan); Japan Science and Technology Agency, CREST (Japan); Shiratani, Masaharu [Department of Electronics, Kyushu University, 744 Moto-oka, Nishi-ku, Fukuoka 819-0395 (Japan); Japan Science and Technology Agency, CREST (Japan); Sekine, Makoto; Hori, Masaru [Plasma Nanotechnology Research Center, Nagoya University Furo-cho, Chikusa-ku, Nagoya 464-8603 (Japan); Japan Science and Technology Agency, CREST (Japan)

    2012-11-15

    Interactions between Ar-O{sub 2} mixture plasmas and Zn thin film on polyethylene terephthalate (PET) were investigated using the combinatorial plasma process analyzer, on the basis of nondestructive depth analyses of chemical bonding states at Zn thin film and Zn/PET interface via hard X-ray photoelectron spectroscopy (HXPES). After the Ar-O{sub 2} plasma exposure, peak-area ratio of O 1 s to Zn 2p{sub 3/2} evaluated from the HXPES spectra is found to increase with increasing the ion saturation current Multiplication-Sign time and saturated at the value obtained from ZnO. The HXPES C 1 s spectra measured at a take-off angle (TOA) of 80 Degree-Sign showed insignificant change in oxygen functionalities (O=C-O bond and C-O bond) after the deposition of Zn thin film and the plasma exposure. Whereas, the HXPES C 1 s spectra measurement at a TOA of 20 Degree-Sign suggested that the oxygen functionalities degraded in shallower regions up to about a few nanometer from the Zn/PET interface due to deposition of Zn thin film. However, after the plasma exposure, oxidation of PET substrate at the degraded layer of Zn/PET interface was caused by oxygen radicals and/or ions, which diffused through the Zn thin film.

  15. Validated physical models and parameters of bulk 3C-SiC aiming for credible technology computer aided design (TCAD) simulation

    Science.gov (United States)

    Arvanitopoulos, A.; Lophitis, N.; Gyftakis, K. N.; Perkins, S.; Antoniou, M.

    2017-10-01

    The cubic form of SiC (β- or 3C-) compared to the hexagonal α-SiC polytypes, primarily 4H- and 6H-SiC, has lower growth cost and can be grown heteroepitaxially in large area silicon (Si) wafers which makes it of special interest. This in conjunction with the recently reported growth of improved quality 3C-SiC, make the development of devices an imminent objective. However, the readiness of models that accurately predict the material characteristics, properties and performance is an imperative requirement for attaining the design and optimization of functional devices. The purpose of this study is to provide and validate a comprehensive set of models alongside with their parameters for bulk 3C-SiC. The validation process revealed that the proposed models are in a very good agreement to experimental data and confidence ranges were identified. This is the first piece of work achieving that for 3C-SiC. Considerably, it constitutes the necessary step for finite element method simulations and technology computer aided design.

  16. Photocarrier radiometry for predicting the degradation of electrical parameters of monocrystalline silicon (c-Si) solar cell irradiated by 100 KeV proton beams

    Energy Technology Data Exchange (ETDEWEB)

    Song, P. [School of Mechatronics Engineering, Harbin Institute of Technology, Harbin 150001 (China); Liu, J.Y., E-mail: ljywlj@hit.edu.cn [School of Mechatronics Engineering, Harbin Institute of Technology, Harbin 150001 (China); State Key Laboratory of Robotics and System (HIT), Harbin 150001 (China); Yuan, H.M.; Oliullah, Md.; Wang, F. [School of Mechatronics Engineering, Harbin Institute of Technology, Harbin 150001 (China); Wang, Y., E-mail: songpengkevin@126.com [School of Mechatronics Engineering, Harbin Institute of Technology, Harbin 150001 (China); State Key Laboratory of Robotics and System (HIT), Harbin 150001 (China)

    2016-09-15

    In this study, the monocrystalline silicon (c-Si) solar cell irradiated by 100 KeV proton beams at various fluences is investigated. A one-dimensional two-layer carrier density wave model has been developed to estimate the minority carrier lifetime of n-region and p-region of the non-irradiated c-Si solar cell by best fitting with the experimental photocarrier radiometry (PCR) signal (the amplitude and the phase). Furthermore, the lifetime is used to determine the initial defect density of the quasi-neutral region (QNR) of the solar cell to predict its I–V characteristics. The theoretically predicted short-circuit current density (J{sub sc}), and open-circuit voltage (V{sub oc}) of the non-irradiated samples are in good agreement with experiment. Then a three-region defect distribution model for the c-Si solar cell irradiated by proton beams is carried out to describe the defect density distribution according to Monte Carlo simulation results and the initial defect density of the non-irradiated sample. Finally, we find that the electrical measurements of J{sub sc} and V{sub oc} of the solar cells irradiated at different fluences using 100 KeV proton beams are consistent with the PCR predicting results.

  17. Effect of 3C-SiC intermediate layer in GaN—based light emitting diodes grown on Si(111) substrate

    Science.gov (United States)

    Zhu, Youhua; Wang, Meiyu; Li, Yi; Tan, Shuxin; Deng, Honghai; Guo, Xinglong; Yin, Haihong; Egawa, Takashi

    2017-03-01

    GaN-based light emitting diodes (LEDs) have been grown by metalorganic chemical vapor deposition on Si(111) substrate with and without 3C-SiC intermediate layer (IL). Structural property has been characterized by means of atomic force microscope, X-ray diffraction, and transmission electron microscope measurements. It has been revealed that a significant improvement in crystalline quality of GaN and superlattice epitaxial layers can be achieved by using 3C-SiC as IL. Regarding of electrical and optical characteristics, it is clearly observed that the LEDs with its IL have a smaller leakage current and higher light output power comparing with the LEDs without IL. The better performance of LEDs using 3C-SiC IL can be contributed to both of the improvements in epitaxial layers quality and light extraction efficiency. As a consequence, in terms of optical property, a double enhancement of the light output power and external quantum efficiency has been realized.

  18. Mimicry of the regulatory role of urokinase in lamellipodia formation by introduction of a non-native interdomain disulfide bond in its receptor

    DEFF Research Database (Denmark)

    Gårdsvoll, Henrik; Kjærgaard, Magnus; Jacobsen, Benedikte

    2011-01-01

    for the somatomedin B domain of vitronectin compared with uPAR(wt), thus recapitulating the improved affinity that accompanies uPA-uPAR(wt) complex formation. This functional mimicry is, intriguingly, operational also in a cellular setting, where it controls lamellipodia formation in uPAR-transfected HEK293 cells...

  19. A comparative first-principles study of orbital hybridization in two-dimensional C, Si, and Ge.

    Science.gov (United States)

    Wang, Shaoqing

    2011-07-07

    Information on orbital hybridization is very important to understand the structural, physical, and chemical properties of a material. Results of a comparative first-principles study on the behaviours of orbital hybridization in the two-dimensional single-element phases by carbon, silicon, and germanium are presented. From the well-known three-dimensional hexagonal lonsdaleite structure, in which the atoms are in ideal sp(3)-bonding, the layer spacing along c-axis is gradually stretched to simulate the evolutions of structural and electronic properties from three-dimensional to two-dimensional lattice configurations in the three materials. A turning point of the total system energy due to the sp(3) to sp(2) transition is observed during this process in carbon. In contrast, no such phenomenon is found in silicon and germanium. The differences in electronic structure and bonding behaviour are further examined through comparative investigation of atomic angular-momentum projected density of states and electronic energy band spectrums of these materials. We demonstrate that the valence electronic orbital in the two-dimensional hexagonal crystals of Si and Ge shows sp(3)-like behaviour for the partial hybridization of s and p(z), which leads to their different lattice configurations to graphene. The role of π-bonds in stabilizing the flat configuration of graphene is also discussed. This journal is © the Owner Societies 2011

  20. Controlling superstructural ordering in the clathrate-I Ba 8 M 16 P 30 (M = Cu, Zn) through the formation of metal–metal bonds

    Energy Technology Data Exchange (ETDEWEB)

    Dolyniuk, J.; Whitfield, P. S.; Lee, K.; Lebedev, O. I.; Kovnir, K.

    2017-01-01

    Order–disorder–order phase transitions in the clathrate-I Ba8Cu16P30 were induced and controlled by aliovalent substitutions of Zn into the framework. Unaltered Ba8Cu16P30 crystallizes in an ordered orthorhombic (Pbcn) clathrate-I superstructure that maintains complete segregation of metal and phosphorus atoms over 23 different crystallographic positions in the clathrate framework. The driving force for the formation of this Pbcn superstructure is the avoidance of Cu–Cu bonds. This superstructure is preserved upon aliovalent substitution of Zn for Cu in Ba8Cu16-xZnxP30 with 0 < x < 1.6 (10% Zn/Mtotal), but vanishes at greater substitution concentrations. Higher Zn concentrations (up to 35% Zn/Mtotal) resulted in the additional substitution of Zn for P in Ba8M16+yP30-y (M = Cu, Zn) with 0 ≤ y ≤ 1. This causes the formation of Cu–Zn bonds in the framework, leading to a collapse of the orthorhombic superstructure into the more common cubic subcell of clathrate-I (Pm[3 with combining macron]n). In the resulting cubic phases, each clathrate framework position is jointly occupied by three different elements: Cu, Zn, and P. Detailed structural characterization of the Ba–Cu–Zn–P clathrates-I via single crystal X-ray diffraction, joint synchrotron X-ray and neutron powder diffractions, pair distribution function analysis, electron diffraction and high-resolution electron microscopy, along with elemental analysis, indicates that local ordering is present in the cubic clathrate framework, suggesting the evolution of Cu–Zn bonds. For the compounds with the highest Zn content, a disorder–order transformation is detected due to the formation of another superstructure with trigonal symmetry and Cu–Zn bonds in the clathrate-I framework. It is shown that small changes in the composition, synthesis, and crystal structure have significant impacts on the structural and transport properties of Zn-substituted Ba8Cu16P30.

  1. Protección contra la oxidación de materiales compuestos SiC(C/SiC mediante la combinación de recubrimientos de silicatos de itrio y sílice

    Directory of Open Access Journals (Sweden)

    Aparicio, M.

    2001-12-01

    Full Text Available The factor which currently precludes the use of carbon fibre reinforced silicon carbide (C/SiC in high temperature structural applications is the oxidation of carbon fibres at temperatures greater than 450ºC (1. For this reason, it is necessary to develop coatings capable of protecting C/SiC components from oxidation for extended periods at 1600ºC. Conventional coatings consist of multilayers of different materials with complementary antioxidant properties. The objective of this work was to develop a multilayer coating consisted by a bonding layer of SiC, a intermediate layer of yttrium silicates: Y2Si2O7 and Y2SiO5, and an external layer of SiO2. Different techniques have been used to prepare the layers: painting with policarbosilane solutions, slip-coating and sol-gel, respectively. The behaviour against oxidation of coated composite material has been evaluated, and the samples before and after oxidation has been characterised by SEM. The cracking of SiC coating leads to a very low oxidation resistance at low temperatures. Only when the substrate is protected by the trilayer coating the reduction of the oxidation rate is considerable, and the weight loss is reduced from 50% (with a SiC coating to 15%.

    El principal inconveniente para la utilización de los materiales compuestos C/SiC en aplicaciones estructurales de alta temperatura es la elevada velocidad de oxidación de la fibra de carbono por encima de 450°C (1. Por esta razón, es necesario el desarrollo de recubrimientos capaces de proteger de la oxidación a estos materiales durante periodos prolongados a temperaturas de hasta 1600°C. Habitualmente, los recubrimientos están formados por multicapas con características antioxidantes complementarias. El objetivo de este trabajo ha sido el desarrollo de un recubrimiento multicapa formado por una capa interior de SiC, una intermedia de silicatos de itrio: Y2Si2O7 y Y2SiO5, y una exterior de SiO2. En su procesamiento se han

  2. Accumulation of β-Conglycinin in Soybean Cotyledon through the Formation of Disulfide Bonds between α′- and α-Subunits1[W][OA

    Science.gov (United States)

    Wadahama, Hiroyuki; Iwasaki, Kensuke; Matsusaki, Motonori; Nishizawa, Keito; Ishimoto, Masao; Arisaka, Fumio; Takagi, Kyoko; Urade, Reiko

    2012-01-01

    β-Conglycinin, one of the major soybean (Glycine max) seed storage proteins, is folded and assembled into trimers in the endoplasmic reticulum and accumulated into protein storage vacuoles. Prior experiments have used soybean β-conglycinin extracted using a reducing buffer containing a sulfhydryl reductant such as 2-mercaptoethanol, which reduces both intermolecular and intramolecular disulfide bonds within the proteins. In this study, soybean proteins were extracted from the cotyledons of immature seeds or dry beans under nonreducing conditions to prevent the oxidation of thiol groups and the reduction or exchange of disulfide bonds. We found that approximately half of the α′- and α-subunits of β-conglycinin were disulfide linked, together or with P34, prior to amino-terminal propeptide processing. Sedimentation velocity experiments, size-exclusion chromatography, and two-dimensional polyacrylamide gel electrophoresis (PAGE) analysis, with blue native PAGE followed by sodium dodecyl sulfate-PAGE, indicated that the β-conglycinin complexes containing the disulfide-linked α′/α-subunits were complexes of more than 720 kD. The α′- and α-subunits, when disulfide linked with P34, were mostly present in approximately 480-kD complexes (hexamers) at low ionic strength. Our results suggest that disulfide bonds are formed between α′/α-subunits residing in different β-conglycinin hexamers, but the binding of P34 to α′- and α-subunits reduces the linkage between β-conglycinin hexamers. Finally, a subset of glycinin was shown to exist as noncovalently associated complexes larger than hexamers when β-conglycinin was expressed under nonreducing conditions. PMID:22218927

  3. S-glutathionylation of glyceraldehyde-3-phosphate dehydrogenase induces formation of C150-C154 intrasubunit disulfide bond in the active site of the enzyme.

    Science.gov (United States)

    Barinova, K V; Serebryakova, M V; Muronetz, V I; Schmalhausen, E V

    2017-12-01

    Glyceraldehyde-3-phosphate dehydrogenase (GAPDH) is a glycolytic protein involved in numerous non-glycolytic functions. S-glutathionylated GAPDH was revealed in plant and animal tissues. The role of GAPDH S-glutathionylation is not fully understood. Rabbit muscle GAPDH was S-glutathionylated in the presence of H 2 O 2 and reduced glutathione (GSH). The modified protein was assayed by MALDI-MS analysis, differential scanning calorimetry, dynamic light scattering, and ultracentrifugation. Incubation of GAPDH in the presence of H 2 O 2 together with GSH resulted in the complete inactivation of the enzyme. In contrast to irreversible oxidation of GAPDH by H 2 O 2 , this modification could be reversed in the excess of GSH or dithiothreitol. By data of MALDI-MS analysis, the modified protein contained both mixed disulfide between Cys150 and GSH and the intrasubunit disulfide bond between Cys150 and Cys154 (different subunits of tetrameric GAPDH may contain different products). S-glutathionylation results in loosening of the tertiary structure of GAPDH, decreases its affinity to NAD + and thermal stability. The mixed disulfide between Cys150 and GSH is an intermediate product of S-glutathionylation: its subsequent reaction with Cys154 results in the intrasubunit disulfide bond in the active site of GAPDH. The mixed disulfide and the C150-C154 disulfide bond protect GAPDH from irreversible oxidation and can be reduced in the excess of thiols. Conformational changes that were observed in S-glutathionylated GAPDH may affect interactions between GAPDH and other proteins (ligands), suggesting the role of S-glutathionylation in the redox signaling. The manuscript considers one of the possible mechanisms of redox regulation of cell functions. Copyright © 2017 Elsevier B.V. All rights reserved.

  4. Self assembly of dialkoxo bridged dinuclear Fe(III) complex of pyridoxal Schiff base with C-C bond formation - structure, spectral and magnetic properties

    Czech Academy of Sciences Publication Activity Database

    Murašková, V.; Szabó, N.; Pižl, M.; Hoskovcová, I.; Dušek, Michal; Huber, Š.; Sedmidubský, D.

    2017-01-01

    Roč. 461, May (2017), s. 111-119 ISSN 0020-1693 R&D Projects: GA ČR(CZ) GA15-12653S; GA MŠk LO1603 EU Projects: European Commission(XE) CZ.2.16/3.1.00/24510 Institutional support: RVO:68378271 Keywords : iron (III) dinuclear complex * dialkoxo bridged pyridoxal Schiff base * C-C bond * crystal structure * magnetic properties Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 2.002, year: 2016

  5. Carbocyclic C-C Bond Formation: Intramolecular Radical Ring Closure to Yield Diastereomerically Pure (7'S-Me- or 7'R-Me-) Carba-LNA Nucleotide Analogs.

    Science.gov (United States)

    Plashkevych, Oleksandr; Upadhayaya, Ram Shankar; Chattopadhyaya, Jyoti

    2017-06-19

    In light of the impressive gene-silencing properties of carba-LNA modified oligo DNA and RNA, both in antisense RNA and siRNA approaches, which have been confirmed as proof-of-concept for biochemical applications in post-transcriptional gene silencing, we envision the true potential of carba-LNA modifications to be revealed soon. Herein we provide detailed protocols for synthesis of carba-LNA-A, -G, -5-Me C, and -T nucleosides on a medium/large scale (gram scale), as well as important guidelines for incorporation of these modified carba-LNAs into DNA or RNA oligonucleotides. Creation of a stereoselective C-C bond during the 5-exo radical intramolecular cyclization involves trapping of a C2' radical intermediate intramolecularly by the vicinal double bond of a C4'-tethered ─CH2 -CH═CH2 group. All diastereomers of substituted carba-LNAs are now available in pure form. The present procedure allows carba-LNA to be commercialized for medicinal or biotechnological purposes. © 2017 by John Wiley & Sons, Inc. Copyright © 2017 John Wiley & Sons, Inc.

  6. Unprecedented Reaction Pathway of Sterically Crowded Calcium Complexes: Sequential C-N Bond Cleavage Reactions Induced by C-H Bond Activations.

    Science.gov (United States)

    Yang, Yang; Wang, Haobing; Ma, Haiyan

    2017-01-17

    Five bis(quinolylmethyl)-(1H-indolylmethyl)amine (BQIA) compounds, that is, {(quinol-8-yl-CH2 )2 NCH2 (3-Br-1H-indol-2-yl)} (L(1) H) and {[(8-R(3) -quinol-2-yl)CH2 ]2 NCH(R(2) )[3-R(1) -1H-indol-2-yl]} (L(2-5) H) (L(2) H: R(1) =Br, R(2) =H, R(3) =H; L(3) H: R(1) =Br, R(2) =H, R(3) =iPr; L(4) H: R(1) =H, R(2) =CH3 , R(3) =iPr; L(5) H: R(1) =H, R(2) =nBu, R(3) =iPr) were synthesized and used to prepare calcium complexes. The reactions of L(1-5) H with silylamido calcium precursors (Ca[N(SiMe2 R)2 ]2 (THF)2 , R=Me or H) at room temperature gave heteroleptic products (L(1, 2) )CaN(SiMe3 )2 (1, 2), (L(3, 4) )CaN(SiHMe2 )2 (3 a, 4 a) and homoleptic complexes (L(3, 5) )2 Ca (D3, D5). NMR and X-ray analyses proved that these calcium complexes were stabilized through Ca⋅⋅⋅C-Si, Ca⋅⋅⋅H-Si or Ca⋅⋅⋅H-C agostic interactions. Unexpectedly, calcium complexes ((L(3-5) )CaN(SiMe3 )2 ) bearing more sterically encumbered ligands of the same type were extremely unstable and underwent C-N bond cleavage processes as a consequence of intramolecular C-H bond activation, leading to the exclusive formation of (E)-1,2-bis(8-isopropylquinol-2-yl)ethane. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Nonaqueous and halide-free route to crystalline BaTiO3, SrTiO3, and (Ba,Sr)TiO3 nanoparticles via a mechanism involving C-C bond formation.

    Science.gov (United States)

    Niederberger, Markus; Garnweitner, Georg; Pinna, Nicola; Antonietti, Markus

    2004-07-28

    A novel nonaqueous route for the preparation of nanocrystalline BaTiO(3), SrTiO(3), and (Ba,Sr)TiO(3) has been developed. In a simple one-pot reaction process, the elemental alkaline earth metals are directly dissolved in benzyl alcohol at slightly elevated temperatures. After the addition of Ti(O(i)Pr)(4), the reaction mixture is heated to 200 degrees C, resulting in the formation of a white precipitate. XRD measurements prove the exclusive presence of the perovskite phase without any other crystalline byproducts such as BaCO(3) or TiO(2). TEM investigations reveal that the BaTiO(3) nanoparticles are nearly spherical in shape with diameters ranging from 4 to 5 nm. The SrTiO(3) particles display less uniform particle shapes, and the size varies between 5 and 10 nm. Lattice fringes observed in HRTEM measurements further prove the high crystallinity of the nanoparticles. Surprisingly, GC-MS analysis of the reaction solution after hydrothermal treatment shows that hardly any ether formation occurs during the BaTiO(3) synthesis. Instead, the presence of 4-phenyl-2-butanol in stoichiometric amounts gives evidence that the formation mechanism proceeds mainly via a novel pathway involving C-C bond formation between benzyl alcohol and the isopropanolate ligand.

  8. Molecular Orbital and Density Functional Study of the Formation, Charge Transfer, Bonding and the Conformational Isomerism of the Boron Trifluoride (BF3 and Ammonia (NH3 Donor-Acceptor Complex

    Directory of Open Access Journals (Sweden)

    Dulal C. Ghosh

    2004-09-01

    Full Text Available The formation of the F3B–NH3 supermolecule by chemical interaction of its fragment parts, BF3 and NH3, and the dynamics of internal rotation about the ‘B–N’ bond have been studied in terms of parameters provided by the molecular orbital and density functional theories. It is found that the pairs of frontier orbitals of the interacting fragments have matching symmetry and are involved in the charge transfer interaction. The donation process stems from the HOMO of the donor into the LUMO of the acceptor and simultaneously, back donation stems from the HOMO of acceptor into the LUMO of the donor. The density functional computation of chemical activation in the donor and acceptor fragments, associated with the physical process of structural reorganization just prior to the event of chemical reaction, indicates that BF3 becomes more acidic and NH3 becomes more basic, compared to their separate equilibrium states. Theoretically it is observed that the chemical reaction event of the formation of the supermolecule from its fragment parts is in accordance with the chemical potential equalization principle of the density functional theory and the electronegativity equalization principle of Sanderson. The energetics of the chemical reaction, the magnitude of the net charge transfer and the energy of the newly formed bond are quite consistent, both internally and with the principle of maximum hardness, PMH. The dynamics of the internal rotation of one part with respect to the other part of the supermolecule about the ‘B–N’ bond mimics the pattern of the conformational isomerism of the isostructural ethane molecule. It is also observed that the dynamics and evolution of molecular conformations as a function of dihedral angles is also in accordance with the principle of maximum hardness, PMH. Quite consistent with spectroscopic predictions, the height of the molecule

  9. LAMMPS Framework for Dynamic Bonding and an Application Modeling DNA

    DEFF Research Database (Denmark)

    Svaneborg, Carsten

    2012-01-01

    We have extended the Large-scale Atomic/Molecular Massively Parallel Simulator (LAMMPS) to support directional bonds and dynamic bonding. The framework supports stochastic formation of new bonds, breakage of existing bonds, and conversion between bond types. Bond formation can be controlled...... and bond types. When breaking bonds, all angular and dihedral interactions involving broken bonds are removed. The framework allows chemical reactions to be modeled, and use it to simulate a simplistic, coarse-grained DNA model. The resulting DNA dynamics illustrates the power of the present framework....... to limit the maximal functionality of a bead with respect to various bond types. Concomitant with the bond dynamics, angular and dihedral interactions are dynamically introduced between newly connected triplets and quartets of beads, where the interaction type is determined from the local pattern of bead...

  10. An Iterated GMM Procedure for Estimating the Campbell-Cochrane Habit Formation Model, with an Application to Danish Stock and Bond Returns

    DEFF Research Database (Denmark)

    Engsted, Tom; Møller, Stig Vinther

    2010-01-01

    We suggest an iterated GMM approach to estimate and test the consumption based habit persistence model of Campbell and Cochrane, and we apply the approach on annual and quarterly Danish stock and bond returns. For comparative purposes we also estimate and test the standard constant relative risk......-aversion (CRRA) model. In addition, we compare the pricing errors of the different models using Hansen and Jagannathan's specification error measure. The main result is that for Denmark the Campbell-Cochrane model does not seem to perform markedly better than the CRRA model. For the long annual sample period...... covering more than 80 years there is absolutely no evidence of superior performance of the Campbell-Cochrane model. For the shorter and more recent quarterly data over a 20-30 year period, there is some evidence of counter-cyclical time-variation in the degree of risk-aversion, in accordance...

  11. An iterated GMM procedure for estimating the Campbell-Cochrane habit formation model, with an application to Danish stock and bond returns

    DEFF Research Database (Denmark)

    Engsted, Tom; Møller, Stig V.

    We suggest an iterated GMM approach to estimate and test the consumption based habit persistence model of Campbell and Cochrane (1999), and we apply the approach on annual and quarterly Danish stock and bond returns. For comparative purposes we also estimate and test the standard CRRA model....... In addition, we compare the pricing errors of the different models using Hansen and Jagannathan's (1997) specification error measure. The main result is that for Denmark the Campbell-Cochrane model does not seem to perform markedly better than the CRRA model. For the long annual sample period covering more...... than 80 years there is absolutely no evidence of superior performance of the Campbell-Cochrane model. For the shorter and more recent quarterly data over a 20-30 year period, there is some evidence of counter-cyclical time-variation in the degree of risk-aversion, in accordance with the Campbell...

  12. Rapid carbon-carbon bond formation and cleavage revealed by carbon isotope exchange between the carboxyl carbon and inorganic carbon in hydrothermal fluids

    Science.gov (United States)

    Glein, C. R.; Cody, G. D.

    2013-12-01

    The carbon isotopic composition of organic compounds in water-rock systems (e.g., hydrothermal vents, sedimentary basins, and carbonaceous meteorites) is generally interpreted in terms of the isotopic composition of the sources of such molecules, and the kinetic isotope effects of metabolic or abiotic reactions that generate or transform such molecules. This hinges on the expectation that the carbon isotopic composition of many organic compounds is conserved under geochemical conditions. This expectation is reasonable in light of the strength of carbon-carbon bonds (ca. 81 kcal/mol); in general, environmental conditions conducive to carbon-carbon bond cleavage typically lead to transformations of organic molecules (decarboxylation is a notable example). Geochemically relevant reactions that involve isotopic exchange between carbon atoms in organic molecules and inorganic forms of carbon with no change in molecular structure appear to be rare. Notwithstanding such rarity, there have been preliminary reports of relatively rapid carbon isotope exchange between the carboxyl group in carboxylic acids and carbon dioxide in hot water [1,2]. We have performed laboratory hydrothermal experiments to gain insights into the mechanism of this surprising reaction, using phenylacetate as a model structure. By mass spectrometry, we confirm that the carboxyl carbon undergoes facile isotopic exchange with 13C-labeled bicarbonate at moderate temperatures (i.e., 230 C). Detailed kinetic analysis reveals that the reaction rate is proportional to the concentrations of both reactants. Further experiments demonstrate that the exchange reaction only occurs if the carbon atom adjacent to the carboxyl carbon is bonded to a hydrogen atom. As an example, no carbon isotope exchange was observed for benzoate in experiments lasting up to one month. The requirement of an alpha C-H bond suggests that enolization (i.e., deprotonation of the H) is a critical step in the mechanism of the exchange

  13. Hemoglobin polymerization via disulfide bond formation in the hypoxia-tolerant turtle Trachemys scripta: implications for antioxidant defense and O2 transport

    DEFF Research Database (Denmark)

    Petersen, Asbjørn Graver; Petersen, Steen Vang; Frische, Sebastian

    2018-01-01

    The ability of many reptilian hemoglobins (Hbs) to form high-molecular weight polymers, albeit known for decades, has not been investigated in detail. Given that turtle Hbs often contain a high number of cysteine (Cys), potentially contributing to the red blood cell defense against reactive oxygen...... species, we have examined whether polymerization of Hb could occur via intermolecular disulfide bonds in red blood cells of freshwater turtle Trachemys scripta, a species that is highly tolerant of hypoxia and oxidative stress. We find that one of the two Hb isoforms of the hemolysate, HbA, is prone......A of HbA is a key element of the antioxidant capacity of turtle red blood cells....

  14. Influence of N-type μc-SiOx:H intermediate reflector and top cell material properties on the electrical performance of "micromorph" tandem solar cells

    Science.gov (United States)

    Chatterjee, P.; Roca i Cabarrocas, P.

    2018-01-01

    Amorphous silicon (a-Si:H) / micro-crystalline silicon (μc-Si:H), "micromorph" tandem solar cells have been investigated using a detailed electrical - optical model. Although such a tandem has good light absorption over the entire visible spectrum, the a-Si:H top cell suffers from strong light-induced degradation (LID). To improve matters, we have replaced a-Si:H by hydrogenated polymorphous silicon (pm-Si:H), a nano-structured silicon thin film with lower LID than a-Si:H. But the latter's low current carrying capacity necessitates a thicker top cell for current-matching, again leading to LID problems. The solution is to introduce a suitable intermediate reflector (IR) at the junction between the sub-cells, to concentrate light of the shorter visible wavelengths into the top cell. Here we assess the suitability of N-type micro-crystalline silicon oxide (μc-SiOx:H) as an IR. The sensitivity of the solar cell performance to the complex refractive index, thickness and texture of such a reflector is studied. We conclude that N-μc-SiOx:H does concentrate light into the top sub-cell, thus reducing its required thickness for current-matching. However the IR also reflects light right out of the device; so that the initial efficiency suffers. The advantage of such an IR is ultimately seen in the stabilized state since the LID of a thin top cell is low. We also find that for high stabilized efficiencies, the IR should be flat (having no texture of its own). Our study indicates that we may expect to reach 15% stable tandem micromorph efficiency.

  15. Investigation of forced and isothermal chemical vapor infiltrated SiC/SiC ceramic matrix composites. Final report

    Energy Technology Data Exchange (ETDEWEB)

    Sankar, J.; Kelkar, A.D.; Vaidyanathan, R. [North Carolina Agricultural and Technical State Univ., Greensboro, NC (United States). Dept. of Mechanical Engineering

    1993-09-01

    Mechanical properties of two different layups for each of the forced CVI (41 specimens) and isothermal CVI (36 specimens) materials were investigated in air at room temperature (RT), 1000C, and at room temperature after thermal shock (RT/TS) and exposure to oxidation (RT/OX). The FCVI specimens had a nominal interfacial coating thickness of 0.3 {mu}m of pyrolytic carbon, while CVI specimens had a coating thickness of 0.1 {mu}m. Effect of reinforcement and interfacial bond on mechanical properties of composite were investigated. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were employed to analyze the fiber-matrix interface and the toughening mechanisms in this ceramic composite system.

  16. Synthesis, characterization, and wear and friction properties of variably structured SiC/Si elements made from wood by molten Si impregnation

    DEFF Research Database (Denmark)

    Dhiman, Rajnish; Rana, Kuldeep; Bengu, Erman

    2012-01-01

    We have synthesized pre-shaped SiC/Si ceramic material elements from charcoal (obtained from wood) by impregnation with molten silicon, which takes place in a two-stage process. In the first process, a porous structure of connected micro-crystals of β-SiC is formed, while, in the second process...... ceramic material can be achieved, thus suggesting new industrial applications. The structure and composition of numerous as-synthesized samples were characterized in detail by using a wide range of techniques. Wear and friction properties were also investigated, with polished samples. The properties found...

  17. SEMICONDUCTOR DEVICES: An optically controlled SiC lateral power transistor based on SiC/SiCGe super junction structure

    Science.gov (United States)

    Hongbin, Pu; Lin, Cao; Jie, Ren; Zhiming, Chen; Yagong, Nan

    2010-04-01

    An optically controlled SiC/SiCGe lateral power transistor based on superjunction structure has been proposed, in which n-SiCGe/p-SiC superjunction structure is employed to improve device figure of merit. Performance of the novel optically controlled power transistor was simulated using Silvaco Atlas tools, which has shown that the device has a very good response to the visible light and the near infrared light. The optoelectronic responsivities of the device at 0.5 μm and 0.7 μm are 330 mA/W and 76.2 mA/W at 2 V based voltage, respectively.

  18. Spin-orbit corrections to the indirect nuclear spin-spin coupling constants in XH4 (X=C, Si, Ge, and Sn)

    DEFF Research Database (Denmark)

    Kirpekar, Sheela; Jensen, Hans Jørgen Aagaard; Oddershede, Jens

    1997-01-01

    Using the quadratic response function at the ab initio SCF level of approximation we have calculated the relativistic corrections from the spin-orbit Hamiltonian, HSO, to the indirect nuclear spin-spin coupling constants of XH4 (X = C, Si, Ge, and Sn). We find that the spin-orbit contributions...... to JX-H are small, amounting only to about 1% for JSn-H. For the geminal H-H coupling constants the relativistic corrections are numerically smaller than for JH-H, but in some cases relatively larger compared to the actual magnitude of JH-H. We also investigate the use of an effective one-electron spin...

  19. Metal organic vapor phase epitaxy growth of (Al)GaN heterostructures on SiC/Si(111) templates synthesized by topochemical method of atoms substitution

    DEFF Research Database (Denmark)

    Rozhavskaya, Mariia M.; Kukushkin, Sergey A.; Osipov, Andrey V.

    2017-01-01

    crystalline interfaces with epitaxial relationship between SiC/Si and AlN/SiC layers. Optimization of SiC morphology and AlN seed layer thickness facilitates the growth of GaN layers free of pits (v-defects). It is also found that Si doping eliminates these defects in the case of growth on SiC templates...... with non-optimized surface morphology. Thus, synthesis of thin SiC buffer layer is suggested as a solution for the interface problems at the initial stage of III-N on Si epitaxy....

  20. H{sub 2}-Ar dilution for improved c-Si quantum dots in P-doped SiN{sub x}:H thin film matrix

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Jia [Shaanxi Engineering Lab for Advanced Energy Technology, School of Materials Science and Engineering, Shaanxi Normal University, Xi’an 710119 (China); Zhang, Weijia, E-mail: zwjghx@126.com [Center of Condensed Matter and Material Physics, School of Physics and Nuclear Energy Engineering, Beihang University, Beijing, 100191 (China); Liu, Shengzhong, E-mail: szliu@dicp.ac.cn [Shaanxi Engineering Lab for Advanced Energy Technology, School of Materials Science and Engineering, Shaanxi Normal University, Xi’an 710119 (China); State key Laboratory of Catalysis, iChEM, Dalian Institute of Chemical Physics, Dalian National Laboratory for Clean Energy, Chinese Academy of Sciences, Dalian 116023 (China)

    2017-02-28

    Highlights: • Phosphorous-doped SiN{sub x}:H thin films containing c-Si QDs were prepared by PECVD in H{sub 2}-Ar mixed dilution under low temperature. • QD density and QD size can be controlled by tuning H{sub 2}/Ar flow ratio. • The sample prepared at the H{sub 2}/Ar flow ratio of 100/100 possesses both wide band gap and excellent conductivity. • Detail discussion has been presented for illustrating the influence of H{sub 2}/Ar mixed dilution on the crystallization process and P-doping. - Abstract: Phosphorus-doped hydrogenated silicon nitride (SiN{sub x}:H) thin films containing crystalline silicon quantum dot (c-Si QD) was prepared by plasma enhanced chemical vapor deposition (PECVD) using hydrogen-argon mixed dilution. The effects of H{sub 2}/Ar flow ratio on the structural, electrical and optical characteristics of as-grown P-doped SiN{sub x}:H thin films were systematically investigated. Experimental results show that crystallization is promoted by increasing the H{sub 2}/Ar flow ratio in dilution, while the N/Si atomic ratio is higher for thin film deposited with argon-rich dilution. As the H{sub 2}/Ar flow ratio varies from 100/100 to 200/0, the samples exhibit excellent conductivity owing to the large volume fraction of c-Si QDs and effective P-doping. By adjusting the H{sub 2}/Ar ratio to 100/100, P-doped SiN{sub x}:H thin film containing tiny and densely distributed c-Si QDs can be obtained. It simultaneously possesses wide optical band gap and high dark conductivity. Finally, detailed discussion has been made to analyze the influence of H{sub 2}-Ar mixed dilution on the properties of P-doped SiN{sub x}:H thin films.

  1. Examples of reductive azo cleavage and oxidative azo bond formation on Re2(CO)10 template: isolation and characterization of Re(III) complexes of new azo-aromatic ligands.

    Science.gov (United States)

    Paul, Nanda D; Samanta, Subhas; Mondal, Tapan K; Goswami, Sreebrata

    2011-08-15

    A new example of simultaneous reductive azo bond cleavage and oxidative azo bond formation in an azo-aromatic ligand is introduced. The chemical transformation is achieved by the reaction of Re(2)(CO)(10) with the ligand 2-[(2-N-Arylamino)phenylazo]pyridine (HL(1)). A new and unexpected mononuclear rhenium complex [Re(L(1))(L(3))] (1) was isolated from the above reaction. The new azo-aromatic ligand, H(2)L(3) (H(2)L(3) = 2, 2'-dianilinoazobenzene) is formed in situ from HL(1). A similar reaction of Re(2)(CO)(10) and a closely related azo-ligand, 2,4-ditert-butyl-6-(pyridin-2-ylazo)-phenol (HL(2)), resulted in a seven coordinated compound [Re(L(2)){(L(4))(•-)}(2)] (2; HL(4) = 2-amino-4,6-ditert-butyl-phenol) via reductive cleavage of the azo bond. The complexes have been characterized by using a host of physical methods: X-ray crystallography, nuclear magnetic resonance (NMR), cyclic voltammetry, ultraviolet-visible (UV-vis), electron paramagnetic resonance (EPR) spectroscopy, and density functional theory (DFT). The experimental structures are well reproduced by density functional theory calculations and support the overall electronic structures of the above compounds. Complex 1 is a closed shell singlet, while complex 2 exemplifies a singlet diradical complex where the two partially oxidized aminophenoleto ligands are coupled to each other, yielding the observed diamagnetic ground state. Complexes 1 and 2 showed two successive one-electron redox responses. EPR spectral studies in corroboration with DFT results indicated that all of the redox processes occur at the ligand center without affecting the trivalent state of the metal ion. © 2011 American Chemical Society

  2. A new face of phenalenyl-based radicals in the transition metal-free C-H arylation of heteroarenes at room temperature: trapping the radical initiatorviaC-C σ-bond formation.

    Science.gov (United States)

    Ahmed, Jasimuddin; P, Sreejyothi; Vijaykumar, Gonela; Jose, Anex; Raj, Manthan; Mandal, Swadhin K

    2017-11-01

    The radical-mediated transition metal-free approach for the direct C-H bond functionalization of arenes is considered as a cost effective alternative to transition metal-based catalysis. An organic ligand-based radical plays a key role by generating an aryl radical which undergoes a subsequent functionalization process. The design principle of the present study takes advantage of a relatively stable odd alternant hydrocarbon-based phenalenyl (PLY) radical. In this study, the first transition metal-free catalyzed direct C-H arylation of a variety of heteroarenes such as azoles, furan, thiophene and pyridine at room temperature has been reported using a phenalenyl-based radical without employing any photoactivation step. This protocol has been successfully applied to the gram scale synthesis of core moieties of bioactive molecules. The phenalenyl-based radical initiator has been characterized crystallographically by trapping it via the formation of a C-C σ-bond between the phenalenyl radical and solvent-based radical species.

  3. Ten-gram scale SiC@SiO2 nanowires: high-yield synthesis towards industrialization, in situ growth mechanism and their peculiar photoluminescence and electromagnetic wave absorption properties.

    Science.gov (United States)

    Li, Z J; Yu, H Y; Song, G Y; Zhao, J; Zhang, H; Zhang, M; Meng, A L; Li, Q D

    2017-02-01

    SiC@SiO2 nanowires, as a functional nanocomposite, have attracted widespread attention due to their fascinating performance and broad application prospect. However, the low-cost, high yield preparation of large-scale SiC@SiO2 nanowires is still a bottleneck, which hinders their industrial application. Herein, a carbothermal reduction strategy has been developed to synthesize SiC@SiO2 nanowires, which breaks through the handicap of the traditional growth pattern that uses the aid of a substrate. Systematic characterization results illustrate that the yield of the as-obtained products greatly depends on the heating rate, and ten-gram scale SiC@SiO2 nanowires (∼27.2 g) composed of a cubic β-SiC core and homogeneous amorphous SiO2 coating are achieved under the optimum process parameters. The in situ mechanisms of expansion-insertion-growth and inhibition of expansion-package-obstruction are proposed to rationally interpret the growth process of SiC@SiO2 nanowires and the effect of various heating rates, respectively. Furthermore, the SiC@SiO2 nanowires display violet-blue photoluminescence and electromagnetic wave absorption properties. This study not only provides some beneficial suggestions for the commercial production of SiC@SiO2 nanowires, but also reveals promising applications of SiC@SiO2 nanowires in the optical and electromagnetic shielding fields. Moreover, the developed novel in situ growth mechanism enriches the growth theory of one-dimension nanomaterials and offers inspiration for their industrial-scale production.

  4. Vers une ingénierie de bandes des cellules solaires à hétérojonctions a-Si:H / c-Si. Rôle prépondérant de l'hydrogène.

    OpenAIRE

    Damon-Lacoste, J.

    2007-01-01

    fin de rédaction en avril 2007. Pas retouché.; This thesis is the first such work in France on a-Si:H/c-Si heterojunction solar cells. This technology is based on the deposition of amorphous silicon onto crystalline silicon substrates, thus enabling the fabrication of high efficiency solar cells entirely at low temperatures (< 200 °C). It also makes it possible to process very thin c-Si substrates (

  5. Nano-Bonding of Silicon Oxides-based surfaces at Low Temperature: Bonding Interphase Modeling via Molecular Dynamics and Characterization of Bonding Surfaces Topography, Hydro-affinity and Free Energy

    Science.gov (United States)

    Whaley, Shawn D.

    In this work, a new method, "Nanobonding(TM)" [1,2] is conceived and researched to bond Si-based surfaces, via nucleation and growth of a 2 D silicon oxide SiOxHx interphase connecting the surfaces at the nanoscale across macroscopic domains. Nanobonding cross-bridges two smooth surfaces put into mechanical contact in an O2/H 2O mixed ambient below T ≤200 °C via arrays of SiOxH x molecules connecting into a continuous macroscopic bonding interphase. Nano-scale surface planarization via wet chemical processing and new spin technology are compared via Tapping Mode Atomic Force Microscopy (TMAFM) , before and after nano-bonding. Nanobonding uses precursor phases, 2D nano-films of beta-cristobalite (beta-c) SiO2, nucleated on Si(100) via the Herbots-Atluri (H-A) method [1]. beta-c SiO2 on Si(100) is ordered and flat with atomic terraces over 20 nm wide, well above 2 nm found in native oxides. When contacted with SiO2 this ultra-smooth nanophase can nucleate and grow domains with cross-bridging molecular strands of hydroxylated SiOx, instead of point contacts. The high density of molecular bonds across extended terraces forms a strong bond between Si-based substrates, nano- bonding [2] the Si and silica. A new model of beta-cristobalite SiO2 with its axis aligned along Si[100] direction is simulated via ab-initio methods in a nano-bonded stack with beta-c SiO2 in contact with amorphous SiO2 (a-SiO2), modelling cross-bridging molecular bonds between beta-c SiO2 on Si(100) and a-SiO2 as during nanobonding. Computed total energies are compared with those found for Si(100) and a-SiO2 and show that the presence of two lattice cells of !-c SiO2 on Si(100) and a-SiO2 lowers energy when compared to Si(100)/ a-SiO 2 Shadow cone calculations on three models of beta-c SiO2 on Si(100) are compared with Ion Beam Analysis of H-A processed Si(100). Total surface energy measurements via 3 liquid contact angle analysis of Si(100) after H-A method processing are also compared. By

  6. Flexible SiC/Si3N4 Composite Nanofibers with in Situ Embedded Graphite for Highly Efficient Electromagnetic Wave Absorption.

    Science.gov (United States)

    Wang, Peng; Cheng, Laifei; Zhang, Yani; Zhang, Litong

    2017-08-30

    SiC/Si3N4 composite nanofibers with in situ embedded graphite, which show highly efficient electromagnetic (EM) wave absorption performance in gigahertz frequency, were prepared by electrospinning with subsequent polymer pyrolysis and annealing. By means of incorporating graphite and Si3N4 into SiC, the EM wave absorption properties of the nanofibers were improved. The relationship among processing, fiber microstructure, and their superior EM wave absorption performance was systematically investigated. The EM wave absorption capability and effective absorption bandwidth (EAB) of nanofibers can be simply controlled by adjusting annealing atmosphere and temperature. The nanofibers after annealing at 1300 °C in Ar present a minimum reflection loss (RL) of -57.8 dB at 14.6 with 5.5 GHz EAB. The nanofibers annealed in N2 at 1300 °C exhibit a minimum RL value of -32.3 dB at a thickness of 2.5 mm, and the EAB reaches 6.4 GHz over the range of 11.3-17.7 GHz. The highly efficient EM wave absorption performance of nanofibers are closely related to dielectric loss, which originated from interfacial polarization and dipole polarization. The excellent absorbing performance together with wider EAB endows the composite nanofibers potential to be used as reinforcements in polymers and ceramics (SiC, Si3N4, SiO2, Al2O3, etc.) to improve their EM wave absorption performance.

  7. Growth of 3C-SiC on 150-mm Si(100) substrates by alternating supply epitaxy at 1000 deg. C

    Energy Technology Data Exchange (ETDEWEB)

    Wang Li, E-mail: l.wang@griffith.edu.au; Dimitrijev, Sima; Han, Jisheng; Iacopi, Alan; Hold, Leonie; Tanner, Philip; Harrison, H. Barry

    2011-07-29

    To lower deposition temperature and reduce thermal mismatch induced stress, heteroepitaxial growth of single-crystalline 3C-SiC on 150 mm Si wafers was investigated at 1000 deg. C using alternating supply epitaxy. The growth was performed in a hot-wall low-pressure chemical vapor deposition reactor, with silane and acetylene being employed as precursors. To avoid contamination of Si substrate, the reactor was filled in with oxygen to grow silicon dioxide, and then this thin oxide layer was etched away by silane, followed by a carbonization step performed at 750 deg. C before the temperature was ramped up to 1000 deg. C to start the growth of SiC. Microstructure analyses demonstrated that single-crystalline 3C-SiC is epitaxially grown on Si substrate and the film quality is improved as thickness increases. The growth rate varied from 0.44 to 0.76 {+-} 0.02 nm/cycle by adjusting the supply volume of SiH{sub 4} and C{sub 2}H{sub 2}. The thickness nonuniformity across wafer was controlled with {+-} 1%. For a prime grade 150 mm virgin Si(100) wafer, the bow increased from 2.1 to 3.1 {mu}m after 960 nm SiC film was deposited. The SiC films are naturally n type conductivity as characterized by the hot-probe technique.

  8. Fracture Mechanisms For SiC Fibers And SiC/SiC Composites Under Stress-Rupture Conditions at High Temperatures

    Science.gov (United States)

    DiCarlo, James A.; Yun, Hee Mann; Hurst, Janet B.; Viterna, L. (Technical Monitor)

    2002-01-01

    The successful application of SiC/SiC ceramic matrix composites as high-temperature structural materials depends strongly on maximizing the fracture or rupture life of the load-bearing fiber and matrix constituents. Using high-temperature data measured under stress-rupture test conditions, this study examines in a mechanistic manner the effects of various intrinsic and extrinsic factors on the creep and fracture behavior of a variety of SiC fiber types. It is shown that although some fiber types fracture during a large primary creep stage, the fiber creep rate just prior to fracture plays a key role in determining fiber rupture time (Monkman-Grant theory). If it is assumed that SiC matrices rupture in a similar manner as fibers with the same microstructures, one can develop simple mechanistic models to analyze and optimize the stress-rupture behavior of SiC/SiC composites for applied stresses that are initially below matrix cracking.

  9. Expression of hypoallergenic Der f 2 derivatives with altered intramolecular disulphide bonds induces the formation of novel ER-derived protein bodies in transgenic rice seeds.

    Science.gov (United States)

    Yang, Lijun; Hirose, Sakiko; Suzuki, Kazuya; Hiroi, Takachika; Takaiwa, Fumio

    2012-05-01

    House dust mites (HDM) are the most common source of indoor allergens and are associated with allergic diseases worldwide. To benefit allergic patients, safer and non-invasive mucosal routes of oral administration are considered to be the best alternative to conventional allergen-specific immunotherapy. In this study, transgenic rice was developed expressing derivatives of the major HDM allergen Der f 2 with reduced Der f 2-specific IgE reactivity by disrupting intramolecular disulphide bonds in Der f 2. These derivatives were produced specifically as secretory proteins in the endosperm tissue of seeds under the control of the endosperm-specific glutelin GluB-1 promoter. Notably, modified Der f 2 derivatives aggregated in the endoplasmic reticulum (ER) lumen and were deposited in a unique protein body (PB)-like structure tentatively called the Der f 2 body. Der f 2 bodies were characterized by their intracellular localization and physico-chemical properties, and were distinct from ER-derived PBs (PB-Is) and protein storage vacuoles (PB-IIs). Unlike ER-derived organelles such as PB-Is, Der f 2 bodies were rapidly digested in simulated gastric fluid in a manner similar to that of PB-IIs. Oral administration in mice of transgenic rice seeds containing Der f 2 derivatives encapsulated in Der f 2 bodies suppressed Der f 2-specific IgE and IgG production compared with that in mice fed non-transgenic rice seeds, and the effect was dependent on the type of Der f 2 derivative expressed. These results suggest that engineered hypoallergenic Der f 2 derivatives expressed in the rice seed endosperm could serve as a basis for the development of viable strategies for the oral delivery of vaccines against HDM allergy.

  10. [2 + 2]-type Reaction of Metal-Metal σ-Bond with Fullerene Forming an η1-C60 Metal Complex: Mechanistic Details of Formation Reaction and Prediction of a New η1-C60 Metal Complex.

    Science.gov (United States)

    Zheng, Hong; Zhao, Xiang; Sakaki, Shigeyoshi

    2017-06-05

    C60[CpRu(CO)2]2 is only one transition-metal fullerene complex with pure η1-coordinated bonds, which was recently synthesized through the reaction between dinuclear Ru complex [CpRu(CO)2]2 and C60. Though new properties can be expected in the η1-coordinated metal-fullerene complex, its characteristic features are unclear, and the [2 + 2]-type formation reaction is very slow with a very small yield. A density functional theory study discloses that the η1-coordinated bond is formed by a large overlap between the Ru dσ orbital and C pσ one involved in the lowest unoccupied molecular orbital (LUMO) (π*) of C60 unlike the well-known η2-coordinated metal-fullerene complex which has a π-type coordinate bond with metal dπ orbital. The binding energy per one Ru-C bond is much smaller than those of η2-coordinated Pt(PMe3)2(C60) and IrH(CO)(PH3)2(C60) because the Ru d orbital exists at low energy. The formation reaction occurs via Ru-Ru bond cleavage on the C60 surface followed by a direction change of CpRu(CO)2 to afford C60[CpRu(CO)2]2 in a stepwise manner via two asymmetrical transition states to avoid a symmetry-forbidden character. The calculated Gibbs activation energy (ΔG°‡) is very large and the Gibbs reaction energy (ΔG°) is moderately negative, which are consistent with a very slow reaction rate and very small yield. The charge transfer from CpRu(CO)2 to fullerene CT(Ru → C60) is important in the reaction, but it is small due to the presence of the Ru d orbital at low energy, which is the reason for the large ΔG°‡ and moderately negative ΔG°. The use of Li+@C60 is theoretically predicted to accelerate the reaction and increase the yield of Li+@C60[CpRu(CO)2]2, because the CT(Ru → C60) is enhanced by the low energy LUMO of Li+@C60. It is also predicted that Li+@C60[Re(CO)4(PMe3)]2 is a next promising target for the synthesis of the η1-coordinated metal-fullerene complex, but syntheses of C60[Co(CO)4]2, C60[Re(CO)5]2, Li+@C60[Co(CO)4]2, and

  11. Formation of a sandwich-structure assisted, relatively long-lived sulfur-centered three-electron bonded radical anion in the reduction of a bis(1-substituted-uracilyl) disulfide in aqueous solution.

    Science.gov (United States)

    Wenska, Grazyna; Filipiak, Piotr; Asmus, Klaus-Dieter; Bobrowski, Krzysztof; Koput, Jacek; Marciniak, Bronislaw

    2008-08-14

    The one-electron reduction of bis[1-(2',3',5'-tri-O-acetylribosyl)uracil-4-yl] disulfide, initiated by hydrated electrons in a radiation chemical study, has been shown to yield 1-(2',3',5'-tri-O-acetylribosyl)-4-thiouracil as a stable molecular product. The reduction reaction leads, in the first instance, to a transient, albeit remarkably stable disulfide radical anion. This is characterized by a 2-center-3-electron bond with two bonding sigma-electrons and an antibonding sigma*-electron in the sulfur-sulfur bridge, (-S therefore S-)(-). It receives its stability from a sandwich-structure with the two uracilyl moieties facing each other (possibly further assisted by the 2',3',5'-tri-O-acetylribosyl substituents). A considerable lengthening of the original disulfide bridge from 2.02 to 2.73 A in the radical anion seems to facilitate the interaction of the heterocycles and leads to a gain in stabilization energy of 24 and 33 kcal/mol (100 and 140 kJ/mol) as evaluated by UMP2/cc-pVTZ and UMP2/cc-pVDZ calculations, respectively. The (-S therefore S-)(-) bonded radical anion shows a broad optical absorption band with lambdamax=450 nm, epsilonmax=6000 M(-1) cm(-1), and a half-width of 1.0 eV. It exists in equilibrium with the conjugated 1-(2',3',5'-tri- O-acetylribosyl)uracil-4-yl thiyl radical -S(*), and the corresponding thiolate, -S(-). The rate determining step for the disappearance of the disulfide radical anion appears to be protonation of both the radical anion and the free thiolate by reaction with H(+)aq. Absolute rate constants have been measured for these protonation processes, for the formation of the stable thiouridine product, and for the electron transfer from the disulfide radical anion to molecular oxygen. With the (-S therefore S-)(-) -S(*) + -S(-) equilibrium lying very much on the left-hand side, the reduced disulfide system exhibits predominantly reducing properties whereas any oxidizing property of the conjugated thiyl radical has only little if any

  12. Carbon-carbon bond formation and pyrrole synthesis via the [3,3] sigmatropic rearrangement of O-vinyl oxime ethers.

    Science.gov (United States)

    Wang, Heng-Yen; Mueller, Daniel S; Sachwani, Rachna M; Londino, Hannah N; Anderson, Laura L

    2010-05-21

    A new method for the synthesis of 2,4- and 2,3,4-substituted pyrroles in two or three steps from commercially available ketones and allyl hydroxylamine is described. An iridium-catalyzed isomerization reaction has been developed to convert O-allyl oximes to O-vinyl oximes, which undergo a facile [3,3] rearrangement to form 1,4-imino aldehyde Paal-Knorr intermediates that cyclize to afford the corresponding pyrroles. Optimization and examples of the isomerization and pyrrole formation are discussed.

  13. Dependencies of photoelectric properties of SiC/Si structures grown by the method of atoms substitution on synthesis time

    Science.gov (United States)

    Grashchenko, A. S.; Kukushkin, S. A.; Osipov, A. V.; Feoktistov, N. A.

    2017-07-01

    This paper is dedicated to an exploration of the photoelectric properties of Si-SiC structures grown by the substitution method on silicon substrates of (001) orientation. For the samples with the synthesis times of 40, 60, 90, 120 and 900 s, magnitudes of the saturation currents are determined and the coefficients of efficiency are calculated. The obtained dependencies of the photoelectric characteristics on the synthesis time are explained using the theory of formation of dilatation dipoles during the synthesis by the method of atoms substitution.

  14. Formation, Characterization, and O-O Bond Activation of a Peroxomanganese(III) Complex Supported by a Cross-Clamped Cyclam Ligand.

    Science.gov (United States)

    Colmer, Hannah E; Howcroft, Anthony W; Jackson, Timothy A

    2016-03-07

    Although there have been reports describing the nucleophilic reactivity of peroxomanganese(III) intermediates, as well as their conversion to high-valent oxo-bridged dimers, it remains a challenge to activate peroxomanganese(III) species for conversion to high-valent, mononuclear manganese complexes. Herein, we report the generation, characterization, and activation of a peroxomanganese(III) adduct supported by the cross-clamped, macrocyclic Me2EBC ligand (4,11-dimethyl-1,4,8,11-tetraazabicyclo[6.6.2]hexadecane). This ligand is known to support high-valent, mononuclear Mn(IV) species with well-defined spectroscopic properties, which provides an opportunity to identify mononuclear Mn(IV) products from O-O bond activation of the corresponding Mn(III)-peroxo adduct. The peroxomanganese(III) intermediate, [Mn(III)(O2)(Me2EBC)](+), was prepared at low-temperature by the addition of KO2 to [Mn(II)(Cl)2(Me2EBC)] in CH2Cl2, and this complex was characterized by electronic absorption, electron paramagnetic resonance (EPR), and Mn K-edge X-ray absorption (XAS) spectroscopies. The electronic structure of the [Mn(III)(O2)(Me2EBC)](+) intermediate was examined by density functional theory (DFT) and time-dependent (TD) DFT calculations. Detailed spectroscopic investigations of the decay products of [Mn(III)(O2)(Me2EBC)](+) revealed the presence of mononuclear Mn(III)-hydroxo species or a mixture of mononuclear Mn(IV) and Mn(III)-hydroxo species. The nature of the observed decay products depended on the amount of KO2 used to generate [Mn(III)(O2)(Me2EBC)](+). The Mn(III)-hydroxo product was characterized by Mn K-edge XAS, and shifts in the pre-edge transition energies and intensities relative to [Mn(III)(O2)(Me2EBC)](+) provide a marker for differences in covalency between peroxo and nonperoxo ligands. To the best of our knowledge, this work represents the first observation of a mononuclear Mn(IV) center upon decay of a nonporphyrinoid Mn(III)-peroxo center.

  15. Modélisation et caractérisation des joints collés à hautes vitesses de déformation Modeling and characterization of bonded joints at high strain rates

    Directory of Open Access Journals (Sweden)

    Bourel B.

    2013-11-01

    Full Text Available Ce papier traite de la modélisation de joints collés pour les structures soumises à des sollicitations de type crash. Cette nouvelle modélisation basée sur un élément cohésif tient compte du comportement viscoplastique, de l'endommagement ainsi que de la rupture de l'adhésive. Sensible à la vitesse de déformation l'identification du critère de rupture nécessite une base expérimentale allant jusqu'à de très hautes vitesses de déformations. Un nouveau dispositif d'essais a donc été mis en place sur les barres de Hopkinson afin de solliciter des assemblages à haute vitesse et sous différents angles de chargement. This paper deals with the modeling of bonded joints for structures subjected to dynamic crash loading. This new model based on a cohesive element takes into account the viscoelastic behavior, the damage and the failure of the adhesive. Due to the strain rate sensitivity, the identification of failure criterion requires experimental tests, up to very high strain rates. A new testing device has then been set up on the Hopkinson bar in order to load the assemblies with high strain rates and with different angles.

  16. Diagraphies de cimentation : vers une analyse de la qualité du contact ciment-formation Cement Logging: Toward an Analysis of the Quality of Cement-Formation Bonding

    Directory of Open Access Journals (Sweden)

    Isambourg P.

    2006-11-01

    Full Text Available Les compagnies pétrolières ont un réel besoin d'évaluer correctement les cimentations de leurs puits : l'étanchéité entre les différentes zones est-elle assurée? Pour ce faire, les outils soniques et ultra-soniques ont été mis au point. Jusqu'à présent, la qualité du contactcasing-ciment était analysée quantitativement et celle du contactciment-formation était analysée qualitativement par les spécialistes (outil VDL. Le progrès le plus important que l'on pouvait apporter dans les logsde cimentation était de détecter les défauts à l'interface ciment-formation. C'est ce que nous avons fait dans le cadre d'un projet financé par l'ARTEP (Association de Recherche sur les Techniques d'Exploitation du Pétrole comprenant Total, Gaz de France GDF, Institut Français du Pétrole (IFP, et Elf Aquitaine Production (EAP. Les expériences laboratoires effectuées au Service Analyse FLuides de Boussens ont été conçues en injectant du ciment entre un casing et une formation-simulée avec présence, ou non, de boue d'épaisseur variable. Des formations rapides ou lentes, ainsi que des ciments, rapides ou lents, ont été utilisés. Les échos ultrasoniques, obtenus à l'aide d'une sonde CET en céramique, ont été enregistrés et analysés. La théorie, comme les expériences, ont montré que les échos ultrasoniques sont modifiés en présence de boue et/ou de gaz. Les relations entre la forme de l'onde ultrasonique et la présence de boue et de gaz entre le ciment et la formation ont été établies. Une procédure de traitement est proposée avec ses limites. Oil companies have a real need to make a correct assessment of cementing jobs in their wells. Is the seal ensured between different zones? To do this, sonic and ultrasonic logging tools have been developed. Up to now, the quality of the casing-cement contacthas been analyzed quantitatively, and that of the cement-formation contacthas been analyzed qualitatively by

  17. Formation of diphenylphosphanylbutadienyl complexes by insertion of two P-coordinated alkynylphosphanes into a PtbondC6F5 bond: detection of intermediate and reaction products.

    Science.gov (United States)

    Ara, Irene; Forniés, Juan; García, Ana; Gómez, Julio; Lalinde, Elena; Moreno, M Teresa

    2002-08-16

    The reactions between cis-[M(C(6)F(5))(2)(PPh(2)CtriplebondCR)(2)] (M=Pt, Pd; R=Ph, tBu, Tol 2, 3) or cis-[Pt(C(6)F(5))(2)(PPh(2)CtriplebondCR)(PPh(2)CtriplebondCtBu)] (R=Ph 4, Tol 5) and cis-[Pt(C(6)F(5))(2)(thf)(2)] 1 have been investigated. Whereas [M](PPh(2)CtriplebondCtBu)(2) ([M]=cis-M(C(6)F(5))(2)) is inert towards 1, the analogous reactions starting from [M](PPh(2)CtriplebondCR)(2) or [Pt](PPh(2)CtriplebondCR)(PPh(2)CtriplebondCtBu) (R=Ph, Tol) afford unusual binuclear species [Pt(C(6)F(5))(S)mu-[C(R')dbondC(PPh(2))C(PPh(2))doublebondC(R)(C(6)F(5))]M(C(6)F(5))(2)] (R=R'=Ph, Tol, M=Pt 6 a,c, M=Pd 7 a,c; M=Pt, R'=tBu, R=Ph 8, Tol 9) containing a bis(diphenylphosphanyl)butadienyl bridging ligand formed by an unprecedented sequential insertion reaction of two P-coordinated PPh(2)CtriplebondCR ligands into a PtbondC(6)F(5) bond. Although in solution the presence of coordinated solvent S (S=(thf)(x)(H(2)O)(y)) in 6, 7 is suggested by NMR spectroscopy, X-ray diffraction analyses of different crystals of the mixed complex [Pt(C(6)F(5))mu-[C(tBu)doublebondC(PPh(2))C(PPh(2))doublebondC(Tol)(C(6)F(5))]Pt(C(6)F(5))(2)] 9 unequivocally establish that in the solid state the steric crowding of the new diphenylbutadienyl ligand formed stabilizes an unusual coordinatively unsaturated T-shaped 3-coordinated platinum(II) center. Structure determinations of the mononuclear precursors cis-[Pt(C(6)F(5))(2)(PPh(2)CtriplebondCR)(2)] (R=Ph, tBu, Tol) have been carried out to evaluate the factors affecting the insertion processes. The reactions of the platinum complexes 6 towards neutral ligands (L=CO, py, PPh(2)H, CNtBu) in a 1:1 molar ratio afford related diplatinum derivatives 10-13, whereas treatment with CNtBu (1:2 molar ratio) or 2,2'-bipy (1:1 molar ratio) results in the opening of the chelating ring to give cis,cis-[Pt(C(6)F(5))(L)(2)mu-[1-kappaC(1):2-kappaPP'-C(R)doublebondC(PPh(2))C(PPh(2))doublebondC(R)(C(6)F(5))]Pt(C(6)F(5))(2)] (14, 15). The unsaturated or solvento

  18. Materiales compuestos C/SiC para aplicaciones estructurales de alta temperatura. Parte I: estabilidad termodinámica y química

    Directory of Open Access Journals (Sweden)

    Aparicio, M.

    2000-12-01

    Full Text Available The development of aero-engine and aircraft industry is aimed to hypersonic technology, efficiency enhancements and pollutant emission reductions. This objective can only be reached by increasing the operating temperatures, utilising new materials which mechanical properties are retained up to high temperatures. SiC matrix composites reinforced with carbon fibres (C/SiC are good examples with very good bending and thermal shock resistance at temperatures up to 1600ºC as well as low density. However, the fact which currently inhibits the application of these materials is the high oxidation rate of carbon fibres at temperatures above 450ºC. In the first part of the paper, a review of the most important properties and oxidation mechanisms of C and SiC has been carried out. The influence of each material disposition, individually and as composite, has been analysed.

    El desarrollo de la industria aeroespacial se orienta actualmente hacia la tecnología hipersónica, el incremento en el rendimiento de las reacciones de combustión y la reducción de la emisión de contaminantes. Estos objetivos sólo pueden alcanzarse aumentando la temperatura de combustión, para lo cual es necesario desarrollar nuevos materiales que conserven sus propiedades mecánicas hasta temperaturas muy elevadas. Entre ellos se encuentran los materiales compuestos de matriz de SiC reforzada con fibra continua de carbono (C/SiC, cuyas propiedades más importantes son una elevada resistencia a flexión y al choque térmico desde temperatura ambiente hasta 1600ºCy su reducido peso específico. Sin embargo, el principal problema que acompaña a los materiales compuestos C/SiC es la elevada velocidad de oxidación de la fibra de carbono a partir de 450ºC. En la primera parte del trabajo se realiza una revisión de las características más relevantes del carbono y SiC, y de su comportamiento frente a la oxidación, tanto por separado como formando parte de materiales

  19. Chemical stabilization and improved thermal resilience of molecular arrangements: possible formation of a surface network of bonds by multiple pulse atomic layer deposition.

    Science.gov (United States)

    de Pauli, Muriel; Matos, Matheus J S; Siles, Pablo F; Prado, Mariana C; Neves, Bernardo R A; Ferreira, Sukarno O; Mazzoni, Mário S C; Malachias, Angelo

    2014-08-14

    In this work, we make use of an atomic layer deposition (ALD) surface reaction based on trimethyl-aluminum (TMA) and water to modify O-H terminated self-assembled layers of octadecylphosphonic acid (OPA). The structural modifications were investigated by X-ray reflectivity, X-ray diffraction, and atomic force microscopy. We observed a significant improvement in the thermal stability of ALD-modified molecules, with the existence of a supramolecular packing structure up to 500 °C. Following the experimental observations, density functional theory (DFT) calculations indicate the possibility of formation of a covalent network with aluminum atoms connecting OPA molecules at terrace surfaces. Chemical stability is also achieved on top of such a composite surface, inhibiting further ALD oxide deposition. On the other hand, in the terrace edges, where the covalent array is discontinued, the chemical conditions allow for oxide growth. Analysis of the DFT results on band structure and density of states of modified OPA molecules suggests that besides the observed thermal resilience, the dielectric character of OPA layers is preserved. This new ALD-modified OPA composite is potentially suitable for applications such as dielectric layers in organic devices, where better thermal performance is required.

  20. Understanding Bonds - Denmark

    DEFF Research Database (Denmark)

    Rimmer, Nina Røhr

    2016-01-01

    a specified rate of interest during the life of the bond and to repay the face value of the bond (the principal) when it “matures,” or comes due. Among the types of bonds you can choose from are: Government securities, municipal bonds, corporate bonds, mortgage and asset-backed securities, federal agency...

  1. Steady-state analytical model of suspended p-type 3C-SiC bridges under consideration of Joule heating

    Science.gov (United States)

    Balakrishnan, Vivekananthan; Dinh, Toan; Phan, Hoang-Phuong; Kozeki, Takahiro; Namazu, Takahiro; Viet Dao, Dzung; Nguyen, Nam-Trung

    2017-07-01

    This paper reports an analytical model and its validation for a released microscale heater made of 3C-SiC thin films. A model for the equivalent electrical and thermal parameters was developed for the two-layer multi-segment heat and electric conduction. The model is based on a 1D energy equation, which considers the temperature-dependent resistivity and allows for the prediction of voltage-current and power-current characteristics of the microheater. The steady-state analytical model was validated by experimental characterization. The results, in particular the nonlinearity caused by temperature dependency, are in good agreement. The low power consumption of the order of 0.18 mW at approximately 310 K indicates the potential use of the structure as thermal sensors in portable applications.

  2. Comment on “Structural, elastic, electronic, magnetic and optical properties of RbSrX (C, SI, Ge) half-Heusler compounds”

    Energy Technology Data Exchange (ETDEWEB)

    Jalilian, Jaafar, E-mail: jaafarjalilian@gmail.com [Young Researchers and Elite Club, Kermanshah Branch, Islamic Azad University, Kermanshah (Iran, Islamic Republic of); Motiepour, Pouria [Electrical Engineering Department, Technical and Vocational University, Kermanshs (Iran, Islamic Republic of)

    2015-12-15

    In a recent article by Ahmad et al. (2015) [1] structural, elastic, electronic, magnetic and optical properties of RbSrX (C, Si, Ge) half-Heusler compounds have been studied by the first principles calculations. After studying this article, we found that there are some physical and computational mistakes in electronic and optical properties sections. In investigating optical properties, they did not consider intraband transitions contribution in complex dielectric function term, while this term has significant effect on optical spectra for half-metallic materials. - Highlights: • The spin up channel is more occupied than the spin down channel. • The intraband transition has remarkable effects on optical properties of half-metallic materials. • The intraband transitions increase reflectance in low energy ranges.

  3. Creep, Fatigue and Fracture Behavior of Environmental Barrier Coating and SiC-SiC Ceramic Matrix Composite Systems: The Role of Environment Effects

    Science.gov (United States)

    Zhu, Dongming; Ghosn, Louis J.

    2015-01-01

    Advanced environmental barrier coating (EBC) systems for low emission SiCSiC CMC combustors and turbine airfoils have been developed to meet next generation engine emission and performance goals. This presentation will highlight the developments of NASAs current EBC system technologies for SiC-SiC ceramic matrix composite combustors and turbine airfoils, their performance evaluation and modeling progress towards improving the engine SiCSiC component temperature capability and long-term durability. Our emphasis has also been placed on the fundamental aspects of the EBC-CMC creep and fatigue behaviors, and their interactions with turbine engine oxidizing and moisture environments. The EBC-CMC environmental degradation and failure modes, under various simulated engine testing environments, in particular involving high heat flux, high pressure, high velocity combustion conditions, will be discussed aiming at quantifying the protective coating functions, performance and durability, and in conjunction with damage mechanics and fracture mechanics approaches.

  4. The design and optimization of two low frequency energy harvesters employing 3C-SiC/AlN/Mo composite layers

    Energy Technology Data Exchange (ETDEWEB)

    Iqbal, Abid, E-mail: abid.iqbal@griffithuni.edu.au; Mohd-Yasin, Faisal, E-mail: abid.iqbal@griffithuni.edu.au; Dimitrijev, Sima, E-mail: abid.iqbal@griffithuni.edu.au [Queensland Micro- and Nanotechnology Centre, Griffith University, Brisbane, QLD 4111 (Australia)

    2014-10-24

    This paper presents the design and simulation of twocantilever-based energy harvesters that employs cubic silicon carbide on silicon (3C-SiC-on-Si) wafer as the base material and bottom electrode. Aluminum Nitride (AlN) is employed as the piezoelectric/middle layer due to its excellent material properties and high stability in varying temperature and harsh environment. Molybdenum (Mo) serves as the top layer/electrode. The thickness of the structural layers are optimized through MATLAB and also analyzed via Finite Element Analysis using Intellisuite. Two designs are proposed at low resonant frequency, one with conventional cantilever beam, the other being a T-shaped cantilever beam. Both structures are simulated and their performances are compared.

  5. Materiales compuestos C/SiC para aplicaciones estructurales de alta temperatura. Parte II: Sistemas de protección contra la oxidación

    Directory of Open Access Journals (Sweden)

    Aparicio, M.

    2001-02-01

    Full Text Available The fact which currently excludes the use of C/SiC composites in high temperature structural applications is the high oxidation rate of carbon fibres at temperatures higher than 450ºC. In this second part of the paper, a review of the different oxidation protection systems, including inhibitors, surface modification of composites, coatings and previous infiltration of the substrates, has been carried out. The addition of inhibitors reduces the oxidation rate, but only up to 850ºC, while the surface modification of composites leads to thin coatings with poor thermal shock resistance. On the other hand, the external layers are the most usual method employed because allows combining different compositions and thicknesses. The multilayer coatings are especially interesting in applications with wide temperature range and thermal shocks requirements. The infiltration of substrate porosity improves slightly the oxidation resistance of C/SiC composites reducing the oxygen accessibility to carbon fibres. However, the infiltration complements very well the oxidation protection performance of a coating system at low temperature, since these normally present open cracks due to mismatch between coating and substrate thermal expansion coefficients.

    La utilización de los materiales compuestos C/SiC en aplicaciones estructurales a alta temperatura está limitada por la elevada velocidad de oxidación de la fibra de carbono a temperaturas superiores de 450ºC. En esta segunda parte del trabajo se realiza una revisión de las posibilidades de protección contra la oxidación de estos materiales, incluyendo inhibidores, modificación superficial del material compuesto, recubrimientos e infiltración previa del sustrato. La eficacia de los inhibidores de la reacción de oxidación esta restringida a temperaturas de hasta 850ºC, mientras que la modificación superficial del material compuesto da lugar a capas delgadas y poco resistentes a los ciclos t

  6. Lamb waves propagation along 3C-SiC/AlN membranes for application in temperature-compensated, high-sensitivity gravimetric sensors.

    Science.gov (United States)

    Caliendo, Cinzia; D'Amico, Arnaldo; Lo Castro, Fabio

    2013-01-02

    The propagation of the fundamental quasi-symmetric Lamb mode S(0) travelling along 3C-SiC/c-AlN composite plates is theoretically studied with respect to the AlN and SiC film thickness, the acoustic wave propagation direction and the electrical boundary conditions. The temperature effects on the phase velocity have been considered for four AlN/SiC-based electroacoustic coupling configurations, specifically addressing the design of temperature-compensated, enhanced-coupling, GHz-range electroacoustic devices. The gravimetric sensitivity and resolution of the four temperature-stable SiC/AlN composite structures are theoretically investigated with respect to both the AlN and SiC sensing surface. The SiC/AlN-based sensor performances are compared to those of surface acoustic waves and Lamb S(0) mode mass sensors implemented on bulk conventional piezoelectric materials and on thin suspended membranes.

  7. Lamb Waves Propagation along 3C-SiC/AlN Membranes for Application in Temperature-Compensated, High-Sensitivity Gravimetric Sensors

    Science.gov (United States)

    Caliendo, Cinzia; D'Amico, Arnaldo; Castro, Fabio Lo

    2013-01-01

    The propagation of the fundamental quasi-symmetric Lamb mode S0 travelling along 3C-SiC/c-AlN composite plates is theoretically studied with respect to the AlN and SiC film thickness, the acoustic wave propagation direction and the electrical boundary conditions. The temperature effects on the phase velocity have been considered for four AlN/SiC-based electroacoustic coupling configurations, specifically addressing the design of temperature-compensated, enhanced-coupling, GHz-range electroacoustic devices. The gravimetric sensitivity and resolution of the four temperature-stable SiC/AlN composite structures are theoretically investigated with respect to both the AlN and SiC sensing surface. The SiC/AlN-based sensor performances are compared to those of surface acoustic waves and Lamb S0 mode mass sensors implemented on bulk conventional piezoelectric materials and on thin suspended membranes. PMID:23282585

  8. Residue-free reactive ion etching of 3C-SiC and 6H-SiC in fluorinated mixture plasmas

    Energy Technology Data Exchange (ETDEWEB)

    Yih, P.H.; Steckl, A.J. [Univ. of Cincinnati, OH (United States)

    1995-08-01

    The authors report on residue-free reactive ion etching (RIE) of 3C-SiC and 6H-SiC in mixtures of fluorinated gases consisting of a primary (CHF{sub 3}) and a secondary gas (CF{sub 4}, NF{sub 3}, and SF{sub 6}). The corresponding etch rate, etched surface morphology, anisotropic profile, and process reproducibility are obtained at different levels of CHF{sub 3}. The advantage of this approach is to eliminate gas additives (H{sub 2} and O{sub 2}) while maintaining the residue-free RIE and high process portability. The effect of SiC doping concentration and dopant type on obtaining residue-free RIE is reported along with the effects of plasma pressure and RF power. Etching mechanisms, plasma chemistry, and optimized etching conditions are also discussed.

  9. Computer Aided Multi-scale Design of SiC-Si3N4 Nanoceramic Composites for High-Temperature Structural Applications

    Energy Technology Data Exchange (ETDEWEB)

    Vikas Tomer; John Renaud

    2010-08-31

    It is estimated that by using better and improved high temperature structural materials, the power generation efficiency of the power plants can be increased by 15% resulting in significant cost savings. One such promising material system for future high-temperature structural applications in power plants is Silicon Carbide-Silicon Nitride (SiC-Si{sub 3}N{sub 4}) nanoceramic matrix composites. The described research work focuses on multiscale simulation-based design of these SiC-Si{sub 3}N{sub 4} nanoceramic matrix composites. There were two primary objectives of the research: (1) Development of a multiscale simulation tool and corresponding multiscale analyses of the high-temperature creep and fracture resistance properties of the SiC-Si{sub 3}N{sub 4} nanocomposites at nano-, meso- and continuum length- and timescales; and (2) Development of a simulation-based robust design optimization methodology for application to the multiscale simulations to predict the range of the most suitable phase morphologies for the desired high-temperature properties of the SiC-Si{sub 3}N{sub 4} nanocomposites. The multiscale simulation tool is based on a combination of molecular dynamics (MD), cohesive finite element method (CFEM), and continuum level modeling for characterizing time-dependent material deformation behavior. The material simulation tool is incorporated in a variable fidelity model management based design optimization framework. Material modeling includes development of an experimental verification framework. Using material models based on multiscaling, it was found using molecular simulations that clustering of the SiC particles near Si{sub 3}N{sub 4} grain boundaries leads to significant nanocomposite strengthening and significant rise in fracture resistance. It was found that a control of grain boundary thicknesses by dispersing non-stoichiometric carbide or nitride phases can lead to reduction in strength however significant rise in fracture strength. The

  10. Low-cost high-haze films based on ZnO nanorods for light scattering in thin c-Si solar cells

    Science.gov (United States)

    Strano, V.; Smecca, E.; Depauw, V.; Trompoukis, C.; Alberti, A.; Reitano, R.; Crupi, I.; Gordon, I.; Mirabella, S.

    2015-01-01

    Light scattering from ZnO nanorods (NR) is investigated, modeled, and applied to a solar cell. ZnO NR (120-1300 nm long, 280-60 nm large), grown by low-cost chemical bath deposition at 90 °C, exhibit diffused-to-total transmitted light as high as 70% and 30% in the 400 and 1000 nm wavelength range, respectively. Data and scattering simulation show that ZnO NR length plays a crucial role in light diffusion effect. A transparent ZnO NR film grown on glass and placed on top of a 1 μm thick c-Si solar cell is shown to enhance the light-current conversion efficiency for wavelengths longer than 600 nm.

  11. Optical design of GaN/In(x)Ga(1-x)N/cSi tandem solar cells with triangular diffraction grating.

    Science.gov (United States)

    Lin, Leo Jyun-Hong; Chiou, Yih-Peng

    2015-06-01

    Optical design in enhancing optical absorption of group-III-nitride- and multiple quantum well-based GaN/InxGa1-xN/cSi dual-junction tandem solar cells with triangular diffraction grating is simulated and optimized by using combined two-dimensional rigorous coupled wave analysis and transfer matrix methods. This paper thoroughly examines these phenomena of optical absorption affected by antireflection coatings, multiple thin-film layers and diffraction gratings with the integrated perspectives of semiconductor physics and electromagnetic theory for the first time. An improvement of 58% in absorption compared to the prototype SC is obtained which means more than 80% of incoming light (hυ > EgSi) can be harvested in this thin-film (< 4 μm in total) design.

  12. Influences of Asymmetrically Distributed Defect States at Rear c-Si/a-Si:H Interface on Performances of Silicon Hetero-Junction Solar Cells

    Science.gov (United States)

    Wang, Junkang; Xu, Jingping; Lei, Qingsong; Wang, Lisheng

    2013-08-01

    The performances of silicon double hetero-junction solar cells are investigated by the numerical simulator "Automat For Simulation of Hetero-structures (AFORS-HET)". Asymmetrical distribution of acceptor and donor defect states at the rear hetero-junction interface is introduced in both a-Si:H(n)/c-Si(p)/a-Si:H(p+) and a-Si:H(p)/c-Si(n)/a-Si:H(n+) structures in our study. The influences of total defect density and rear emitter parameters (doping concentration and band discontinuity to silicon substrate) on performances of the solar cells are analyzed. The simulated results indicate that the npp+ cells with acceptor dominated defect states at the rear interface can obtain better performances, and the same for the pnn+ cells with donor dominated defect states. Moreover, the npp+ cells are more sensitive to the total interface defect density and its distribution mode due to the unfavorable band offset between the absorber and the rear emitter. But when total defect density is small, the npp+ cells show more sensitivity to change of the doping concentration at the rear emitter than the pnn+ cells, and conversely, the pnn+ cells show more sensitivity to the distribution mode of defect states at the rear emitter than the npp+ cells. Due to weaker inherent back diffusion ability of minority carrier, the pnn+ cells with moderate band offset (0.25 0.37 eV) at the rear hetero-junction are more sensitive to the incentive effect of localized charges at the interface formed by asymmetrically distributed defect states, and the interface with donor dominated defect states is a better option for the pnn+ cells when the total defect density is relatively small.

  13. Chemical Bonds II

    Science.gov (United States)

    Sanderson, R. T.

    1972-01-01

    The continuation of a paper discussing chemical bonding from a bond energy viewpoint, with a number of examples of single and multiple bonds. (Part I appeared in volume 1 number 3, pages 16-23, February 1972.) (AL)

  14. What Determines Bond Costs. Municipal Bonds Series.

    Science.gov (United States)

    Young, Douglas; And Others

    Public officials in small towns who participate infrequently in the bond market need information about bond financing. This publication, one in a series of booklets published by the Western Rural Development Center using research gathered between 1967-77, discusses factors influencing the marketability and cost of bond financing for towns and…

  15. ZrB2-SiC as a protective coating for C/SiC composites: Effect of high temperature oxidation on thermal shock property and protection mechanism

    Directory of Open Access Journals (Sweden)

    Xiang Yang

    2016-06-01

    Full Text Available ZrB2-SiC coating was prepared on C/SiC composites surface by slurry method, and then the thermal fatigue behavior of ZrB2-SiC coated C/SiC composites was studied. The composition of the coating layers was characterized by XRD, SEM and EDS. With the thickness was 200 μm, the coating was ZrB2 and SiC. During thermal cycle between 1773 K in air and 373 K in boiling water, the weight of the ZrB2-SiC coated composites decreased lightly. The decrease of the flexural strength during the thermal cycle was primarily due to the debonding of the fiber–matrix interfaces and the oxidation of the coated samples. Compared with the uncoated C/SiC composites, the coating played an important role in enhancing the resistance to the thermal shock.

  16. Wire bonding in microelectronics

    CERN Document Server

    Harman, George G

    2010-01-01

    Wire Bonding in Microelectronics, Third Edition, has been thoroughly revised to help you meet the challenges of today's small-scale and fine-pitch microelectronics. This authoritative guide covers every aspect of designing, manufacturing, and evaluating wire bonds engineered with cutting-edge techniques. In addition to gaining a full grasp of bonding technology, you'll learn how to create reliable bonds at exceedingly high yields, test wire bonds, solve common bonding problems, implement molecular cleaning methods, and much more. Coverage includes: Ultrasonic bonding systems and technologies, including high-frequency systems Bonding wire metallurgy and characteristics, including copper wire Wire bond testing Gold-aluminum intermetallic compounds and other interface reactions Gold and nickel-based bond pad plating materials and problems Cleaning to improve bondability and reliability Mechanical problems in wire bonding High-yield, fine-pitch, specialized-looping, soft-substrate, and extreme-temperature wire bo...

  17. DETECTING DOMAIN BOUNDARIES IN PROTEINS THROUGH PLOTTING OF THE ENERGY OF NON-BONDED INTERACTIONS (ENBI AS A FUNCTION OF PROGRESSIVE IN SILICO TRUNCATION OF CHAINS IN NATIVE STRUCTURAL FORMAT

    Directory of Open Access Journals (Sweden)

    Purnananda Guptasarma

    2012-12-01

    Full Text Available Several methods exist for the detection of domain boundaries in proteins. Different methods exploit different structural-biochemical characteristics distinguishing, and defining, protein domains. However, perhaps because ‘domains’ remain poorly defined, no single method has proved to be entirely satisfactory. Here, a new approach to defining and detecting domains is presented, along with some preliminary data from three proteins, in the form of a proof-of-concept. It is argued from first principles that protein domain boundaries may be identified through plotting of variations in the energy of non-bonded interactions of a naturally-occurring protein as a function of varying chain length (in native structural format. Such plots may be expected to show a broadly descending trend as a function of increasing chain length, marked by slope changes at domain boundaries. The approach is demonstrated with three multi-domain, single-subunit proteins, porcine pepsin (4PEP, thymidylate synthase (4TMS and aconitase (5ACN.

  18. A new reaction mode of germanium-silicon bond formation: insertion reactions of H₂GeLiF with SiH₃X (X = F, Cl, Br).

    Science.gov (United States)

    Yan, Bingfei; Li, Wenzuo; Xiao, Cuiping; Li, Qingzhong; Cheng, Jianbo

    2013-10-01

    A combined density functional and ab initio quantum chemical study of the insertion reactions of the germylenoid H2GeLiF with SiH3X (X = F, Cl, Br) was carried out. The geometries of all the stationary points of the reactions were optimized using the DFT B3LYP method and then the QCISD method was used to calculate the single-point energies. The theoretical calculations indicated that along the potential energy surface, there were one precursor complex (Q), one transition state (TS), and one intermediate (IM) which connected the reactants and the products. The calculated barrier heights relative to the respective precursors are 102.26 (X = F), 95.28 (X = Cl), and 84.42 (X = Br) kJ mol(-1) for the three different insertion reactions, respectively, indicating the insertion reactions should occur easily according to the following order: SiH3-Br > SiH3-Cl > SiH3-F under the same situation. The solvent effects on the insertion reactions were also calculated and it was found that the larger the dielectric constant, the easier the insertion reactions. The elucidations of the mechanism of these insertion reactions provided a new reaction model of germanium-silicon bond formation.

  19. Sodium dichloroiodate promoted C-C bond cleavage: An efficient ...

    Indian Academy of Sciences (India)

    SAKET B BHAGAT

    2018-02-01

    Feb 1, 2018 ... benzimidazoles/benzothiazoles/benzoxazoles under mild conditions. This tandem process involved a C-C bond cleavage and C-N bond formation. Keywords. Benzimidazole/benzothiazole/benzoxazole; β-diketones; NaICl2; C-C bond cleavage. 1. Introduction. Nitrogen-containing five-member heterocyclic ...

  20. Creep/Stress Rupture Behavior of 3D Woven SiC/SiC Composites with Sylramic-iBN, Super Sylramic-iBN and Hi-Nicalon-S Fibers at 2700F in Air

    Science.gov (United States)

    Bhatt, R. T.

    2017-01-01

    To determine the influence of fiber types on creep durability, 3D SiC/SiC CMCs were fabricated with Sylramic-iBN, super Sylramic-iBN and Hi-Nicalon-S fibers and the composite specimens were then tested under isothermal tensile creep at 14820C at 69, 103 and 138 MPa for up to 300hrs in air. The failed specimens were examined by scanning electron microscopy (SEM) and computed tomography (CT) for fracture mode analysis. The creep data of these composites are compared with those of other SiC/SiC composites in the literature. The results of this study will be presented.

  1. cellules solaires à hétérojonction a-Si : H/c-Si : évaluation et amélioration de la face arrière

    OpenAIRE

    Martin De Nicolas, Silvia

    2012-01-01

    Amongst available silicon-based photovoltaic technologies, a-Si:H/c-Si heterojunctions (HJ) have raised growing attention because of their potential for further efficiency improvement and cost reduction. In this thesis, research on n-type a-Si:H/c-Si heterojunction solar cells developed at the Institute National de l’Énergie Solaire is presented. Technological and physical aspects of HJ devices are reviewed, with the focus on the comprehension of the back side role. Then, an extensive work to...

  2. IMPACT OF PHYSICAL AND CHEMICAL MUD CONTAMINATION ON WELLBORE CEMENT- FORMATION SHEAR BOND STRENGTH Authors: Arome Oyibo1 and Mileva Radonjic1 * 1. Craft and Hawkins Department of Petroleum Engineering, 2131 Patrick F. Taylor Hall, Louisiana State University, Baton Rouge, LA 70803, aoyibo1@tigers.lsu.edu, mileva@lsu.edu

    Science.gov (United States)

    Oyibo, A. E.

    2013-12-01

    Wellbore cement has been used to provide well integrity through zonal isolation in oil & gas wells and geothermal wells. Cementing is also used to provide mechanical support for the casing and protect the casing from corrosive fluids. Failure of cement could be caused by several factors ranging from poor cementing, failure to completely displace the drilling fluids to failure on the path of the casing. A failed cement job could result in creation of cracks and micro annulus through which produced fluids could migrate to the surface which could lead to sustained casing pressure, contamination of fresh water aquifer and blow out in some cases. In addition, cement failures could risk the release of chemicals substances from hydraulic fracturing into fresh water aquifer during the injection process. To achieve proper cementing, the drilling fluid should be completely displaced by the cement slurry. However, this is hard to achieve in practice, some mud is usually left on the wellbore which ends up contaminating the cement afterwards. The purpose of this experimental study is to investigate the impact of both physical and chemical mud contaminations on cement-formation bond strength for different types of formations. Physical contamination occurs when drilling fluids (mud) dries on the surface of the formation forming a mud cake. Chemical contamination on the other hand occurs when the drilling fluids which is still in the liquid form interacts chemically with the cement during a cementing job. We investigated the impact of the contamination on the shear bond strength and the changes in the mineralogy of the cement at the cement-formation interface to ascertain the impact of the contamination on the cement-formation bond strength. Berea sandstone and clay rich shale cores were bonded with cement cores with the cement-formation contaminated either physically or chemically. For the physically contaminated composite cores, we have 3 different sample designs: clean

  3. Revisiting Hydrogen Bond Thermodynamics in Molecular Simulations.

    Science.gov (United States)

    Sapir, Liel; Harries, Daniel

    2017-06-13

    In processes involving aqueous solutions and in almost every biomolecular interaction, hydrogen bonds play important roles. Though weak compared to the covalent bond, hydrogen bonds modify the stability and conformation of numerous small and large molecules and modulate their intermolecular interactions. We propose a simple methodology for extracting hydrogen bond strength from atomistic level simulations. The free energy associated with hydrogen bond formation is conveniently calculated as the reversible work required to reshape a completely random pair probability distribution reference state into the one found in simulations where hydrogen bonds are formed. Requiring only the probability density distribution of donor-acceptor pairs in the first solvation shell of an electronegative atom, the method uniquely defines the free energy, entropy, and enthalpy of the hydrogen bond. The method can be easily extended to molecules other than water and to multiple component mixtures. We demonstrate and apply this methodology to hydrogen bonds that form in molecular dynamics simulations between water molecules in pure water, as well as to bonds formed between different molecules in a binary mixture of a sugar (trehalose) and water. Finally, we comment on how the method should be useful in assessing the role of hydrogen bonds in different molecular mechanisms.

  4. Bond strengthening in oral bacterial adhesion to salivary conditioning films

    NARCIS (Netherlands)

    van der Mei, Henderina; Rustema-Abbing, Mina; de Vries, Jacob; Busscher, Hendrik

    Transition from reversible to irreversible bacterial adhesion is a highly relevant but poorly understood step in initial biofilm formation. We hypothesize that in oral biofilm formation, irreversible adhesion is caused by bond strengthening due to specific bacterial interactions with salivary

  5. Peptide Bond Formations through Flow Chemistry.

    Science.gov (United States)

    Ahmed, N

    2017-10-04

    Peptides and proteins play important roles in body functions(1) ,(2) and are used exclusively in drug discoveries, having advantages because of their high biological activity, high specificity, and low toxicity. For peptide synthesis, researchers mostly use the solid-phase peptide synthesis (SPPS)(3) with modern modifications.(4) However, scientists failed to overcome two main factors; the concentration and time required for peptide coupling. The flow-based technology may help in the rapid production of peptides due to having advantages over batch reactions(5-7) in terms of productivity, heat and mixing efficiency, safety, and reproducibility. Herein, we discussed both solution and solid phase synthesis of peptides in flow.(8-12) This article is protected by copyright. All rights reserved. This article is protected by copyright. All rights reserved.

  6. A first principles analysis of the effect of hydrogen concentration in hydrogenated amorphous silicon on the formation of strained Si-Si bonds and the optical and mobility gaps

    Energy Technology Data Exchange (ETDEWEB)

    Legesse, Merid; Nolan, Michael, E-mail: Michael.nolan@tyndall.ie; Fagas, Giorgos, E-mail: Georgios.fagas@tyndall.ie [Tyndall National Institute, University College Cork, Lee Maltings, Dyke Parade, Cork (Ireland)

    2014-05-28

    In this paper, we use a model of hydrogenated amorphous silicon generated from molecular dynamics with density functional theory calculations to examine how the atomic geometry and the optical and mobility gaps are influenced by mild hydrogen oversaturation. The optical and mobility gaps show a volcano curve as the hydrogen content varies from undersaturation to mild oversaturation, with largest gaps obtained at the saturation hydrogen concentration. At the same time, mid-gap states associated with dangling bonds and strained Si-Si bonds disappear at saturation but reappear at mild oversaturation, which is consistent with the evolution of optical gap. The distribution of Si-Si bond distances provides the key to the change in electronic properties. In the undersaturation regime, the new electronic states in the gap arise from the presence of dangling bonds and strained Si-Si bonds, which are longer than the equilibrium Si-Si distance. Increasing hydrogen concentration up to saturation reduces the strained bonds and removes dangling bonds. In the case of mild oversaturation, the mid-gap states arise exclusively from an increase in the density of strained Si-Si bonds. Analysis of our structure shows that the extra hydrogen atoms form a bridge between neighbouring silicon atoms, thus increasing the Si-Si distance and increasing disorder in the sample.

  7. Formation of an Ion-Pair Molecule with a Single NH+...Cl- Hydrogen Bond: Raman spectra of 1,1,3,3-Tetramethylguanidinium chloride in the solid state, in solution and in the vapor phase

    DEFF Research Database (Denmark)

    Berg, Rolf W.; Riisager, Anders; Fehrmann, Rasmus

    2008-01-01

    scattering spectra are presented and assigned, by comparing to the quantum mechanical calculations. It is concluded that dimeric molecular ion pairs with four N-H+ · · · Cl- hydrogen bonds probably exist in the solutions and are responsible for the relatively high solubility of the “salt” in ethanol......- hydrogen bond, the stretching band of which is causing the band....

  8. The Effect of Nanosized Carbon Black on the Physical and Thermomechanical Properties of Al2O3-SiC-SiO2-C Composite

    Directory of Open Access Journals (Sweden)

    Mohamad Hassan Amin

    2009-01-01

    Full Text Available The effects of using nanosized carbon black in the range of 0–10 weight percentages on the physical and thermomechanical properties of Al2O3-SiC-SiO2–graphite refractory composites were investigated. Nanosized carbon black addition improved the relative heat resistance and oxidation resistance of composites. The bulk density of the composites is reduced with increasing carbon black (CB content. Increase in CB content first causes an increase in the apparent porosity, but at more than 3 wt% amount of CB, a decrease of apparent porosity was observed. The cold crushing strength (CCS increased with increasing CB content in samples fired at 800∘C and in samples fired at 1500∘C when the content is increased to 3 wt%, but the CCS decreased with increasing CB content in samples fired at 1500∘C when the CB content was less than 3 wt%. The composite without CB exhibits the highest value of CCS at firing temperature of 1500∘C.

  9. Use of the Materials Genome Initiative (MGI approach in the design of improved-performance fiber-reinforced SiC/SiC ceramic-matrix composites (CMCs

    Directory of Open Access Journals (Sweden)

    Jennifer S. Snipes

    2016-07-01

    Full Text Available New materials are traditionally developed using costly and time-consuming trial-and-error experimental efforts. This is followed by an even lengthier material-certification process. Consequently, it takes 10 to 20 years before a newly-discovered material is commercially employed. An alternative approach to the development of new materials is the so-called materials-by-design approach within which a material is treated as a complex hierarchical system, and its design and optimization is carried out by employing computer-aided engineering analyses, predictive tools and available material databases. In the present work, the materials-by-design approach is utilized to design a grade of fiber-reinforced (FR SiC/SiC ceramic matrix composites (CMCs, the type of materials which are currently being used in stationary components, and are considered for use in rotating components, of the hot sections of gas-turbine engines. Towards that end, a number of mathematical functions and numerical models are developed which relate CMC constituents’ (fibers, fiber coating and matrix microstructure and their properties to the properties and performance of the CMC as a whole. To validate the newly-developed materials-by-design approach, comparisons are made between experimentally measured and computationally predicted selected CMC mechanical properties. Then an optimization procedure is employed to determine the chemical makeup and processing routes for the CMC constituents so that the selected mechanical properties of the CMCs are increased to a preset target level.

  10. Adhesion of water droplets by low voltage electrowetting on a superhydrophobic surface of a 3C-SiC nanorod network

    Science.gov (United States)

    Khan, Afzal; Sohail, Shiraz; Jacob, Chacko

    2015-12-01

    Adhesion state of a liquid droplet on the superhydrophobic surfaces can be tuned by electrowetting and can be exploited for various applications in microfluidics, lab on chip and biotechnology, etc. Silicon carbide (SiC) can be used for these kinds of studies due to its high chemical and mechanical stability in harsh environment conditions. In this work, a low dc voltage irreversible electrowetting using a deionized water droplet on superhydrophobic hierarchical Au/Pd nanostructures coated 3C-SiC nanorod surface is demonstrated. Strong adhesion of the water droplet to the surface was achieved by changing its adhesion state from low to high and then very high by electrowetting, thereby changing the contact angle from 160° to 75°. The first irreversible transition of water droplet from Cassie regime to Wenzel regime occurred at 16 V due to the drastic increase of the work of adhesion which was found to be 10 times that of the initial value. Finally, the work of adhesion was increased about 20 times its initial value by increasing the applied voltage up to 24 V.

  11. Damage characteristics and constitutive modeling of the 2D C/SiC composite: Part II – Material model and numerical implementation

    Directory of Open Access Journals (Sweden)

    Jun Li

    2015-02-01

    Full Text Available In this work, a macroscopic non-linear constitutive model accounting for damage, inelastic strain and unilateral behavior is proposed for the 2D plain-woven C/SiC composite. A set of scalar damage variables and a new thermodynamic potential expression are introduced in the framework of continuum damage mechanics. In the deduced constitutive equations, the material’s progressive damage deactivation behavior during the compression loading is described by a continuous function, and different deactivation rates under uniaxial and biaxial compression loadings are also considered. In damage evolution laws, the coupling effect among the damage modes and impediment effect of compression stress on the development of shear damage in different plane stress states are taken into account. Besides, the general plasticity theory is applied to describing the evolution of inelastic strain in tension and/or shear stress state. The Tsai–Wu failure criterion is adopted for strength analysis. Additionally, the material model is implemented as a user-defined material subroutine (UMAT and linked to the ABAQUS finite element software, and its performance is demonstrated through several numerical examples.

  12. Electrical transport mechanisms in p{sup +} a-SiC:H/n c-Si heterojunctions: Dark J-V-T characteristics

    Energy Technology Data Exchange (ETDEWEB)

    Cleef, M.W.M. van; Philippens, M.W.H.; Rubinelli, F.A.; Schropp, R.E.I. [Utrecht Univ. (Netherlands); Kolter, M. [Forschungzentrum Juelich (Germany)

    1996-12-31

    In the present paper the authors show results of dark current-voltage measurements performed on p{sup +} a-SiC:H/n c-Si heterojunction diodes at various temperatures (100--400K). They investigated the voltage derivative of these J-V curves in order to distinguish possible current transport mechanisms. It was found that for low temperatures (<300K), the current is determined by recombination of carriers in the crystalline silicon, whereas at high temperature (>300K), by a tunneling mechanism. At room temperature, both mechanisms contribute to the current. By using an equivalent circuit model and detailed numerical simulations the authors have interpreted their experimental characteristics. The simulations done at room temperature, show that at low forward bias voltage the current is controlled by recombination in the crystalline silicon and that at high forward bias voltage by a combination of multi-step tunneling and a-SiC:H series resistance. For interface state densities equal to or higher than 10{sup 12} cm{sup {minus}2}, the recombination was found to be dominated by the states at the amorphous-crystalline silicon interface.

  13. Effect of Environment on Stress-Rupture Behavior of a Carbon Fiber-Reinforced Silicon Carbide (C/SiC) Ceramic Matrix Composite

    Science.gov (United States)

    Verrilli, Michael J.; Opila, Elizabeth J.; Calomino, Anthony; Kiser, J. Douglas

    2002-01-01

    Stress-rupture tests were conducted in air, vacuum, and steam-containing environments to identify the failure modes and degradation mechanisms of a carbon fiber-reinforced silicon carbide (C/SiC) composite at two temperatures, 600 and 1200 C. Stress-rupture lives in air and steam containing environments (50 - 80% steam with argon) are similar for a composite stress of 69 MPa at 1200 C. Lives of specimens tested in a 20% steam/argon environment were about twice as long. For tests conducted at 600 C, composite life in 20% steam/argon was 20 times longer than life in air. Thermogravimetric analysis of the carbon fibers was conducted under similar conditions to the stress-rupture tests. The oxidation rate of the fibers in the various environments correlated with the composite stress-rupture lives. Examination of the failed specimens indicated that oxidation of the carbon fibers was the primary damage mode for specimens tested in air and steam environments at both temperatures.

  14. Tribological Characteristics of C/C-SiC-Cu Composite and Al/SiC Composite Materials under Various Contact Conditions

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Byung-Kook; Shin, Dong-Gap; Kim, Chang-Lae; Kim, Dae-Eun [Yonsei Univ., Seoul (Korea, Republic of); Goo, Byeong-Choon [Korea Railroad Research Institute, Uiwang (Korea, Republic of)

    2017-01-15

    The surface temperature of disc brakes varies during braking, which can affect the friction and wear behavior of braking systems. In order to develop an efficient braking system, the friction and wear behaviors of brake materials need to be clearly understood. In this work, the friction and wear behavior of the C/C-SiC-Cu composite and the Al/SiC composite, which are used in disc braking systems, were investigated. Both the surface temperature and contact pressure were studied. A pin-on-reciprocating tribotester was used for this purpose, in order to control temperature and load. Results showed that the friction varied significantly with temperature and sliding distance. It was found that a transfer layer of compacted wear debris formed on the wear track of the two materials. These layers caused the surface roughness of the wear track to increase. The outcome of this work is expected to serve as a basis for the development of braking systems under various operating conditions.

  15. A New Adaptive Response Surface Model for Reliability Analysis of 2.5D C/SiC Composite Turbine Blade

    Science.gov (United States)

    Chang, Yaning; Sun, Zhigang; Sun, Weiyi; Song, Yingdong

    2017-11-01

    In order to calculate the failure probability of complex structures such as a 2.5D/SiC composites turbine blade and improve the structure safety, a new adaptive model of Response Surface (RS) analysis has been developed in this paper, which can improve the computational efficiency of structural failure problem while ensure the accuracy. The Gaussian Process Regression (GPR) theory was used to establish the RS and reconstruct the performance function of structure. And, an Adaptive Latin hypercube Sampling (ALHS) strategy was adopted in the process of establishing and correcting the RS. Finally the Direct Simulation Monte Carlo(DSMC)was utilized to calculate the failure probability of the performance function replacing the complex structure. Two numerical examples were calculated to validate the accuracy and computational efficiency of the proposed method. Additionally the finite element stress analysis results of 2.5D C/SiC composite turbine blade were used to structural reliability analysis by the proposed method. The approach in this paper provides a new way to evaluate the risk of the complex structures.

  16. Silylation of C-H bonds in aromatic heterocycles by an Earth-abundant metal catalyst

    Science.gov (United States)

    Toutov, Anton A.; Liu, Wen-Bo; Betz, Kerry N.; Fedorov, Alexey; Stoltz, Brian M.; Grubbs, Robert H.

    2015-02-01

    Heteroaromatic compounds containing carbon-silicon (C-Si) bonds are of great interest in the fields of organic electronics and photonics, drug discovery, nuclear medicine and complex molecule synthesis, because these compounds have very useful physicochemical properties. Many of the methods now used to construct heteroaromatic C-Si bonds involve stoichiometric reactions between heteroaryl organometallic species and silicon electrophiles or direct, transition-metal-catalysed intermolecular carbon-hydrogen (C-H) silylation using rhodium or iridium complexes in the presence of excess hydrogen acceptors. Both approaches are useful, but their limitations include functional group incompatibility, narrow scope of application, high cost and low availability of the catalysts, and unproven scalability. For this reason, a new and general catalytic approach to heteroaromatic C-Si bond construction that avoids such limitations is highly desirable. Here we report an example of cross-dehydrogenative heteroaromatic C-H functionalization catalysed by an Earth-abundant alkali metal species. We found that readily available and inexpensive potassium tert-butoxide catalyses the direct silylation of aromatic heterocycles with hydrosilanes, furnishing heteroarylsilanes in a single step. The silylation proceeds under mild conditions, in the absence of hydrogen acceptors, ligands or additives, and is scalable to greater than 100 grams under optionally solvent-free conditions. Substrate classes that are difficult to activate with precious metal catalysts are silylated in good yield and with excellent regioselectivity. The derived heteroarylsilane products readily engage in versatile transformations enabling new synthetic strategies for heteroaromatic elaboration, and are useful in their own right in pharmaceutical and materials science applications.

  17. Chemical bonding in electron-deficient boron oxide clusters: core boronyl groups, dual 3c-4e hypervalent bonds, and rhombic 4c-4e bonds.

    Science.gov (United States)

    Chen, Qiang; Lu, Haigang; Zhai, Hua-Jin; Li, Si-Dian

    2014-04-28

    We explore the structural and bonding properties of the electron-deficient boron oxide clusters, using a series of B3On(-/0/+) (n = 2-4) clusters as examples. Global-minimum structures of these boron oxide clusters are identified via unbiased Coalescence Kick and Basin Hopping searches, which show a remarkable size and charge-state dependence. An array of new bonding elements are revealed: core boronyl groups, dual 3c-4e hypervalent bonds (ω-bonds), and rhombic 4c-4e bonds (o-bonds). In favorable cases, oxygen can exhaust all its 2s/2p electrons to facilitate the formation of B-O bonds. The current findings should help understand the bonding nature of low-dimensional boron oxide nanomaterials and bulk boron oxides.

  18. Dispersão e comportamento reológico de concretos refratários ultra-baixo teor de cimento no sistema Al2O3-SiC-SiO2-C Dispersion and setting control of ultra-low cement refractory castables in the Al2O3-SiC-SiO2-C system

    Directory of Open Access Journals (Sweden)

    I. R. de Oliveira

    2003-03-01

    Full Text Available Concretos refratários no sistema Al2O3-SiC-SiO2-C vêm sendo amplamente utilizados em indústrias siderúrgicas como revestimento de canais de corrida de altos-fornos, em virtude principalmente da sua elevada refratariedade aliada a altas resistências ao choque térmico e ao ataque por escória e metal fundido. Neste trabalho, investigou-se a influência de diferentes tipos de aditivos na trabalhabilidade e dispersão de concretos refratários de ultra-baixo teor de cimento nesse sistema. Apesar da sua alta capacidade de complexar íons de cálcio, moléculas de citrato não foram capazes de controlar adequadamente o tempo de pega do concreto estudado, contradizendo a idéia geral de que os íons de citrato devem ser utilizados para controlar a sua trabalhabilidade. Por outro lado, o aditivo polimetacrilato de sódio mostrou-se eficiente na otimização simultânea da dispersão e da trabalhabilidade do concreto devido provavelmente ao retardamento da dissolução dos íons advindos do cimento.Refractory castables in the Al2O3-SiC-SiO2-C system have been extensively used as linings for blast furnace runners, due mainly to their improved resistance to thermal shock damage and to slag and metal corrosion, respectively. In this work, ULC refractory castables in the Al2O3-SiC-SiO2-C system were prepared in order to evaluate the efficiency of different sort of additives on their dispersion and setting behavior. Although citrate ions are known to be efficient chelating agents, they were not able to properly control the working time of the castable studied, contradicting the general idea that citrate ions are necessary for controlling castable setting. On the other hand, the sodium polymethacrylate additive was found to be more efficient for the simultaneous optimization of the castable dispersion state and working time. This may be attributed to a retardation effect imparted by polymethacrylate molecules on the dissolution of ions from the surface

  19. Significantly Enhanced Dielectric Performances and High Thermal Conductivity in Poly(vinylidene fluoride)-Based Composites Enabled by SiC@SiO2 Core-Shell Whiskers Alignment.

    Science.gov (United States)

    He, Dalong; Wang, Yao; Song, Silong; Liu, Song; Deng, Yuan

    2017-12-27

    Design of composites with ordered fillers arrangement results in anisotropic performances with greatly enhanced properties along a specific direction, which is a powerful tool to optimize physical properties of composites. Well-aligned core-shell SiC@SiO2 whiskers in poly(vinylidene fluoride) (PVDF) matrix has been achieved via a modified spinning approach. Because of the high aspect ratio of SiC whiskers, strong anisotropy and significant enhancement in dielectric constant were observed with permittivity 854 along the parallel direction versus 71 along the perpendicular direction at 20 vol % SiC@SiO2 loading, while little increase in dielectric loss was found due to the highly insulating SiO2 shell. The anisotropic dielectric behavior of the composite is perfectly understood macroscopically to have originated from anisotropic intensity of interfacial polarization based on an equivalent circuit model of two parallel RC circuits connected in series. Furthermore, finite element simulations on the three-dimensional distribution of local electric field, polarization, and leakage current density in oriented SiC@SiO2/PVDF composites under different applied electrical field directions unambiguously revealed that aligned core-shell SiC@SiO2 whiskers with a high aspect ratio significantly improved dielectric performances. Importantly, the thermal conductivity of the composite was synchronously enhanced over 7 times as compared to that of PVDF matrix along the parallel direction at 20 vol % SiC@SiO2 whiskers loading. This study highlights an effective strategy to achieve excellent comprehensive properties for high-k dielectrics.

  20. Redox-controlled hydrogen bonding: turning a superbase into a strong hydrogen-bond donor.

    Science.gov (United States)

    Wild, Ute; Neuhäuser, Christiane; Wiesner, Sven; Kaifer, Elisabeth; Wadepohl, Hubert; Himmel, Hans-Jörg

    2014-05-12

    Herein the synthesis, structures and properties of hydrogen-bonded aggregates involving redox-active guanidine superbases are reported. Reversible hydrogen bonding is switched on by oxidation of the hydrogen-donor unit, and leads to formation of aggregates in which the hydrogen-bond donor unit is sandwiched by two hydrogen-bond acceptor units. Further oxidation (of the acceptor units) leads again to deaggregation. Aggregate formation is associated with a distinct color change, and the electronic situation could be described as a frozen stage on the way to hydrogen transfer. A further increase in the basicity of the hydrogen-bond acceptor leads to deprotonation reactions. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.