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Sample records for reusable transition metal-free

  1. Transition metal-free decarboxylative alkylation reactions.

    PubMed

    Liu, Ping; Zhang, Guanghui; Sun, Peipei

    2016-11-22

    This review summarizes advances in the decarboxylative alkylation of carboxylic acids and their derivatives under transition metal-free conditions in recent years. Unlike most transition metal-catalyzed decarboxylative coupling reactions which tend to undergo catalytic cycles, the mechanisms of reactions under metal-free conditions are usually diverse and even ambiguous in some cases. This article offers an overview of reaction types and their corresponding mechanisms, highlights some of the advantages and limitations, and focuses on introducing UV and visible light-induced, organocatalyst and peroxide promoted radical processes for decarboxylative alkylation and the formation of C-C bonds.

  2. Transition-metal-free trifluoromethylthiolation of N-heteroarenes.

    PubMed

    Honeker, Roman; Ernst, Johannes B; Glorius, Frank

    2015-05-26

    A general and efficient methodology for the direct transition metal free trifluoromethylthiolation of a broad range of biologically relevant N-heteroarenes is reported employing abundant sodium chloride as the catalyst. This method is operationally simple, exhibits high functional group tolerance, and does not require protecting groups.

  3. Transition metal-free olefin polymerization catalyst

    DOEpatents

    Sen, Ayusman; Wojcinski, II, Louis M.; Liu, Shengsheng

    2001-01-01

    Ethylene and/or propylene are polymerized to form high molecular weight, linear polymers by contacting ethylene and/or propylene monomer, in the presence of an inert reaction medium, with a catalyst system which consists essentially of (1) an aluminum alkyl component, such as trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-octylaluminum and diethylaluminum hydride and (2) a Lewis acid or Lewis acid derivative component, such as B (C.sub.6 F.sub.5).sub.3, [(CH.sub.3).sub.2 N (H) (C.sub.6 H.sub.5)].sup.+ [B (C.sub.6 F.sub.5)4].sup.-, [(C.sub.2 H.sub.5).sub.3 NH].sup.+ [B C.sub.6 F.sub.5).sub.4 ],.sup.-, [C(C.sub.6 F.sub.5).sub.3 ].sup.+ [B(C.sub.6 F.sub.5).sub.4 ].sup.-, (C.sub.2 H.sub.5).sub.2 Al(OCH.sub.3), (C.sub.2 H.sub.5).sub.2 Al(2,6-di-t-butyl-4-methylphenoxide), (C.sub.2 H.sub.5)Al(2,6 -di-t-butylphenoxide).sub.2, (C.sub.2 H.sub.5).sub.2 Al(2,6-di-t-butylphonoxide) , 2,6 -di-t-butylphenol.multidot.methylaluminoxane or an alkylaluminoxane, and which may be completely free any transition metal component(s).

  4. Transition-Metal-Free Biomolecule-Based Flexible Asymmetric Supercapacitors.

    PubMed

    Yang, Yun; Wang, Hua; Hao, Rui; Guo, Lin

    2016-09-01

    A transition-metal-free asymmetric supercapacitor (ASC) is successfully fabricated based on an earth-abundant biomass derived redox-active biomolecule, named lawsone. Such an ASC exhibits comparable or even higher energy densities than most of the recently reported transition-metal-based ASCs, and this green ASC generation from renewable resources is promising for addressing current issues of electronic hazard processing, high cost, and unsustainability.

  5. Transition-metal-free chemo- and regioselective vinylation of azaallyls

    NASA Astrophysics Data System (ADS)

    Li, Minyan; Gutierrez, Osvaldo; Berritt, Simon; Pascual-Escudero, Ana; Yeşilçimen, Ahmet; Yang, Xiaodong; Adrio, Javier; Huang, Georgia; Nakamaru-Ogiso, Eiko; Kozlowski, Marisa C.; Walsh, Patrick J.

    2017-10-01

    Direct C(sp3)-C(sp2) bond formation under transition-metal-free conditions offers an atom-economical, inexpensive and environmentally benign alternative to traditional transition-metal-catalysed cross-coupling reactions. A new chemo- and regioselective coupling protocol between 3-aryl-substituted-1,1-diphenyl-2-azaallyl derivatives and vinyl bromides has been developed. This is the first transition-metal-free cross-coupling of azaallyls with vinyl bromide electrophiles and delivers allylic amines in excellent yields (up to 99%). This relatively simple and mild protocol offers a direct and practical strategy for the synthesis of high-value allylic amine building blocks that does not require the use of transition metals, special initiators or photoredox catalysts. Radical clock experiments, electron paramagnetic resonance studies and density functional theory calculations point to an unprecedented substrate-dependent coupling mechanism. Furthermore, an electron paramagnetic resonance signal was observed when the N-benzyl benzophenone ketimine was subjected to silylamide base, supporting the formation of radical species upon deprotonation. The unique mechanisms outlined herein could pave the way for new approaches to transition-metal-free C-C bond formations.

  6. Transition-Metal-Free Fluoroarylation of Diazoacetamides: A Complementary Approach to 3-Fluorooxindoles.

    PubMed

    Dong, Kuiyong; Yan, Bin; Chang, Sailan; Chi, Yongjian; Qiu, Lihua; Xu, Xinfang

    2016-08-05

    An efficient transition-metal-free fluoroarylation reaction of N-aryl diazoacetamides with NFSI (N-fluorobenzenesulfonimide) is described. This reaction directly provides 3-fluorooxindole derivatives in yields of 67-93% with high selectivity via a carbene-free process under mild reaction conditions.

  7. Transition-metal-free synthesis of phenanthridinones from biaryl-2-oxamic acid under radical conditions.

    PubMed

    Yuan, Ming; Chen, Li; Wang, Junwei; Chen, Shenjie; Wang, Kongchao; Xue, Yongbo; Yao, Guangmin; Luo, Zengwei; Zhang, Yonghui

    2015-01-16

    Na2S2O8-promoted decarboxylative cyclization of biaryl-2-oxamic acid for phenanthridinones has been developed. This work illustrates the first example of intramolecular decarboxylative amidation of unactivated arene under transition-metal-free conditions. Additionally, this approach provides an efficient and economical method to access biologically interesting phenanthridinones, an important structure motif in many natural products.

  8. Transition metal-free one-pot synthesis of nitrogen-containing heterocycles.

    PubMed

    Kumari, Simpal; Kishore, Dharma; Paliwal, Sarvesh; Chauhan, Rajani; Dwivedi, Jaya; Mishra, Aakanksha

    2016-02-01

    One-pot heterocyclic synthesis is an exciting research area as it can open routes for the development of otherwise complex transformations in organic synthesis. Heterocyclic compounds show wide spectrum of applications in medicinal chemistry, chemical biology, and materials science. These heterocycles can be generated very efficiently through highly economical and viable routes using one-pot synthesis. In particular, the metal-free one-pot synthetic protocols are highly fascinating due to several advantages for the industrial production of heterocyclic frameworks. This comprehensive review is devoted to the transition metal-free one-pot synthesis of nitrogen-containing heterocycles from the period 2010-2013.

  9. Transition-Metal-Free Stereospecific Cross-Coupling with Alkenylboronic Acids as Nucleophiles.

    PubMed

    Li, Chengxi; Zhang, Yuanyuan; Sun, Qi; Gu, Tongnian; Peng, Henian; Tang, Wenjun

    2016-08-31

    We herein report a transition-metal-free cross-coupling between secondary alkyl halides/mesylates and aryl/alkenylboronic acid, providing expedited access to a series of nonchiral/chiral coupling products in moderate to good yields. Stereospecific SN2-type coupling is developed for the first time with alkenylboronic acids as pure nucleophiles, offering an attractive alternative to the stereospecific transition-metal-catalyzed C(sp(2))-C(sp(3)) cross-coupling.

  10. Transition-metal-free direct alkylation of aryl tetrazoles via intermolecular oxidative C-N formation.

    PubMed

    Wang, Liang; Zhu, Kaiqiang; Chen, Qun; He, Mingyang

    2014-12-05

    A transition-metal-free synthetic approach for constructing alkylated aryl tetrazoles has been developed using n-Bu4NI as the catalyst and t-BuOOH as the oxidant. It involves the direct C-N bond formation through sp(3) C-H activation. A wide range of benzylic C-H substrates (or alkyl ethers) and aryl tetrazoles undergo this reaction smoothly to deliver the corresponding products in good yields.

  11. Transition-Metal-Free C-3 Arylation of Quinoline-4-ones with Arylhydrazines.

    PubMed

    Ravi, Makthala; Chauhan, Parul; Kant, Ruchir; Shukla, Sanjeev K; Yadav, Prem P

    2015-05-15

    A transition-metal-free C-3-arylation of quinolin-4-ones in the presence of base has been achieved by using arylhydrazines as aryl radical source and air as oxidant. The reaction proceeds smoothly at room temperature and does not require any prefunctionalization and N-protection of quinoline-4-ones. The utility of this methodology is further demonstrated in synthesis of quinoline-quinolone hybrid as well as 6-aryl-benzofuro[3,2-c]quinoline scaffold.

  12. Transition-Metal-Free Decarboxylative Photoredox Coupling of Carboxylic Acids and Alcohols with Aromatic Nitriles.

    PubMed

    Lipp, Benjamin; Nauth, Alexander M; Opatz, Till

    2016-08-05

    A transition-metal-free protocol for the redox-neutral light-induced decarboxylative coupling of carboxylic acids with (hetero)aromatic nitriles at ambient temperature is presented. A broad scope of acids and nitriles is accepted, and alcohols can be coupled in a similar fashion through their oxalate half esters. Various inexpensive sources of UV light and even sunlight can be used to achieve this C-C bond formation proceeding through a free radical mechanism.

  13. Transition-metal-free cascade reaction of α-halo-N-tosylhydrazones, indoles and arylboronic acids.

    PubMed

    Wu, Guojiao; Deng, Yifan; Luo, Haiqing; Zhou, Junliang; Li, Tianjiao; Zhang, Yan; Wang, Jianbo

    2016-04-18

    α-Halo-N-tosylhydrazones are employed as reagents for the formation of multiple carbon-carbon bonds in the three-component reactions. In this transformation, a strategy has been designed to generate the diazo intermediate by using a nucleophile to react with the azoalkene intermediate generated in situ from the α-halo-N-tosylhydrazone. The diazo intermediate thus generated further undergoes transition-metal-free C-C bond forming reaction with arylboronic acids.

  14. A one-pot synthetic strategy for construction of the dibenzodiazepine skeleton via a transition metal-free process.

    PubMed

    Fang, Shuai; Niu, Xiaoyi; Zhang, Zeyuan; Sun, Yan; Si, Xiaomeng; Shan, Cuicui; Wei, Lei; Xu, Aiqing; Feng, Lei; Ma, Chen

    2014-09-21

    A one-pot transition metal-free methodology for constructing pharmacologically active dibenzodiazepine derivatives was developed. Fluoro-, bromo- and nitro-substituted aryl aldehydes were applied to this reaction efficiently.

  15. Transition metal free catalytic hydroboration of aldehydes and aldimines by amidinato silane.

    PubMed

    Bisai, Milan Kumar; Pahar, Sanjukta; Das, Tamal; Vanka, Kumar; Sen, Sakya S

    2017-02-21

    The transition metal free catalytic hydroboration of aldehydes and ketones is very limited and has not been reported with a well-defined silicon(iv) compound. Therefore, we chose to evaluate the previously reported silicon(iv) hydride [PhC(NtBu)2SiHCl2], (1) as a single component catalyst and found that it catalyzes the reductive hydroboration of a range of aldehydes with pinacolborane (HBpin) under ambient conditions. In addition, compound 1 can catalyze imine hydroboration. DFT calculation was carried out to understand the mechanism.

  16. Transition metal-free stereospecific access to (E)-(1-fluoro-2-arylvinyl)phosphine borane complexes.

    PubMed

    Rousée, Kevin; Pannecoucke, Xavier; Gaumont, Annie-Claude; Lohier, Jean-François; Morlet-Savary, Fabrice; Lalevée, Jacques; Bouillon, Jean-Philippe; Couve-Bonnaire, Samuel; Lakhdar, Sami

    2017-02-07

    This work describes the first transition metal-free stereospecific synthesis of (E)-(1-fluoro-2-arylvinyl)phosphine boranes through the addition of diarylphosphine-boranes to gem-bromofluoroalkenes in the presence of a base at room temperature. The reaction proceeds well under very mild conditions and tolerates a variety of functionalities. Scope and limitations of the reaction are discussed. Mechanistic investigations have been undertaken and revealed that the reaction takes place through an SRN1 mechanism. The formation of the fluorinated vinyl radical has been evidenced by electron paramagnetic resonance (EPR) experiment.

  17. Transition Metal-Free C3 Arylation of Indoles with Aryl Halides.

    PubMed

    Chen, Ji; Wu, Jimmy

    2017-03-03

    We report an unprecedented transition metal-free coupling of indoles with aryl halides. The reaction is promoted by KOtBu and is regioselective for C3 over N. The use of degassed solvents devoid of oxygen is necessary for the success of the transformation. Preliminary studies implicate a hybrid mechanism that involves both aryne intermediates and non-propagative radical processes. Electron transfer is also a distinct possibility. These conclusions were substantiated by EPR data, isotopic labeling studies, and the use of radical scavengers and electron transfer inhibitors.

  18. Transition-metal-free synthesis of supramolecular ionic alginate-based polyurethanes.

    PubMed

    Daemi, Hamed; Barikani, Mehdi; Sardon, Haritz

    2017-02-10

    Novel high molecular weight alginate-based supramolecular ionic polyurethane (SPU) networks were prepared via the reaction of chemically modified polyanionic alginate and isocyanate-terminated cationic oligourethanes under transition-metal-free conditions. Alginate, a naturally occurring polyanionic carbohydrate diol possessing carboxylate groups, was considered as both chain extender and the anionic part of SPU network. The tailor-made, ionically crosslinked linear alginate-based SPUs illustrated superior thermal stability with a decomposition temperature around 500°C at 10% weight loss which specializes them as highly thermally stable, wonder materials compared to the today's high-tech products.

  19. Regioselective, Transition Metal-Free C-O Coupling Reactions Involving Aryne Intermediates.

    PubMed

    Dong, Yuyang; Lipschutz, Michael I; Tilley, T Don

    2016-04-01

    A new transition-metal-free synthetic method for C-O coupling between various aryl halides and alkoxides is described. This type of transformation is typically accomplished using palladium catalysts containing a specialized phosphine ligand. The reactions reported here can be performed under mild, ambient conditions using certain potassium alkoxides and a range of aryl halides, with iodide and bromide derivatives giving the best results. A likely mechanistic pathway involves the in situ generation of an aryne intermediate, and directing groups on the aryl ring inductively control regioselectivity.

  20. Transition-Metal-Free ipso-Functionalization of Arylboronic Acids and Derivatives.

    PubMed

    Zhu, Chen; Falck, John R

    2014-08-11

    Arylboronic acids and their derivatives have been widely exploited as important synthetic precursors in organic synthesis, materials science, and pharmaceutical development. In addition to numerous applications in transition-metal-mediated cross-coupling reactions, transition-metal-free transformations involving arylboronic acids and derivatives have recently received a surge of attention for converting the C-B bond to C-C, C-N, C-O, and many other C-X bonds. Consequently, a wide range of useful compounds, e.g., phenols, anilines, nitroarenes, and haloarenes, have been readily synthesized. Amongst these efforts, many versatile reagents have been developed and a lot of practical approaches demonstrated. The research in this promising field is summarized in the current review and organized on the basis of the type of bonds being formed.

  1. Transition-Metal-Free ipso-Functionalization of Arylboronic Acids and Derivatives

    PubMed Central

    Zhu, Chen; Falck, John R.

    2014-01-01

    Arylboronic acids and their derivatives have been widely exploited as important synthetic precursors in organic synthesis, materials science, and pharmaceutical development. In addition to numerous applications in transition-metal-mediated cross-coupling reactions, transition-metal-free transformations involving arylboronic acids and derivatives have recently received a surge of attention for converting the C-B bond to C-C, C-N, C-O, and many other C-X bonds. Consequently, a wide range of useful compounds, e.g., phenols, anilines, nitroarenes, and haloarenes, have been readily synthesized. Amongst these efforts, many versatile reagents have been developed and a lot of practical approaches demonstrated. The research in this promising field is summarized in the current review and organized on the basis of the type of bonds being formed. PMID:25414624

  2. Transition-Metal-Free Synthesis of N-Aryl Hydroxamic Acids via Insertion of Arynes.

    PubMed

    Zhang, Lanlan; Geng, Yu; Jin, Zhong

    2016-05-06

    An efficient and transition-metal-free N-arylation of amides via the insertion of arynes into the N-H bonds in the N-alkoxy amides is described. A variety of the reactive functional groups including the reactive aldehyde carbonyl group, furan ring, carbon-carbon double bonds, and free N-H bond of indole are found to be compatible with this process. In particular, the protocol is applicable in the synthesis of structurally diverse N-aryl hydroxamates and hydroxamic acids derived from N-protecting amino acids and peptides. In the presence of multiple amide N-H bonds, the N-arylation reaction can proceed selectively in the N-H bonds of terminal N-OBn amides giving rise to the desired N-aryl hydroxamates.

  3. Open-Shell Phenalenyl in Transition Metal-Free Catalytic C-H Functionalization.

    PubMed

    Paira, Rupankar; Singh, Bhagat; Hota, Pradip Kumar; Ahmed, Jasimuddin; Sau, Samaresh Chandra; Johnpeter, Justin P; Mandal, Swadhin K

    2016-03-18

    Open-shell phenalenyl chemistry has widely been explored in the last five decades demonstrating its potential in various applications including molecular switch, spin memory device, molecular battery, cathode material, etc. In this article, we have explored another new direction of open-shell phenalenyl chemistry toward transition metal-free catalytic C-H functionalization process. A phenalenyl ligand, namely, 9-methylamino-phenalen-1-one (4a), promoted chelation-assisted single electron transfer (SET) process, which facilitates the C-H functionalization of unactivated arenes to form the biaryl products. The present methodology offers a diverse substrate scope, which can be operated without employing any dry or inert conditions and under truly transition metal based catalyst like loading yet avoiding any expensive or toxic transition metal. This not only is the first report on the application of phenalenyl chemistry in C-H functionalization process but also provides a low-catalyst loading organocatalytic system (up to 0.5 mol % catalyst loading) as compared to the existing ones (mostly 20-40 mol %), which has taken advantage of long known phenalenyl based radical stability through the presence of its low-lying nonbonding molecular orbital.

  4. Direct transformation of methyl imines to α-iminonitriles under mild and transition-metal-free conditions.

    PubMed

    Chen, Feng; Huang, Xiaoqiang; Cui, Yuxin; Jiao, Ning

    2013-08-19

    A novel transformation of methyl imines into α-iminonitriles under mild and transition-metal-free conditions is described. Three C sp 3-H bonds are cleaved in a radical pathway at room temperature under air. Simple bromide salts are employed to assist this radical process (see scheme; FG=functional group, PIDA = iodobenzene diacetate, TMS = trimethylsilyl).

  5. Synthesis of indazoles and azaindazoles by intramolecular aerobic oxidative C-N coupling under transition-metal-free conditions.

    PubMed

    Hu, Jiantao; Xu, Huacheng; Nie, Pengju; Xie, Xiaobo; Nie, Zongxiu; Rao, Yu

    2014-04-01

    A transition-metal-free oxidative C-N coupling method has been developed for the synthesis of 1H-azaindazoles and 1H-indazoles from easily accessible hydrazones. The procedure uses TEMPO, a basic additive, and dioxygen gas as the terminal oxidant. This reaction demonstrates better reactivity, functional group tolerance, and broader scope than comparable metal catalyzed reactions.

  6. Transition metal-free intramolecular regioselective couplings of aliphatic and aromatic C-H bonds

    PubMed Central

    Tian, Hua; Yang, Haijun; Zhu, Changjin; Fu, Hua

    2016-01-01

    Cross-dehydrogenative couplings of two different C-H bonds have emerged as an attractive goal in organic synthesis. However, achieving regioselective C-H activation is a great challenge because C-H bonds are ubiquitous in organic compounds. Actually, the regioselective couplings promoted by enzymes are a common occurrence in nature. Herein, we have developed simple, efficient and general transition metal-free intramolecular couplings of alphatic and aromatic C-H bonds. The protocol uses readily available aryl triazene as the radical initiator, cheap K2S2O8 as the oxidant, and the couplings were performed well with excellent tolerance of functional groups. Interestingly, α-carbon configuration of some amino acid residues in the substrates was kept after the reactions, and the couplings for substrates with substituted phenylalanine residues exhibited complete β-carbon diastereoselectivity for induction of the chiral α-carbon. Therefore, the present study should provide a novel strategy for regioselective cross-dehydrogenative couplings of two different C-H bonds. PMID:26822836

  7. Transition metal-free intramolecular regioselective couplings of aliphatic and aromatic C-H bonds.

    PubMed

    Tian, Hua; Yang, Haijun; Zhu, Changjin; Fu, Hua

    2016-01-29

    Cross-dehydrogenative couplings of two different C-H bonds have emerged as an attractive goal in organic synthesis. However, achieving regioselective C-H activation is a great challenge because C-H bonds are ubiquitous in organic compounds. Actually, the regioselective couplings promoted by enzymes are a common occurrence in nature. Herein, we have developed simple, efficient and general transition metal-free intramolecular couplings of alphatic and aromatic C-H bonds. The protocol uses readily available aryl triazene as the radical initiator, cheap K2S2O8 as the oxidant, and the couplings were performed well with excellent tolerance of functional groups. Interestingly, α-carbon configuration of some amino acid residues in the substrates was kept after the reactions, and the couplings for substrates with substituted phenylalanine residues exhibited complete β-carbon diastereoselectivity for induction of the chiral α-carbon. Therefore, the present study should provide a novel strategy for regioselective cross-dehydrogenative couplings of two different C-H bonds.

  8. Transition-metal-free tandem radical thiocyanooxygenation of olefinic amides: a new route to SCN-containing heterocycles.

    PubMed

    Yang, Hua; Duan, Xin-Hua; Zhao, Jing-Feng; Guo, Li-Na

    2015-04-17

    A novel transition-metal-free tandem radical thiocyanooxygenation of olefinic amides with potassium thiocyanate has been developed under mild conditions. This method allows a reliable and practical access to diverse SCN-containing heterocycles bearing a wide range of functional groups in good to excellent yields. Furthermore, this tandem reaction provides a simple method for the construction of C-O and C-S bonds in one step.

  9. Transition-metal-free BF₃-mediated oxidative and non-oxidative cross-coupling of pyridines.

    PubMed

    Chen, Quan; León, Thierry; Knochel, Paul

    2014-08-11

    We report a BF3-mediated direct alkynylation of pyridines at C(2) by using a variety of alkynyllithium reagents (oxidative cross-coupling). Moreover, we have developed a novel transition-metal-free cross-coupling method between alkylmagnesium reagents and 4-substituted pyridines, such as isonicotinonitrile and 4-chloropyridine, by employing BF3⋅OEt2 as a promoter. The combination of these methods enabled us to efficiently prepare a range of di-, tri-, and tetrasubstituted pyridines.

  10. Transition metal-free generation of N-unsubstituted imines from benzyl azides: synthesis of N-unsubstituted homoallylic amines.

    PubMed

    Pramanik, Suman; Reddy, Reddy Rajasekhar; Ghorai, Prasanta

    2015-04-03

    An efficient transition metal-free approach for the generation of N-unsubstituted imines from azides followed by trapping with allyl nucleophile to provide N-unsubstituted homoallylic amines has been described. Although catalytic KO(t)Bu in DMSO is sufficient to allow imine generation, stoichiometric KO(t)Bu is essential in THF. Further, an enantio- and diastereoselective synthesis of homoallylic amines from benzyl azide has also been exemplified.

  11. Synthesis of quinazolines from 2-aminobenzylamines with benzylamines and N-substituted benzylamines under transition metal-free conditions.

    PubMed

    Tiwari, Abhishek R; Bhanage, Bhalchandra M

    2016-12-07

    This work reports the synthesis of quinazolines from 2-aminobenzylamines with N-substituted benzylamines in the presence of molecular iodine. The developed methodology works smoothly under transition-metal free, additive free and solvent free conditions. The use of O2 as a green oxidant makes it a greatly economical, green and sustainable protocol. Moreover, no aqueous work up is required thereby enhancing the efficiency. A series of quinazoline derivatives were synthesized successfully in good to excellent yields.

  12. Ammonia and hydrazine. Transition-metal-catalyzed hydroamination and metal-free catalyzed functionalization

    SciTech Connect

    Bertrand, Guy

    2012-06-29

    high temperatures and long reaction times. To address this issue, we have developed several new families of carbon- and boron-based ligands, which are even better donors. The corresponding metal complexes (particularly gold, rhodium, iridium, and ruthenium) of all these species will be tested in the Markovnikov and anti-Markovnikov hydroamination of alkynes, allenes, and also alkenes with ammonia and hydrazine. We will also develop metal-free catalytic processes for the functionalization of ammonia and hydrazine. By possessing both a lone pair of electrons and an accessible vacant orbital, singlet carbenes resemble and can mimic the chemical behavior of transition metals. Our preliminary results demonstrate that specially designed carbenes can split the N–H bond of ammonia by an initial nucleophilic activation that prevents the formation of Lewis acid-base adducts, which is the major hurdle for the transition metal catalyzed functionalization of NH3. The use of purely organic compounds as catalysts will eliminate the major drawbacks of transition-metal-catalysis technology, which are the excessive cost of metal complexes (metal + ligands) and in many cases the toxicity of the metal.

  13. Understanding the Kinetics and Spectroscopy of Photoredox Catalysis and Transition-Metal-Free Alternatives.

    PubMed

    Pitre, Spencer P; McTiernan, Christopher D; Scaiano, Juan C

    2016-06-21

    Over the past decade, the field of photoredox catalysis has gained increasing attention in synthetic organic chemistry because of its wide applicability in sustainable free-radical-mediated processes. Numerous examples have shown that under carefully optimized conditions, efficient and highly selective processes can be developed through excitation of a photosensitizer using inexpensive, readily available light sources. However, despite all of these recent advancements, some generalizations and/or misconceptions have become part of the photoredox culture, and often many of these discoveries lack in-depth investigations into the excited-state kinetics and underlying mechanisms. In this Account, we begin with a tutorial for understanding both the redox properties of excited states and how to measure the kinetics of excited-state processes. We discuss the generalization of direct excitation of closed-shell species to generate more potent reductive or oxidative excited states, using the helium atom as a quantitative example. We also outline how to apply redox potentials to calculate whether the proposed electron transfer events are thermodynamically feasible. In the second half of our tutorial, we discuss how to measure the kinetics of excited-state processes using techniques such as steady-state and time-resolved fluorescence and transient spectroscopy and how to apply the data using Stern-Volmer and kinetic analysis. Then we shift gears to discuss our recent contributions to the field of photoredox catalysis. Our lab focuses on developing transition-metal-free alternatives to ruthenium and iridium bipyridyl complexes for these transformations, with the goal of developing systems in which the reaction kinetics is more favorable. We have found that methylene blue, a member of the thiazine dye family, can be employed in photoredox processes such as oxidative hydroxylations of arylboronic acids to phenols. Interestingly, we were able to demonstrate that methylene blue is

  14. Sterically Controlled Cu-Catalyzed or Transition-Metal-Free Cross-Coupling of gem-Difluoroalkenes with Tertiary, Secondary, and Primary Alkyl Grignard Reagents.

    PubMed

    Dai, Wenpeng; Shi, Hongyan; Zhao, Xianghu; Cao, Song

    2016-09-02

    A robust copper-catalyzed or transition-metal-free cross-coupling of gem-difluoroalkenes with tertiary, secondary, and primary alkyl Grignard reagents has been developed. Remarkably, the tertiary and secondary alkylation of gem-difluoroalkenes proceeded very smoothly in the presence of 25 mol % of CuCN or under transition-metal-free conditions, affording the tertiary and secondary alkyl-substituted fluoroalkenes in good to excellent yields with excellent Z stereoselectivity.

  15. Solventless oxidative coupling of amines to imines by using transition-metal-free metal-organic frameworks.

    PubMed

    Qiu, Xuan; Len, Christophe; Luque, Rafael; Li, Yingwei

    2014-06-01

    A highly efficient, simple, and versatile transition-metal-free metal-organic framework catalytic system is proposed for the oxidative coupling of amines to imines. The catalytic protocol features high activities and selectivities to target products; compatibility with a variety of substrates, including aliphatic amines and secondary amines; and the possibility to efficiently and selectively promote amine cross-coupling reactions. A high stability and recyclability of the catalyst is also observed under the investigated conditions. Insights into the reaction mechanism indicate the formation of a superoxide species able to efficiently promote oxidative couplings.

  16. Lactamization of sp(2) C-H Bonds with CO2 : Transition-Metal-Free and Redox-Neutral.

    PubMed

    Zhang, Zhen; Liao, Li-Li; Yan, Si-Shun; Wang, Lei; He, Yun-Qi; Ye, Jian-Heng; Li, Jing; Zhi, Yong-Gang; Yu, Da-Gang

    2016-06-13

    The first direct use of carbon dioxide in the lactamization of alkenyl and heteroaryl C-H bonds to synthesize important 2-quinolinones and polyheterocycles in moderate to excellent yields is reported. Carbon dioxide, a nontoxic, inexpensive, and readily available greenhouse gas, acts as an ideal carbonyl source. Importantly, this transition-metal-free and redox-neutral process is eco-friendly and desirable for the pharmaceutical industry. Moreover, these reactions feature a broad substrate scope, good functional group tolerance, facile scalability, and easy product derivatization.

  17. Transition-Metal-Free CO-Releasing BODIPY Derivatives Activatable by Visible to NIR Light as Promising Bioactive Molecules.

    PubMed

    Palao, Eduardo; Slanina, Tomáš; Muchová, Lucie; Šolomek, Tomáš; Vítek, Libor; Klán, Petr

    2016-01-13

    Carbon monoxide-releasing molecules (CORMs) are chemical agents used to administer CO as an endogenous, biologically active molecule. A precise spatial and temporal control over the CO release is the major requirement for their applications. Here, we report the synthesis and properties of a new generation of transition-metal-free carbon monoxide-releasing molecules based on BODIPY chromophores (COR-BDPs) activatable by visible-to-NIR (up to 730 nm) light. We demonstrate their performance for both in vitro and in vivo experimental settings, and we propose the mechanism of the CO release based on steady-state and transient spectroscopy experiments and quantum chemical calculations.

  18. Transition-Metal-Free Synthesis of N-Hydroxy Oxindoles by an Aza-Nazarov-Type Reaction Involving Azaoxyallyl Cations.

    PubMed

    Ji, Wenzhi; Liu, Yahu A; Liao, Xuebin

    2016-10-10

    A novel transition-metal-free method to construct N-hydroxy oxindoles by an aza-Nazarov-type reaction involving azaoxyallyl cation intermediates is described. A variety of functional groups were tolerated under the weak basic reaction conditions and at room temperature. A one-pot process was also developed to make the reaction even more practical. This method provides alternative access to oxindoles and their biologically active derivatives. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Transition-metal-free C-C bond forming reactions of aryl, alkenyl and alkynylboronic acids and their derivatives.

    PubMed

    Roscales, S; Csákÿ, A G

    2014-12-21

    Investigation of new methods for the synthesis of C-C bonds is fundamental for the development of new organic drugs and materials. Aryl-, alkenyl- and alkynylboronic acids and their derivatives constitute attractive reagents towards this end, due to their stability, low toxicity and ease of handling. However, these compounds are only moderately nucleophilic. Consequently, the most popular C-C bond forming reactions of these boronic acids, such as the Suzuki-Miyaura, Heck, and Hayashi-Miyaura reactions, or additions to C=O and C=N bonds, require catalysis by transition metals. However, due to the toxicity and cost of transition metals, some new methods for C-C bond formation using aryl-, alkenyl- and alkynylboronic acids under transition-metal-free conditions are beginning to emerge. In this tutorial review, the recent synthetic advances in this field are highlighted and discussed.

  20. A radical process towards the development of transition-metal-free aromatic carbon-carbon bond-forming reactions.

    PubMed

    Chan, Tek Long; Wu, Yinuo; Choy, Pui Ying; Kwong, Fuk Yee

    2013-11-18

    Transition-metal-free cross-coupling reactions have been a hot topic in recent years. With the aid of a radical initiator, a number of unactivated arene C-H bonds can be directly arylated/functionalized by using aryl halides through homolytic aromatic substitution. Commercially available or specially designed promoters (e.g. diamines, diols, and amino alcohols) have been used to make this synthetically attractive method viable. This protocol offers an inexpensive, yet efficient route to aromatic C-C bond formations since transition metal catalysts and impurities can be avoided by using this reaction system. In this article, we focus on the significance of the reaction conditions (e.g. bases and promoters), which allow this type of reaction to proceed smoothly. Substrate scope limitations and challenges, as well as mechanistic discussion are also included.

  1. Revisiting the Radical Initiation Mechanism of the Diamine-Promoted Transition-Metal-Free Cross-Coupling Reaction.

    PubMed

    Zhang, Li; Yang, Huan; Jiao, Lei

    2016-06-08

    Radical chain reactions leading to C-C bond formation are widely used in organic synthesis, and initiation of the radical chain process usually requires thermolabile radical initiators. Recent studies on transition-metal-free cross-coupling reactions between aryl halides and arenes have demonstrated an unprecedented initiation system for radical chain reactions, where the combination of simple organic additives and a base was used in place of conventional radical initiators. Among them, the combination of N,N'-dimethylethylenediamine (DMEDA) and t-BuOK is one of the most efficient and representative reaction systems, and the radical initiation mechanism of this system has attracted considerable research interest. In this study, through the combination of kinetic studies, deuterium labeling experiments, and DFT calculations, the radical initiation mechanism of the diamine-promoted cross-coupling reaction was carefully reinvestigated. In light of the present study, a mechanistic network of radical initiation in the DMEDA/t-BuOK system was revealed, which differs dramatically from the previously realized single radical initiation pathway. In this mechanism, the diamine acts as a hydrogen atom donor and plays a dual role as both "radical amplifier" and "radical regulator" to initiate the radical chain process as well as to control the concentration of reactive radical species. This represents a rare example of a structurally simple molecule playing such a subtle role in the radical chain reaction system. The present study sheds some light on the novel radical initiation mode in transition-metal-free cross-coupling reactions following a base-promoted homolytic aromatic substitution (BHAS) mechanism, and may also help to understand the mechanism of relevant reactions.

  2. Peroxide-mediated transition-metal-free direct amidation of alcohols with nitroarenes.

    PubMed

    Xiao, Fuhong; Liu, Yong; Tang, Chenglin; Deng, Guo-Jun

    2012-02-17

    An unusual direct amidation of alcohols with nitroarenes mediated by peroxides has been discovered. The reaction tolerated a wide range of functionalities, and various aromatic amides were obtained in moderate to good yields in the absence of transition-metal catalyst. The peroxides and solvents had a significant impact on the reaction yield.

  3. Regioselective formation of 2,4,5-trisubstituted oxazoles through transition-metal free heterocyclization of 1,3-diynes with N,O-bis(trimethylsiyl)acetamide.

    PubMed

    Zhang, Liang; Zhao, Xiaoming

    2015-01-16

    Transition-metal free heterocyclization reaction of 1,3-diynes with N,O-bis(trimethylsiyl)acetamide was accomplished in the presence of t-BuOK and acetonitrile at 120 °C. This method regioselectively gave 2,4,5-trisubstituted oxazoles in yields up to 97%.

  4. Scalable, transition-metal-free direct oxime O-arylation: rapid access to O-arylhydroxylamines and substituted benzo[b]furans.

    PubMed

    Gao, Hongyin; Xu, Qing-Long; Keene, Craig; Kürti, László

    2014-07-14

    O-aryloximes, generated from readily available and inexpensive oximes through transition-metal-free O-arylation, can either be hydrolyzed to O-arylhydroxylamines or conveniently converted to structurally diverse benzo[b]furans through an environmentally benign, one-pot [3,3]-sigmatropic rearrangement/cyclization sequence.

  5. Transition-metal-free coupling reaction of vinylcyclopropanes with aldehydes catalyzed by tin hydride.

    PubMed

    Ieki, Ryosuke; Kani, Yuria; Tsunoi, Shinji; Shibata, Ikuya

    2015-04-13

    Donor-acceptor cyclopropanes are useful building blocks for catalytic cycloaddition reactions with a range of electrophiles to give various cyclic products. In contrast, relatively few methods are available for the synthesis of homoallylic alcohols through coupling of vinylcyclopropanes (VCPs) with aldehydes, even with transition-metal catalysts. Here, we report that the hydrostannation of vinylcyclopropanes (VCPs) was effectively promoted by dibutyliodotin hydride (Bu2 SnIH). The resultant allylic tin compounds reacted easily with aldehydes. Furthermore, the use of Bu2 SnIH was effectively catalytic in the presence of hydrosilane as a hydride source, which established a coupling reaction of VCPs with aldehydes for the synthesis of homoallylic alcohols without the use of transition-metal catalysts. In contrast to conventional catalytic reactions of VCPs, the presented method allowed the use of several VCPs in addition to conventional donor-acceptor cyclopropanes.

  6. Transition-Metal-Free Synthesis of 2-Substituted Methyl Benzo[b]furan-3-carboxylates.

    PubMed

    Kang, Byungsoo; Lee, Min Hyung; Kim, Mijung; Hwang, Jungwoon; Kim, Hyeong Baik; Chi, Dae Yoon

    2015-08-21

    A concise and highly efficient synthetic pathway was developed for 2-substituted methyl benzo[b]furan-3-carboxylates. This method provides convenient and cost-effective access for 2-substituted methyl benzo[b]furan-3-carboxylates without the use of a transition metal catalyst for synthesis. Furthermore, in most cases, this method gives excellent yields and conventional flash column chromatography is not needed for purification.

  7. Transition metal-free aroylation of NH-sulfoximines with methyl arenes.

    PubMed

    Zou, Ya; Xiao, Jing; Peng, Zhihong; Dong, Wanrong; An, Delie

    2015-10-14

    A novel protocol towards N-aroylated sulfoximines from NH-sulfoximines and methyl arenes was herein demonstrated. The reaction took place in the presence of elemental iodine, requiring no external organic solvents, transition metal-catalysts or ligands. The aroylated products were obtained from the oxidative transformation in moderate to excellent yields (up to 94% yield) with a broad substrate scope (35 examples) through a radical pathway.

  8. Employing Arynes in Diels-Alder Reactions and Transition-Metal-Free Multicomponent Coupling and Arylation Reactions.

    PubMed

    Bhojgude, Sachin Suresh; Bhunia, Anup; Biju, Akkattu T

    2016-09-20

    Arynes are highly reactive intermediates having several applications in organic synthesis for the construction of various ortho-disubstituted arenes. Traditionally, arynes are generated in solution from haloarenes under strongly basic conditions. However, the scopes of many of the aryne reactions are limited because of the harsh conditions used for their generation. The renaissance of interest in aryne chemistry is mainly due to the mild conditions for their generation by the fluoride-induced 1,2-elimination of 2-(trimethylsilyl)aryl triflates. This Account is focused on the Diels-Alder reaction of arynes and their transition-metal-free application in multicomponent couplings as well as arylation reactions. The Diels-Alder reaction of arynes is a powerful tool for constructing benzo-fused carbocycles and heterocycles. In 2012, we developed an efficient, broad-scope, and scalable Diels-Alder reaction of pentafulvenes with arynes affording benzonorbornadiene derivatives. Subsequently, we accomplished the Diels-Alder reaction of arynes with dienes such as 1,2-benzoquinones and tropones. Moreover, we uncovered a transition-metal-free protocol for the synthesis of 9,10-dihydrophenanthrenes by the reaction of arynes with styrenes that proceeds via a Diels-Alder/ene-reaction cascade. In addition, we demonstrated the reaction of arynes with indene/benzofurans, which proceeds via a tandem [4 + 2]/[2 + 2] sequence. Multicomponent coupling (MCC) involving arynes mainly comprises the initial addition of a nucleophile to the aryne followed by interception of the aryl anion intermediate with an electrophile (provided the nucleophilic and electrophilic moieties do not belong to the same molecule). We have disclosed aryne MCCs initiated by N-heterocycles such as (iso)quinoline, pyridine, and aziridines. When (iso)quinoline is used as the nucleophilic trigger and N-substituted isatin as the third component, the reaction affords spirooxazino(iso)quinolines via 1,4-dipolar

  9. Transition-metal-free hydration of nitriles using potassium tert-butoxide under anhydrous conditions.

    PubMed

    Midya, Ganesh Chandra; Kapat, Ajoy; Maiti, Subhadip; Dash, Jyotirmayee

    2015-04-17

    Potassium tert-butoxide acts as a nucleophilic oxygen source during the hydration of nitriles to give the corresponding amides under anhydrous conditions. The reaction proceeds smoothly for a broad range of substrates under mild conditions, providing an efficient and economically affordable synthetic route to the amides in excellent yields. This protocol does not need any transition-metal catalyst or any special experimental setup and is easily scalable to bulk scale synthesis. A single-electron-transfer radical mechanism as well as an ionic mechanism have been proposed for the hydration process.

  10. Transition-metal-free B-B and B-interelement reactions with organic molecules.

    PubMed

    Cuenca, Ana B; Shishido, Ryosuke; Ito, Hajime; Fernández, Elena

    2017-01-23

    This review is a guided tour along the activation modes and reactivity of B-B, B-Si, B-N, B-S, B-Se and B-P reagents, in the absence of any transition metal complex. Here are disclosed the general concepts related to the homolytic and heterolytic cleavage of B-B and B-interelement bonds, as well as the generation of new C-B and C-interelement bonds, in a selective way. The greener consequences of these novel routes facilitate the gram scale preparations of target functionalised organic compounds. Intrinsic data about the suggested mechanisms and spectroscopic evidence that supports the innovative theories are provided along the review. Since this is a stimulating area of work that has emerged within the last decade, this overview serves as the basis to understand the new trends and hopefully to generate inspiration for future discoveries in the field.

  11. Transition-Metal-Free Synthesis of 1,3-Butadiene-Containing π-Conjugated Polymers.

    PubMed

    Cai, Xuediao; Liu, Yating; Lu, Tian; Yang, Rui; Luo, Chuxin; Zhang, Qi; Chai, Yonghai

    2016-12-01

    This work describes the synthesis of π-conjugated polymers possessing arylene and 1,3-butadiene alternating units in the main chain by the reaction of α,β-unsaturated ester/nitrile containing γ-H with aromatic/heteroaromatic aldehyde compound. By using 4-(4-formylphenyl)-2-butylene acid ethyl ester as a model monomer, the different polymerization conditions, including catalyst, catalyst amount, and solvent, are optimized. The polymerization of 4-(4-formylphenyl)-2-butylene acid ethyl ester is carried out by refluxing in ethanol for 72 h with 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) as a catalyst to give a 1,3-butadiene-containing π-conjugated polymer, poly(phenylene-1,3-butadiene), in 84.3% yield with M¯n and M¯w/M¯n (PDI) estimated as 6172 and 1.65, respectively. Based on this new methodology, a series of π-conjugated polymers containing 1,3-butadiene units with different substituents are obtained in high yields. A possible mechanism is proposed for the polymerization through a six-membered ring transition state and then a 1,5-H shift intermediate.

  12. NOx Reduction on a Transition Metal-free γ-Al2O3 Catalyst Using Dimethylether (DME)

    SciTech Connect

    Ozensoy, Emrah; Herling, Darrell R.; Szanyi, Janos

    2008-07-15

    NO2 and dimethylether (DME) adsorption as well as DME and NO2 coadsorption on a transition metal-free γ-alumina catalyst were investigated via in-situ transmission Fourier transform infrared spectroscopy (in-situ FTIR), residual gas analysis (RGA) and temperature programmed desorption (TPD) techniques. NO2 adsorption at room temperature leads to the formation of surface nitrates and nitrites. DME adsorption on the alumina surface at 300 K leads to molecularly adsorbed DME, molecularly adsorbed methanol and surface methoxides. Upon heating the DME-exposed alumina to 500-600 K the surface is dominated by methoxide groups. At higher temperatures methoxide groups are converted into formates. At T > 510 K formate decomposition takes place to form H2O(g) and CO(g). DME and NO2 coadsorption at 423 K do not indicate a significant reaction between DME and NO2. However, in similar experiments at 573 K, fast reaction occurs and the methoxides present at 573 K before the NO2 adsorption are converted into formates, simultaneously with the formation of isocyanates. Under these conditions, NCO can further be hydrolyzed into isocyanic acid or ammonia with the help of water which is generated during the formate formation, decomposition and/or NCO formation steps.

  13. Hydride-induced anionic cyclization: an efficient method for the synthesis of 6-H-phenanthridines via a transition-metal-free process.

    PubMed

    Chen, Wei-Lin; Chen, Chun-Yuan; Chen, Yan-Fu; Hsieh, Jen-Chieh

    2015-03-20

    A novel procedure for hydride-induced anionic cyclization has been developed. It includes the reduction of a biaryl bromo-nitrile with a nucleophilic aromatic substitution (S(N)Ar). A range of polysubstituted 6-H-phenanthridines were so obtained in moderate to good yield with good substrate tolerance. This method involves a concise transition-metal-free process and was applied to synthesize natural alkaloids.

  14. Base-promoted synthesis of coumarins from salicylaldehydes and aryl-substituted 1,1-dibromo-1-alkenes under transition-metal-free conditions.

    PubMed

    Liu, Jianming; Zhang, Xin; Shi, Lijun; Liu, Muwen; Yue, Yuanyuan; Li, Fuwei; Zhuo, Kelei

    2014-09-07

    Facile synthesis of coumarin via the tandem reaction of salicylaldehyde with aryl-substituted 1,1-dibromo-1-alkene was developed. This new protocol proceeds smoothly under mild and transition-metal-free conditions, it allows rapid access to coumarins containing various heteroatoms that are more difficult to prepare by traditional methods. Based on the isolated intermediate of 4-(diethylamino)-3-phenylchroman-2-one and detailed mechanistic studies, a credible tandem pathway was proposed.

  15. Transition-metal-free cross-coupling of thioethers with aryl(cyano)iodonium triflates: a facile and efficient method for the one-pot synthesis of thiocyanates.

    PubMed

    Zhu, Dan; Chang, Denghu; Shi, Lei

    2015-04-28

    A novel transition-metal-free cross-coupling method for the one-step synthesis of thiocyanates via the C-S bond cleavage of readily available thioethers with aryl(cyano)-iodonium triflates as the cyanating agent is developed. This process features relatively broad substrate scopes, less-toxic hypervalent iodine reagents, mild operating conditions, excellent functional group compatibilities, and affords various thiocyanates in moderate to good yields.

  16. Transition-metal-free oxidative carboazidation of acrylamides via cascade C-N and C-C bond-forming reactions.

    PubMed

    Qiu, Jun; Zhang, Ronghua

    2014-07-07

    A novel transition-metal-free oxidative carboazidation of acrylamides using inexpensive NaN3 and K2S2O8 was achieved, which not only provided an efficient method to prepare various N3-substituted oxindoles, but also represented a novel strategy for C-N and C-C bond formation via a free-radical cascade process. This transformation exhibits excellent functional group tolerance, affording the desired oxindoles in good to excellent yields.

  17. Transition metal-free direct C-H functionalization of quinones and naphthoquinones with diaryliodonium salts: synthesis of aryl naphthoquinones as β-secretase inhibitors.

    PubMed

    Wang, Dawei; Ge, Bingyang; Li, Liang; Shan, Jie; Ding, Yuqiang

    2014-09-19

    A novel ligand-free, transition metal-free direct C-H functionalization of quinones with diaryliodonium salts has been developed for the first time. The transformation was promoted only through the use of a base and gave aryl quinone derivatives in moderate to good yields. This methodology provided an effective and easy way to synthesize β-secretase inhibitors. The radical trapping experiments showed that this progress was the radical mechanism.

  18. Transition-Metal-Free Cyclopropanation of 2-Aminoacrylates with N-Tosylhydrazones: A General Route to Cyclopropane α-Amino Acid with Contiguous Quaternary Carbon Centers.

    PubMed

    Zhu, Chuanle; Li, Jiawei; Chen, Pengquan; Wu, Wanqing; Ren, Yanwei; Jiang, Huanfeng

    2016-03-18

    Cyclopropanation of 2-aminoacrylates with N-tosylhydrazones could proceed smoothly under transition-metal-free conditions via a [3 + 2] cycloaddition process. This robust protocol exhibits excellent generality, delivering a wide spectrum of cyclopropane α-amino acid esters bearing contiguous quaternary carbon centers in high yields and diastereoselectivities. With these readily available products, the steric convergence of cyclopropane α-amino acids could be readily obtained.

  19. Aqueous Reaction of Alcohols, Organohalides, and Odorless Sodium Thiosulfate under Transition-Metal-Free Conditions: Synthesis of Unsymmetrical Aryl Sulfides via Dual C-S Bond Formation.

    PubMed

    Liu, Bei-Bei; Chu, Xue-Qiang; Liu, Huan; Yin, Ling; Wang, Shun-Yi; Ji, Shun-Jun

    2017-10-06

    A transition-metal-free process for the synthesis of unsymmetrical aryl sulfides via dual C-S bond formation by a one-pot three-component reaction of alcohols, organohalides, and odorless sodium thiosulfate in water has been developed. In addition, the aryl sulfides could also be prepared by the reaction of the corresponding alcohols and Bunte salts under the identical conditions. This protocol provides a green and efficient manner for the construction of various unsymmetrical aryl sulfides.

  20. Transition-metal-free formal decarboxylative coupling of α-oxocarboxylates with α-bromoketones under neutral conditions: a simple access to 1,3-diketones.

    PubMed

    He, Zhen; Qi, Xiaotian; Li, Shiqing; Zhao, Yinsong; Gao, Ge; Lan, Yu; Wu, Yiwei; Lan, Jingbo; You, Jingsong

    2015-01-12

    A transition-metal-free formal decarboxylative coupling reaction between α-oxocarboxylates and α-bromoketones to synthesize 1,3-diketone derivatives is presented. In this reaction, a broad scope of substrates can be employed, and neither a metal-based reagent nor an additional base is required. DFT calculations reveal that this reaction proceeds through a coupling followed by decarboxylation mechanism and the α-bromoketone unprecedentedly serves as a nucleophile under neutral conditions. The rate-determining step is an unusual hydrogen-bond-assisted enolate formation by thermolysis.

  1. gem-Difluoroolefination of Diazo Compounds with TMSCF3 or TMSCF2Br: Transition-Metal-Free Cross-Coupling of Two Carbene Precursors.

    PubMed

    Hu, Mingyou; Ni, Chuanfa; Li, Lingchun; Han, Yongxin; Hu, Jinbo

    2015-11-18

    A new olefination protocol for transition-metal-free cross-coupling of two carbene fragments arising from two different sources, namely, a nonfluorinated carbene fragment resulting from a diazo compound and a difluorocarbene fragment derived from Ruppert-Prakash reagent (TMSCF3) or TMSCF2Br, has been developed. This gem-difluoroolefination proceeds through the direct nucleophilic addition of diazo compounds to difluorocarbene followed by elimination of N2. Compared to previously reported Cu-catalyzed gem-difluoroolefination of diazo compounds with TMSCF3, which possesses a narrow substrate scope due to a demanding requirement on the reactivity of diazo compounds and in-situ-generated CuCF3, this transition-metal-free protocol affords a general and efficient approach to various disubstituted 1,1-difluoroalkenes, including difluoroacrylates, diaryldifluoroolefins, as well as arylalkyldifluoroolefins. In view of the ready availability of diazo compounds and difluorocarbene reagents and versatile transformations of 1,1-difluoroalkenes, this new gem-difluoroolefination method is expected to find wide applications in organic synthesis.

  2. Beyond Metal-Hydrides: Non-Transition-Metal and Metal-Free Ligand-Centered Electrocatalytic Hydrogen Evolution and Hydrogen Oxidation.

    PubMed

    Haddad, Andrew Z; Garabato, Brady D; Kozlowski, Pawel M; Buchanan, Robert M; Grapperhaus, Craig A

    2016-06-29

    A new pathway for homogeneous electrocatalytic H2 evolution and H2 oxidation has been developed using a redox active thiosemicarbazone and its zinc complex as seminal metal-free and transition-metal-free examples. Diacetyl-bis(N-4-methyl-3-thiosemicarbazone) and zinc diacetyl-bis(N-4-methyl-3-thiosemicarbazide) display the highest reported TOFs of any homogeneous ligand-centered H2 evolution catalyst, 1320 and 1170 s(-1), respectively, while the zinc complex also displays one of the highest reported TOF values for H2 oxidation, 72 s(-1), of any homogeneous catalyst. Catalysis proceeds via ligand-centered proton-transfer and electron-transfer events while avoiding traditional metal-hydride intermediates. The unique mechanism is consistent with electrochemical results and is further supported by density functional theory. The results identify a new direction for the design of electrocatalysts for H2 evolution and H2 oxidation that are not reliant on metal-hydride intermediates.

  3. Stereoselective Csp(3) -Csp(2) Bond-Forming Reactions by Transition-Metal-Free Reductive Coupling of Cyclic Tosylhydrazones with Boronic Acids.

    PubMed

    Plaza, Manuel; Pérez-Aguilar, M Carmen; Valdés, Carlos

    2016-04-25

    The reactions between alkenylboronic acids and tosylhydrazones derived from substituted cyclohexanones lead to the construction of disubstituted cyclohexanes with total regio- and stereoselectivity. In these transition-metal-free processes, a Csp(3) -Csp(2) and Csp(3) -H bond are formed on the same carbon atom. The stereoselective reaction is general for 2-, 3-, and 4-substituted cyclohexanone tosylhydrazones, as well as for 2-substituted cyclopentanones. However, no stereoselectivity is observed for acyclic derivatives. DFT computational modeling suggests that the stereoselectivity of the reaction is determined by the approach of the boronic acid to the diazocyclohexane on its most stable chair conformation through an equatorial trajectory. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Transition Metal-Free Selective Double sp(3) C-H Oxidation of Cyclic Amines to 3-Alkoxyamine Lactams.

    PubMed

    Osorio-Nieto, Urbano; Chamorro-Arenas, Delfino; Quintero, Leticia; Höpfl, Herbert; Sartillo-Piscil, Fernando

    2016-09-16

    The first chemical method for selective dual sp(3) C-H functionalization at the alpha-and beta positions of cyclic amines to their corresponding 3-alkoxyamine lactams is reported. Unlike traditional Cα-H oxidation of amines to amides mediated by transition metals, the present protocol, which involves the use of NaClO2/TEMPO/NaClO in either aqueous or organic solvent, not only allows the Cα-H oxidation but also the subsequent functionalization of the unreactive β-methylene group in an unprecedented tandem fashion and using environmentally friendly reactants.

  5. Transition-Metal-Free Deacylative Cleavage of Unstrained C(sp(3))-C(sp(2)) Bonds: Cyanide-Free Access to Aryl and Aliphatic Nitriles from Ketones and Aldehydes.

    PubMed

    Ge, Jing-Jie; Yao, Chuan-Zhi; Wang, Mei-Mei; Zheng, Hong-Xing; Kang, Yan-Biao; Li, Yadong

    2016-01-15

    A transition-metal-free deacylative C(sp(3))-C(sp(2)) bond cleavage for the synthetically practical oxidative amination of ketones and aldehydes to nitriles is first described, using cheap and commercially abundant NaNO2 as the oxidant and the nitrogen source. Various nitriles bearing aryl, heteroaryl, alkyl, and alkenyl groups could be smoothly obtained from ketones and aldehydes in high yields, avoiding highly toxic cyanides or transition metals.

  6. Chemoselective Coupling of 1,1-Bis[(pinacolato)boryl]alkanes for the Transition-Metal-Free Borylation of Aryl and Vinyl Halides: A Combined Experimental and Theoretical Investigation.

    PubMed

    Lee, Yeosan; Baek, Seung-Yeol; Park, Jinyoung; Kim, Seoung-Tae; Tussupbayev, Samat; Kim, Jeongho; Baik, Mu-Hyun; Cho, Seung Hwan

    2017-01-18

    A new transition-metal-free borylation of aryl and vinyl halides using 1,1-bis[(pinacolato)boryl]alkanes as boron sources is described. In this transformation one of the boron groups from 1,1-bis[(pinacolato)boryl]alkanes is selectively transferred to aryl and vinyl halides in the presence of sodium tert-butoxide as the only activator to form organoboronate esters. Under the developed borylation conditions, a broad range of organohalides are borylated with excellent chemoselectivity and functional group compatibility, thus offering a rare example of a transition-metal-free borylation protocol. Experimental and theoretical studies have been performed to elucidate the reaction mechanism, revealing the unusual formation of Lewis acid/base adduct between organohalides and α-borylcarbanion, generated in situ from the reaction of 1,1-bis[(pinacolato)boryl]alkanes with an alkoxide base, to facilitate the borylation reactions.

  7. Transition metal-free one-pot synthesis of fused 1,4-thiazepin-5(4H)-ones and theoretical study of the S-N type smiles rearrangement process.

    PubMed

    Yang, Bingchuan; Tan, Xiaochen; Guo, Ruiying; Chen, Shunwei; Zhang, Zeyuan; Chu, Xianglong; Xie, Caixia; Zhang, Dongju; Ma, Chen

    2014-09-05

    A series of 1,4-thiazepin-5(4H)-one derivatives were synthesized via a transition metal-free one-pot Smiles rearrangement process at room temperature. Regioselective seven-membered heterocycles were constructed in good to excellent yields. To gain an in-depth understanding of the S-N type Smiles rearrangement mechanism, a theoretical study was also performed by quantum chemistry calculations.

  8. Transition-metal-free synthesis of imidazo[2,1-b]thiazoles and thiazolo[3,2-a]benzimidazoles via an S-propargylation/5-exo-dig cyclization/isomerization sequence using propargyl tosylates as substrates.

    PubMed

    Omar, Mohamed A; Frey, Wolfgang; Conrad, Jürgen; Beifuss, Uwe

    2014-11-07

    A transition-metal-free route for the synthesis of several N-fused heterocycles, including thiazolo[3,2-a]benzimidazoles and imidazo[2,1-b]thiazoles, is reported. The reaction between propargyl tosylates and 2-mercaptobenzimidazoles under basic conditions results in 3-substituted thiazolo[3,2-a]benzimidazoles, in yields up to 92% in a single synthesis step. With 2-mercaptoimidazoles as the substrate, the corresponding imidazo[2,1-b]thiazoles were exclusively obtained. The transformation is considered to proceed as an intermolecular S-propargylation that is followed by 5-exo-dig ring closure and double-bond isomerization.

  9. High-Glass-Transition-Temperature Polyimides Developed for Reusable Launch Vehicle Applications

    NASA Technical Reports Server (NTRS)

    Chuang, Kathy; Ardent, Cory P.

    2002-01-01

    Polyimide composites have been traditionally used for high-temperature applications in aircraft engines at temperatures up to 550 F (288 C) for thousands of hours. However, as NASA shifts its focus toward the development of advanced reusable launch vehicles, there is an urgent need for lightweight polymer composites that can sustain 600 to 800 F (315 to 427 C) for short excursions (hundreds of hours). To meet critical vehicle weight targets, it is essential that one use lightweight, high-temperature polymer matrix composites in propulsion components such as turbopump housings, ducts, engine supports, and struts. Composite materials in reusable launch vehicle components will heat quickly during launch and reentry. Conventional composites, consisting of layers of fabric or fiber-reinforced lamina, would either blister or encounter catastrophic delamination under high heating rates above 300 C. This blistering and delamination are the result of a sudden volume expansion within the composite due to the release of absorbed moisture and gases generated by the degradation of the polymer matrix. Researchers at the NASA Glenn Research Center and the Boeing Company (Long Beach, CA) recently demonstrated a successful approach for preventing this delamination--the use of three-dimensional stitched composites fabricated by resin infusion.

  10. Transition-Metal-Free Diarylannulated Sulfide and Selenide Construction via Radical/Anion-Mediated Sulfur-Iodine and Selenium-Iodine Exchange.

    PubMed

    Wang, Ming; Fan, Qiaoling; Jiang, Xuefeng

    2016-11-04

    A facile, straightforward protocol was established for diarylannulated sulfide and selenide construction through S-I and Se-I exchange without transition metal assistance. Elemental sulfur and selenium served as the chalcogen source. Diarylannulated sulfides were systematically achieved from a five- to eight-membered ring. A trisulfur radical anion was demonstrated as the initiator for this radical process via electron paramagnetic resonance (EPR) study. OFET molecules [1]benzothieno[3,2-b][1]benzothiophene (BTBT) and [1]benzothieno[3,2-b][1]benzoselenophene (BTBS) were efficiently established.

  11. Synthesis of 2-oxindoles via 'transition-metal-free' intramolecular dehydrogenative coupling (IDC) of sp2 C–H and sp3 C–H bonds

    PubMed Central

    Bhunia, Subhajit

    2016-01-01

    Summary The synthesis of a variety of 2-oxindoles bearing an all-carbon quaternary center at the pseudo benzylic position has been achieved via a ‘transition-metal-free’ intramolecular dehydrogenative coupling (IDC). The construction of 2-oxindole moieties was carried out through formation of carbon–carbon bonds using KOt-Bu-catalyzed one pot C-alkylation of β-N-arylamido esters with alkyl halides followed by a dehydrogenative coupling. Experimental evidences indicated toward a radical-mediated path for this reaction. PMID:27559367

  12. Reusable fast opening switch

    DOEpatents

    Van Devender, J.P.; Emin, D.

    1983-12-21

    A reusable fast opening switch for transferring energy, in the form of a high power pulse, from an electromagnetic storage device such as an inductor into a load. The switch is efficient, compact, fast and reusable. The switch comprises a ferromagnetic semiconductor which undergoes a fast transition between conductive and metallic states at a critical temperature and which undergoes the transition without a phase change in its crystal structure. A semiconductor such as europium rich europhous oxide, which undergoes a conductor to insulator transition when it is joule heated from its conductor state, can be used to form the switch.

  13. Reusable fast opening switch

    DOEpatents

    Van Devender, John P.; Emin, David

    1986-01-01

    A reusable fast opening switch for transferring energy, in the form of a high power pulse, from an electromagnetic storage device such as an inductor into a load. The switch is efficient, compact, fast and reusable. The switch comprises a ferromagnetic semiconductor which undergoes a fast transition between conductive and insulating states at a critical temperature and which undergoes the transition without a phase change in its crystal structure. A semiconductor such as europium rich europhous oxide, which undergoes a conductor to insulator transition when it is joule heated from its conductor state, can be used to form the switch.

  14. Reusable Software.

    DTIC Science & Technology

    1984-03-01

    overseeing reusable software, the Reusable Software Organization ( RUSO ). This author does not feel at this time that establishment of such a specific...49] have not been accompanied by establishment of RUSO -like activities. There is need, however, for assurance that functions which a RUSO might be...assurance 6. establishment and maintenance of reuse archival facilities and activities. Actual establishment of a RUSO is best dictated by size of the

  15. Investigation of the Qx -Qy Equilibrium in a Metal-Free Phthalocyanine.

    PubMed

    Baeten, Yannick; Fron, Eduard; Ruzié, Christian; Geerts, Yves Henri; Van Der Auweraer, Mark

    2015-12-21

    Phthalocyanines (Pcs) have attracted a lot of interest as small molecules for organic electronics. However, some excited-state properties of metal-free phthalocyanines, as for example, the dynamics of the transition between the nondegenerate Qx and Qy states in a metal-free phthalocyanine, have not been fully established. This effect results in a blue-shifted shoulder with low intensity in the Pc fluorescence spectrum. This shoulder was suggested to be related to emission from the more energetic Qy state. By using ultrafast femtosecond transient absorption, we have found a clear equilibrium between the Qx and Qy state of metal-free phthalocyanines in solution.

  16. Reusable Software.

    DTIC Science & Technology

    1985-01-01

    demonstration aid aimed at helping Air Traffic Controllers integrate aircraft taking off into the traffic flying out of the United Kingdom airspace. D/DP...AD-A16B 886 REUSABLE SOFTMARE(U) ROYAL SIGNALS AND RADAR t ESTABLISHMENT MALVERN ( ENGLAND ) L N SINCOX ET AL. t985 I RSRE-MEMO-3884 DRIC-BR-99098...official statement by the UK Civil Aviation Authority. Copyright C Controller HMSO London 1985 Work done under contract to the UK Civil Aviation Authority

  17. Carbon-based metal-free catalysts

    NASA Astrophysics Data System (ADS)

    Liu, Xien; Dai, Liming

    2016-11-01

    Metals and metal oxides are widely used as catalysts for materials production, clean energy generation and storage, and many other important industrial processes. However, metal-based catalysts suffer from high cost, low selectivity, poor durability, susceptibility to gas poisoning and have a detrimental environmental impact. In 2009, a new class of catalyst based on earth-abundant carbon materials was discovered as an efficient, low-cost, metal-free alternative to platinum for oxygen reduction in fuel cells. Since then, tremendous progress has been made, and carbon-based metal-free catalysts have been demonstrated to be effective for an increasing number of catalytic processes. This Review provides a critical overview of this rapidly developing field, including the molecular design of efficient carbon-based metal-free catalysts, with special emphasis on heteroatom-doped carbon nanotubes and graphene. We also discuss recent advances in the development of carbon-based metal-free catalysts for clean energy conversion and storage, environmental protection and important industrial production, and outline the key challenges and future opportunities in this exciting field.

  18. Application of a stream-aquifer model to Monument Creek for development of a method to estimate transit losses for reusable water, El Paso County, Colorado

    USGS Publications Warehouse

    Kuhn, Gerhard; Arnold, L. Rick

    2006-01-01

    The U.S. Geological Survey, in cooperation with Colorado Springs Utilities, the Colorado Water Conservation Board, and the El Paso County Water Authority, began a study in 2004 to (1) apply a stream-aquifer model to Monument Creek, (2) use the results of the modeling to develop a transit-loss accounting program for Monument Creek, (3) revise the existing transit-loss accounting program for Fountain Creek to incorporate new water-management strategies and allow for incorporation of future changes in water-management strategies, and (4) integrate the two accounting programs into a single program with a Web-based user interface. The purpose of this report is to present the results of applying a stream-aquifer model to the Monument Creek study reach.Transit losses were estimated for reusable-water flows in Monument Creek that ranged from 1 to 200 cubic feet per second (ft3/s) and for native streamflows that ranged from 0 to 1,000 ft3/s. Transit losses were estimated for bank-storage, channel-storage, and evaporative losses. The same stream-aquifer model used in the previously completed (1988) Fountain Creek study was used in the Monument Creek study.Sixteen model nodes were established for the Monument Creek study reach, defining 15 subreaches. Channel length, aquifer length, and aquifer width for the subreaches were estimated from available topographic and geologic maps. Thickness of alluvial deposits and saturated thickness were estimated using lithologic and water-level data from about 100 wells and test holes in or near the Monument Creek study reach. Estimated average transmissivities for the subreaches ranged from 2,000 to 12,000 feet squared per day, and a uniform value of 0.20 was used for storage coefficient.Qualitative comparison of recorded and simulated streamflow at the downstream node for the calibration and verification simulations indicated that the two streamflows compared reasonably well. No adjustments were made to the model parameters. Differences

  19. Preparation of substituted phenanthridines from the coupling of aryldiazonium salts with nitriles: a metal free approach.

    PubMed

    Ramanathan, Mani; Liu, Shiuh-Tzung

    2015-05-15

    A transition metal free approach for the synthesis of substituted phenanthridines from the coupling reaction of aryldiazonium tetrafluoroborates with nitriles has been developed. This operationally simple protocol proceeds through a substitution of aryldiazonium with nitriles followed by an intramolecular arylation to provide the corresponding phenanthridines in moderate to excellent yields.

  20. Metal-free transfer hydrogenation of olefins via dehydrocoupling catalysis

    PubMed Central

    Pérez, Manuel; Caputo, Christopher B.; Dobrovetsky, Roman; Stephan, Douglas W.

    2014-01-01

    A major advance in main-group chemistry in recent years has been the emergence of the reactivity of main-group species that mimics that of transition metal complexes. In this report, the Lewis acidic phosphonium salt [(C6F5)3PF][B(C6F5)4] 1 is shown to catalyze the dehydrocoupling of silanes with amines, thiols, phenols, and carboxylic acids to form the Si-E bond (E = N, S, O) with the liberation of H2 (21 examples). This catalysis, when performed in the presence of a series of olefins, yields the concurrent formation of the products of dehydrocoupling and transfer hydrogenation of the olefin (30 examples). This reactivity provides a strategy for metal-free catalysis of olefin hydrogenations. The mechanisms for both catalytic reactions are proposed and supported by experiment and density functional theory calculations. PMID:25002489

  1. Reusable Autonomy

    NASA Technical Reports Server (NTRS)

    Truszkowski, Walt; Obenschain, Arthur F. (Technical Monitor)

    2002-01-01

    highlights some of the major issues that need to be addressed when considering the situation where Group A is composed of software-based agents (not their human counterparts) and they migrate from one mission support system to another. This paper will address: - definition of an agent architecture appropriate to support reuse; - identification of non-mission-specific agent capabilities required; - appropriate knowledge representation schemes for mission-specific knowledge; - agent interface with mission-specific knowledge (a type of Learning); development of a fully-operational group of cooperative software agents for ground system support; architecture and operation of a repository of reusable agents that could be the source of intelligent components for realizing an autonomous (or nearly autonomous) agent-based ground system, and an agent-based approach to repository management and operation (an intelligent interface for human use of the repository in a ground-system development activity).

  2. Metal-Free Motifs for Solar Fuel Applications

    NASA Astrophysics Data System (ADS)

    Ilic, Stefan; Zoric, Marija R.; Kadel, Usha Pandey; Huang, Yunjing; Glusac, Ksenija D.

    2017-05-01

    Metal-free motifs, such as graphitic carbon nitride, conjugated polymers, and doped nanostructures, are emerging as a new class of Earth-abundant materials for solar fuel devices. Although these metal-free structures show great potential, detailed mechanistic understanding of their performance remains limited. Here, we review important experimental and theoretical findings relevant to the role of metal-free motifs as either photoelectrodes or electrocatalysts. First, the light-harvesting characteristics of metal-free photoelectrodes (band energetics, exciton binding energies, charge carrier mobilities and lifetimes) are discussed and contrasted with those in traditional inorganic semiconductors (such as Si). Second, the mechanistic insights into the electrocatalytic oxygen reduction and evolution reactions, hydrogen evolution reaction, and carbon dioxide reduction reaction by metal-free motifs are summarized, including experimental surface-sensitive spectroscopy findings, studies on small molecular models, and computational modeling of these chemical transformations.

  3. Reactivity of Metal-Free and Metal-Associated Amyloid-β with Glycosylated Polyphenols and Their Esterified Derivatives.

    PubMed

    Korshavn, Kyle J; Jang, Milim; Kwak, Yeon Ju; Kochi, Akiko; Vertuani, Silvia; Bhunia, Anirban; Manfredini, Stefano; Ramamoorthy, Ayyalusamy; Lim, Mi Hee

    2015-12-10

    Both amyloid-β (Aβ) and transition metal ions are shown to be involved in the pathogenesis of Alzheimer's disease (AD), though the importance of their interactions remains unclear. Multifunctional molecules, which can target metal-free and metal-bound Aβ and modulate their reactivity (e.g., Aβ aggregation), have been developed as chemical tools to investigate their function in AD pathology; however, these compounds generally lack specificity or have undesirable chemical and biological properties, reducing their functionality. We have evaluated whether multiple polyphenolic glycosides and their esterified derivatives can serve as specific, multifunctional probes to better understand AD. The ability of these compounds to interact with metal ions and metal-free/-associated Aβ, and further control both metal-free and metal-induced Aβ aggregation was investigated through gel electrophoresis with Western blotting, transmission electron microscopy, UV-Vis spectroscopy, fluorescence spectroscopy, and NMR spectroscopy. We also examined the cytotoxicity of the compounds and their ability to mitigate the toxicity induced by both metal-free and metal-bound Aβ. Of the polyphenols investigated, the natural product (Verbascoside) and its esterified derivative (VPP) regulate the aggregation and cytotoxicity of metal-free and/or metal-associated Aβ to different extents. Our studies indicate Verbascoside represents a promising structure for further multifunctional tool development against both metal-free Aβ and metal-Aβ.

  4. Reactivity of Metal-Free and Metal-Associated Amyloid-β with Glycosylated Polyphenols and Their Esterified Derivatives

    NASA Astrophysics Data System (ADS)

    Korshavn, Kyle J.; Jang, Milim; Kwak, Yeon Ju; Kochi, Akiko; Vertuani, Silvia; Bhunia, Anirban; Manfredini, Stefano; Ramamoorthy, Ayyalusamy; Lim, Mi Hee

    2015-12-01

    Both amyloid-β (Aβ) and transition metal ions are shown to be involved in the pathogenesis of Alzheimer’s disease (AD), though the importance of their interactions remains unclear. Multifunctional molecules, which can target metal-free and metal-bound Aβ and modulate their reactivity (e.g., Aβ aggregation), have been developed as chemical tools to investigate their function in AD pathology; however, these compounds generally lack specificity or have undesirable chemical and biological properties, reducing their functionality. We have evaluated whether multiple polyphenolic glycosides and their esterified derivatives can serve as specific, multifunctional probes to better understand AD. The ability of these compounds to interact with metal ions and metal-free/-associated Aβ, and further control both metal-free and metal-induced Aβ aggregation was investigated through gel electrophoresis with Western blotting, transmission electron microscopy, UV-Vis spectroscopy, fluorescence spectroscopy, and NMR spectroscopy. We also examined the cytotoxicity of the compounds and their ability to mitigate the toxicity induced by both metal-free and metal-bound Aβ. Of the polyphenols investigated, the natural product (Verbascoside) and its esterified derivative (VPP) regulate the aggregation and cytotoxicity of metal-free and/or metal-associated Aβ to different extents. Our studies indicate Verbascoside represents a promising structure for further multifunctional tool development against both metal-free Aβ and metal-Aβ.

  5. Knowledge-based reusable software synthesis system

    NASA Technical Reports Server (NTRS)

    Donaldson, Cammie

    1989-01-01

    The Eli system, a knowledge-based reusable software synthesis system, is being developed for NASA Langley under a Phase 2 SBIR contract. Named after Eli Whitney, the inventor of interchangeable parts, Eli assists engineers of large-scale software systems in reusing components while they are composing their software specifications or designs. Eli will identify reuse potential, search for components, select component variants, and synthesize components into the developer's specifications. The Eli project began as a Phase 1 SBIR to define a reusable software synthesis methodology that integrates reusabilityinto the top-down development process and to develop an approach for an expert system to promote and accomplish reuse. The objectives of the Eli Phase 2 work are to integrate advanced technologies to automate the development of reusable components within the context of large system developments, to integrate with user development methodologies without significant changes in method or learning of special languages, and to make reuse the easiest operation to perform. Eli will try to address a number of reuse problems including developing software with reusable components, managing reusable components, identifying reusable components, and transitioning reuse technology. Eli is both a library facility for classifying, storing, and retrieving reusable components and a design environment that emphasizes, encourages, and supports reuse.

  6. Transition-metal-free Chemoselective Oxidative C-C Coupling of the sp(3) C-H Bond of Oxindoles with Arenes and Addition to Alkene: Synthesis of 3-Aryl Oxindoles, and Benzofuro- and Indoloindoles.

    PubMed

    Sattar, Moh; Rathore, Vandana; Prasad, Ch Durga; Kumar, Sangit

    2017-04-04

    A transition-metal (TM)-free and halogen-free NaOtBu-mediated oxidative cross-coupling between the sp(3) C-H bond of oxindoles and sp(2) C-H bond of nitroarenes has been developed to access 3-aryl substituted and 3,3-aryldisubstituted oxindoles in DMSO at room temperature in a short time. Interestingly, the sp(3) C-H bond of oxindoles could also react with styrene under TM-free conditions for the practical synthesis of quaternary 3,3-disubstituted oxindoles. The synthesized 3-oxindoles have also been further transformed into advanced heterocycles, that is, benzofuroindoles, indoloindoles, and substituted indoles. Mechanistic experiments of the reaction suggests the formation of an anion intermediate from the sp(3) C-H bond of oxindole by tert-butoxide base in DMSO. The addition of nitrobenzene to the in-situ generated carbanion leads to the 3-(nitrophenyl)oxindolyl carbanion in DMSO which is subsequently oxidized to 3-(nitro-aryl) oxindole by DMSO.

  7. Reusable Software Technology

    NASA Technical Reports Server (NTRS)

    Morgan, Timothy E.

    1995-01-01

    The objective of the Reusable Software System (RSS) is to provide NASA Langley Research Center and its contractor personnel with a reusable software technology through the Internet. The RSS is easily accessible, provides information that is extractable, and the capability to submit information or data for the purpose of scientific research at NASA Langley Research Center within the Atmospheric Science Division.

  8. The Role of Halogen Bonding in Metal Free phosphors

    NASA Astrophysics Data System (ADS)

    Hashemi, Hossein; Jung, Jaehun; Bregman, Avi; Kieffer, John; Kim, Jinsang

    Metal-organic phosphors can achieve theoretical efficiencies four times greater than their fluorescent analogues in Electroluminescence device, but they still have stability issue in case of blue emitting heavy-metal complexes and the price of transition metal like iridium has skyrocketed which discourages commercialization of OLEDs for solid-state lighting. By minimizing radiative loss due to vibrational effects and enhancing spin-orbit coupling via halogen bonding between aldehyde and heavy halide in an organic crystal, efficient room-temperature phosphorescence has been achieved. Therefore, the enhanced spin-orbit coupling necessary for phosphorescence is thought to be due to the halogen bonding that is present in the crystalline form. Here, the electronic and optical properties of purely organic phosphor candidates are explored using density functional theory (DFT), time-dependent density functional theory (TDDFT), GW and BSE methods. These calculations are compared with the absorption, fluorescence, and phosphorescence experimental spectra in their crystals as well as solution forms to elucidate the underlying the role of halogen bonding for phosphorescence mechanism. These results are used to guide future metal-free organic phosphors.

  9. Metal-free syn-dioxygenation of alkenes.

    PubMed

    Rawling, Michael J; Tomkinson, Nicholas C O

    2013-03-07

    Reactions employing inexpensive reagents from sustainable sources and with low toxicity are becoming increasingly desirable from an academic and industrial perspective. A fascinating example of a synthetic transformation that requires development of alternative procedures is the osmium catalysed dihydroxylation. Recently there has been considerable interest in achieving this reaction through metal-free procedures. This review describes the methods available for metal-free syn-dioxygenation of alkenes.

  10. Suppressing molecular motions for enhanced room-temperature phosphorescence of metal-free organic materials

    PubMed Central

    Kwon, Min Sang; Yu, Youngchang; Coburn, Caleb; Phillips, Andrew W.; Chung, Kyeongwoon; Shanker, Apoorv; Jung, Jaehun; Kim, Gunho; Pipe, Kevin; Forrest, Stephen R.; Youk, Ji Ho; Gierschner, Johannes; Kim, Jinsang

    2015-01-01

    Metal-free organic phosphorescent materials are attractive alternatives to the predominantly used organometallic phosphors but are generally dimmer and are relatively rare, as, without heavy-metal atoms, spin–orbit coupling is less efficient and phosphorescence usually cannot compete with radiationless relaxation processes. Here we present a general design rule and a method to effectively reduce radiationless transitions and hence greatly enhance phosphorescence efficiency of metal-free organic materials in a variety of amorphous polymer matrices, based on the restriction of molecular motions in the proximity of embedded phosphors. Covalent cross-linking between phosphors and polymer matrices via Diels–Alder click chemistry is devised as a method. A sharp increase in phosphorescence quantum efficiency is observed in a variety of polymer matrices with this method, which is ca. two to five times higher than that of phosphor-doped polymer systems having no such covalent linkage. PMID:26626796

  11. Suppressing molecular motions for enhanced room-temperature phosphorescence of metal-free organic materials

    NASA Astrophysics Data System (ADS)

    Kwon, Min Sang; Yu, Youngchang; Coburn, Caleb; Phillips, Andrew W.; Chung, Kyeongwoon; Shanker, Apoorv; Jung, Jaehun; Kim, Gunho; Pipe, Kevin; Forrest, Stephen R.; Youk, Ji Ho; Gierschner, Johannes; Kim, Jinsang

    2015-12-01

    Metal-free organic phosphorescent materials are attractive alternatives to the predominantly used organometallic phosphors but are generally dimmer and are relatively rare, as, without heavy-metal atoms, spin-orbit coupling is less efficient and phosphorescence usually cannot compete with radiationless relaxation processes. Here we present a general design rule and a method to effectively reduce radiationless transitions and hence greatly enhance phosphorescence efficiency of metal-free organic materials in a variety of amorphous polymer matrices, based on the restriction of molecular motions in the proximity of embedded phosphors. Covalent cross-linking between phosphors and polymer matrices via Diels-Alder click chemistry is devised as a method. A sharp increase in phosphorescence quantum efficiency is observed in a variety of polymer matrices with this method, which is ca. two to five times higher than that of phosphor-doped polymer systems having no such covalent linkage.

  12. Peroxide promoted tunable decarboxylative alkylation of cinnamic acids to form alkenes or ketones under metal-free conditions.

    PubMed

    Ji, Jing; Liu, Ping; Sun, Peipei

    2015-05-01

    A tunable decarboxylative alkylation of cinnamic acids with alkanes was developed to form alkenes or ketones under transition metal-free conditions. In the presence of DTBP or DTBP/TBHP, the reaction gave alkenes and ketones respectively via a radical mechanism in moderate to good yields.

  13. First-principles prediction of metal-free magnetism and intrinsic half-metallicity in graphitic carbon nitride.

    PubMed

    Du, Aijun; Sanvito, Stefano; Smith, Sean C

    2012-05-11

    Transition metal-free magnetism and half-metallicity recently has been the subject of intense research activity due to its potential in spintronics application. Here we, for the first time, demonstrate via density functional theory that the most recently experimentally realized graphitic carbon nitride (g-C4N3) displays a ferromagnetic ground state. Furthermore, this novel material is predicted to possess an intrinsic half-metallicity never reported to date. Our results highlight a new promising material toward realistic metal-free spintronics application.

  14. Charge and Energy Transfer in the Metal-free Indoline Dyes for Dye-sensitized Solar Cells

    NASA Astrophysics Data System (ADS)

    Diao, Li-ying; Gu, Wen-xiang; Chen, Yue-hui; Ma, Feng-cai

    2006-06-01

    Metal-free indoline dyes for dye-sensitized solar cells were studied by employing quantum chemistry methods. Comparative study of the properties of both ground and excited states of metal-free indoline dyes for dye- sensitized solar cells revealed: (i) as the number of rhodanine rings increases, the energy difference between HOMO and LUMO decreases and there is a red shift in the absorption spectrum with the binding energy increased, and the transition dipole moment decreased; (ii) Based on an analysis of charge differential density, we observed that the charge and energy are transfered from the phenylethenyl to the indoline and rhodanine rings; (iii) The electron-hole coherences are mainly on the indoline and rhodanine rings, and the exciton sizes are 30 and 40 atoms for indoline dyes with one and two rhodanline rings, respectively. These results serve as a good example of computer-aided design in metal-free indoline dyes for dye-sensitized solar cells.

  15. Reusable Component Services

    EPA Pesticide Factsheets

    The Reusable Component Services (RCS) is a super-catalog of components, services, solutions and technologies that facilitates search, discovery and collaboration in order to promote quality and savings in software development through sharing and re-use

  16. Reusable Mechanical Pin Puller

    NASA Technical Reports Server (NTRS)

    Ngo, Son; Farley, Rodger; Devine, ED

    1991-01-01

    Reusable mechanical pin puller relatively simple spring-loaded trigger mechanism. Designed to save money and increase safety as substitute for costly and potentially dangerous pyrotechnic pin pullers used in development and testing of deployment mechanisms.

  17. Reusable Mechanical Pin Puller

    NASA Technical Reports Server (NTRS)

    Ngo, Son; Farley, Rodger; Devine, ED

    1991-01-01

    Reusable mechanical pin puller relatively simple spring-loaded trigger mechanism. Designed to save money and increase safety as substitute for costly and potentially dangerous pyrotechnic pin pullers used in development and testing of deployment mechanisms.

  18. PARTS: (Plasma Accelerated Reusable Transport System)

    NASA Astrophysics Data System (ADS)

    Aherne, Michael; Davis, Phil; England, Matt; Gustavsson, Jake; Pankow, Steve; Sampaio, Chere; Savella, Phil

    2002-01-01

    The Plasma Accelerated Reusable Transport System (PARTS) is an unmanned cargo shuttle intended to ferry large payloads to and from Martian orbit using a highly efficient VAriable Specific Impulse Magnetoplasma Rocket (VASIMR). The design of PARTS focuses on balancing cost and minimizing transit time for a chosen payload consisting of vehicles, satellites, and other components provided by interested parties.

  19. Metal-Free Atom Transfer Radical Polymerization of Methyl Methacrylate with ppm Level of Organic Photocatalyst.

    PubMed

    Huang, Zhicheng; Gu, Yu; Liu, Xiaodong; Zhang, Lifen; Cheng, Zhenping; Zhu, Xiulin

    2016-10-28

    It is well known that the recently developed photoinduced metal-free atom transfer radical polymerization (ATRP) has been considered as a promising methodology to completely eliminate transition metal residue in polymers. However, a serious problem needs to be improved, namely, large amount of organic photocatalysts should be used to keep the controllability over molecular weights and molecular weight distributions. In this work, a novel photocatalyst 1,2,3,5-tetrakis(carbazol-9-yl)-4,6-dicyanobenzene (4CzIPN) with strong excited state reduction potential is successfully used to mediate a metal-free ATRP of methyl methacrylate just with parts per million (ppm) level usage under irradiation of blue light emitting diode at room temperature, using ethyl α-bromophenyl-acetate as a typical initiator with high initiator efficiency. The polymerization kinetic study, multiple controlled "on-off" light switching cycle regulation, and chain extension experiment confirm the "living"/controlled features of this promising photoinduced metal-free ATRP system with good molecular weight control in the presence of ppm level photocatalyst 4CzIPN.

  20. Reusable Security Requirements

    DTIC Science & Technology

    2016-06-13

    2003 by Carnegie Mellon University page 1 Carnegie Mellon Software Engineering Institute Reusable Security Requirements RE’2003 RHAS’03 Workshop...12 September 2003 Donald Firesmith Acquisition Improvement Team Acquisition Support Program Software Engineering Institute (SEI) Carnegie Mellon...PERFORMING ORGANIZATION NAME(S) AND ADDRESS(ES) Carnegie Mellon University, Software Engineering Institute,Pittsburgh,PA,15213 8. PERFORMING

  1. Reusable Release Mechanism

    NASA Technical Reports Server (NTRS)

    Bunker, J. W.; Ritchie, R. S.

    1984-01-01

    Slider release mechanism reusable. Bears heavy loads while latched, yet gives smooth release motion. Release effected by explosively driving perpendicular slider out of engagement with load-bearing shank. Device has potential industrial applications such as emergency release of lifting cables from helicopters, cranes and hoists.

  2. REUSABLE REACTION VESSEL

    DOEpatents

    Soine, T.S.

    1963-02-26

    This patent shows a reusable reaction vessel for such high temperature reactions as the reduction of actinide metal chlorides by calcium metal. The vessel consists of an outer metal shell, an inner container of refractory material such as sintered magnesia, and between these, a bed of loose refractory material impregnated with thermally conductive inorganic salts. (AEC)

  3. Metal-free heterogeneous catalysis for sustainable chemistry.

    PubMed

    Su, Dang Sheng; Zhang, Jian; Frank, Benjamin; Thomas, Arne; Wang, Xinchen; Paraknowitsch, Jens; Schlögl, Robert

    2010-02-22

    The current established catalytic processes used in chemical industries use metals, in many cases precious metals, or metal oxides as catalysts. These are often energy-consuming and not highly selective, wasting resources and producing greenhouse gases. Metal-free heterogeneous catalysis using carbon or carbon nitride is an interesting alternative to some current industrialized chemical processes. Carbon and carbon nitride combine environmental acceptability with inexhaustible resources and allow a favorable management of energy with good thermal conductivity. Owing to lower reaction temperatures and increased selectivity, these catalysts could be candidates for green chemistry with low emission and an efficient use of the chemical feedstock. This Review highlights some recent promising activities and developments in heterogeneous catalysis using only carbon and carbon nitride as catalysts. The state-of-the-art and future challenges of metal-free heterogeneous catalysis are also discussed.

  4. Noble-metal-free plasmonic photocatalyst: hydrogen doped semiconductors

    PubMed Central

    Ma, Xiangchao; Dai, Ying; Yu, Lin; Huang, Baibiao

    2014-01-01

    The unique capacity of localized surface plasmon resonance (LSPR) offers a new opportunity to overcome the limited efficiency of semiconductor photocatalyst. Here we unravel that LSPR, which usually occurs in noble metal nanoparticles, can be realized by hydrogen doping in noble-metal-free semiconductor using TiO2 as a model photocatalyst. Moreover, its LSPR is located in infrared region, which supplements that of noble metal whose LSPR is generally in the visible region, making it possible to extend the light response of photocatalyst to infrared region. The near field enhancement is shown to be comparable with that of noble-metal nanoparticles, indicating that highly enhanced light absorption rate can be expected. The present work can provide a key guideline for the creation of highly efficient noble-metal-free plasmonic photocatalysts and have a much wider impact in infrared bioimaging and spectroscopy where infrared LSPR is essential. PMID:24496400

  5. Metal-Free Carbon Materials for CO2 Electrochemical Reduction.

    PubMed

    Duan, Xiaochuan; Xu, Jiantie; Wei, Zengxi; Ma, Jianmin; Guo, Shaojun; Wang, Shuangyin; Liu, Huakun; Dou, Shixue

    2017-09-11

    The rapid increase of the CO2 concentration in the Earth's atmosphere has resulted in numerous environmental issues, such as global warming, ocean acidification, melting of the polar ice, rising sea level, and extinction of species. To search for suitable and capable catalytic systems for CO2 conversion, electrochemical reduction of CO2 (CO2 RR) holds great promise. Emerging heterogeneous carbon materials have been considered as promising metal-free electrocatalysts for the CO2 RR, owing to their abundant natural resources, tailorable porous structures, resistance to acids and bases, high-temperature stability, and environmental friendliness. They exhibit remarkable CO2 RR properties, including catalytic activity, long durability, and high selectivity. Here, various carbon materials (e.g., carbon fibers, carbon nanotubes, graphene, diamond, nanoporous carbon, and graphene dots) with heteroatom doping (e.g., N, S, and B) that can be used as metal-free catalysts for the CO2 RR are highlighted. Recent advances regarding the identification of active sites for the CO2 RR and the pathway of reduction of CO2 to the final product are comprehensively reviewed. Additionally, the emerging challenges and some perspectives on the development of heteroatom-doped carbon materials as metal-free electrocatalysts for the CO2 RR are included. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Flexible reusable mandrels

    NASA Technical Reports Server (NTRS)

    Willden, Kurtis S. (Inventor)

    1995-01-01

    A reusable laminate mandrel which is unaffected by extreme temperature changes. The flexible laminate mandrel is comprised of sheets stacked to produce the required configuration, a cover wrap that applies pressure to the mandrel laminate, maintaining the stack cross-section. Then after use, the mandrels can be removed, disassembled, and reused. In the method of extracting the flexible mandrel from one end of a composite stiffener, individual ones of the laminae of the flexible mandrel or all are extracted at the same time, depending on severity of the contour.

  7. Noble metal-free hydrogen evolution catalysts for water splitting.

    PubMed

    Zou, Xiaoxin; Zhang, Yu

    2015-08-07

    Sustainable hydrogen production is an essential prerequisite of a future hydrogen economy. Water electrolysis driven by renewable resource-derived electricity and direct solar-to-hydrogen conversion based on photochemical and photoelectrochemical water splitting are promising pathways for sustainable hydrogen production. All these techniques require, among many things, highly active noble metal-free hydrogen evolution catalysts to make the water splitting process more energy-efficient and economical. In this review, we highlight the recent research efforts toward the synthesis of noble metal-free electrocatalysts, especially at the nanoscale, and their catalytic properties for the hydrogen evolution reaction (HER). We review several important kinds of heterogeneous non-precious metal electrocatalysts, including metal sulfides, metal selenides, metal carbides, metal nitrides, metal phosphides, and heteroatom-doped nanocarbons. In the discussion, emphasis is given to the synthetic methods of these HER electrocatalysts, the strategies of performance improvement, and the structure/composition-catalytic activity relationship. We also summarize some important examples showing that non-Pt HER electrocatalysts could serve as efficient cocatalysts for promoting direct solar-to-hydrogen conversion in both photochemical and photoelectrochemical water splitting systems, when combined with suitable semiconductor photocatalysts.

  8. Metal-free carbonaceous electrocatalysts and photocatalysts for water splitting.

    PubMed

    Xu, You; Kraft, Markus; Xu, Rong

    2016-05-31

    Water splitting driven by sunlight or renewable resource-derived electricity has attracted great attention for sustainable production of hydrogen from water. Current research interest in this field is focused on the development of earth-abundant photo- or electrocatalytic materials with high activity and long-term stability for hydrogen and/or oxygen evolution reactions. Due to their unique properties and characteristics, carbon and related carbon-based materials show great potential to replace some of the existing precious metal catalysts in water splitting technology. This tutorial review summarizes the recent significant progress in the fabrication and application of metal-free carbonaceous materials as photo- or electrocatalysts for water splitting. Synthetic strategies and applications of various carbonaceous materials, including graphitic carbon nitride (g-C3N4), graphene, carbon nanotubes (CNTs) as well as other forms of carbon-containing materials, for electrochemical or photochemical water splitting are presented, accompanied by a discussion of the key scientific issues and prospects for the future development of metal-free photo- and electrocatalysts.

  9. Application of a stream-aquifer model to Monument Creek for development of a method to estimate transit losses for reusable water, El Paso County, Colorado

    USGS Publications Warehouse

    Kuhn, Gerhard; Arnold, L. Rick

    2006-01-01

    The U.S. Geological Survey, in cooperation with Colorado Springs Utilities, the Colorado Water Conservation Board, and the El Paso County Water Authority, began a study in 2004 to (1) apply a stream-aquifer model to Monument Creek, (2) use the results of the modeling to develop a transit-loss accounting program for Monument Creek, (3) revise the existing transit-loss accounting program for Fountain Creek to incorporate new water-management strategies and allow for incorporation of future changes in water-management strategies, and (4) integrate the two accounting programs into a single program with a Web-based user interface. The purpose of this report is to present the results of applying a stream-aquifer model to the Monument Creek study reach. More...

  10. Reusable Surface Insulation

    NASA Technical Reports Server (NTRS)

    1997-01-01

    Advanced Flexible Reusable Surface Insulation, developed by Ames Research Center, protects the Space Shuttle from the searing heat that engulfs it on reentry into the Earth's atmosphere. Initially integrated into the Space Shuttle by Rockwell International, production was transferred to Hi-Temp Insulation Inc. in 1974. Over the years, Hi-Temp has created many new technologies to meet the requirements of the Space Shuttle program. This expertise is also used commercially, including insulation blankets to cover aircrafts parts, fire barrier material to protect aircraft engine cowlings and aircraft rescue fire fighter suits. A Fire Protection Division has also been established, offering the first suit designed exclusively by and for aircraft rescue fire fighters. Hi-Temp is a supplier to the Los Angeles City Fire Department as well as other major U.S. civil and military fire departments.

  11. A computational experiment to study hydrogenations of various unsaturated compounds catalyzed by a rationally designed metal-free catalyst.

    PubMed

    Zhao, Lili; Lu, Gang; Huang, Fang; Wang, Zhi-Xiang

    2012-04-21

    Metal-free hydrogenation has been proposed to be a green alternative to the conventional hydrogenation mediated by precious transition metal complexes. Thanks to the discovery of FLP (frustrated Lewis pair) chemistry, the field has recently witnessed significant progress. Inspired by the FLP idea of synergically utilizing the catalytic effects of Lewis acid and base, we previously proposed a strategy to construct metal-free active sites for H(2) activation and designed a metal-free molecule (1) that shows high reactivity toward H(2). Encouraged by the recent experimental successes in applying the strategy, we have computationally explored if 1 can go further to serve as a catalyst to promote the hydrogenations of various unsaturated compounds examined by ethylene (CH(2)=CH(2) (4)), silyl enol ether (CH(2)=C(Me)OSiMe(3) (5)), imines (Me(2)C=NMe (6) and Ph(Me)C=NMe (7)), and ketone (Ph(Me)C=O (9)). The energetic results predicted at the M05-2X(IEFPCM, solvent = THF)/6-311++G** level indicate that these reactions have feasible kinetics and thermodynamics for experimental realization. The hydride transfer step follows the concerted mechanism, although the transfer process has asynchronous character for silyl enol ether (5) and imines (6 and 7). In addition, we have investigated the binding of CO(2) to 1 and the 1-mediated hydrogenation of CO(2).

  12. Reusable State Machine Code Generator

    NASA Astrophysics Data System (ADS)

    Hoffstadt, A. A.; Reyes, C.; Sommer, H.; Andolfato, L.

    2010-12-01

    The State Machine model is frequently used to represent the behaviour of a system, allowing one to express and execute this behaviour in a deterministic way. A graphical representation such as a UML State Chart diagram tames the complexity of the system, thus facilitating changes to the model and communication between developers and domain experts. We present a reusable state machine code generator, developed by the Universidad Técnica Federico Santa María and the European Southern Observatory. The generator itself is based on the open source project architecture, and uses UML State Chart models as input. This allows for a modular design and a clean separation between generator and generated code. The generated state machine code has well-defined interfaces that are independent of the implementation artefacts such as the middle-ware. This allows using the generator in the substantially different observatory software of the Atacama Large Millimeter Array and the ESO Very Large Telescope. A project-specific mapping layer for event and transition notification connects the state machine code to its environment, which can be the Common Software of these projects, or any other project. This approach even allows to automatically create tests for a generated state machine, using techniques from software testing, such as path-coverage.

  13. Hydrogen evolution by a metal-free electrocatalyst.

    PubMed

    Zheng, Yao; Jiao, Yan; Zhu, Yihan; Li, Lu Hua; Han, Yu; Chen, Ying; Du, Aijun; Jaroniec, Mietek; Qiao, Shi Zhang

    2014-04-28

    Electrocatalytic reduction of water to molecular hydrogen via the hydrogen evolution reaction may provide a sustainable energy supply for the future, but its commercial application is hampered by the use of precious platinum catalysts. All alternatives to platinum thus far are based on nonprecious metals, and, to our knowledge, there is no report about a catalyst for electrocatalytic hydrogen evolution beyond metals. Here we couple graphitic-carbon nitride with nitrogen-doped graphene to produce a metal-free hybrid catalyst, which shows an unexpected hydrogen evolution reaction activity with comparable overpotential and Tafel slope to some of well-developed metallic catalysts. Experimental observations in combination with density functional theory calculations reveal that its unusual electrocatalytic properties originate from an intrinsic chemical and electronic coupling that synergistically promotes the proton adsorption and reduction kinetics.

  14. Nonlinear Optothermal Properties of Metal-Free Phthalocyanine

    NASA Technical Reports Server (NTRS)

    Abdeldayem, Hossin A.; Frazier, Donald O.; Penn, Benjamin G.; Smith, David D.; Banks, Curtis E.

    1998-01-01

    The nonlinear optical properties of metal-free phthalocyanine (MFPC) thin films were examined using the second harmonic at 532 nm from a pulsed Nd:YAG laser, and the cw He-Ne , and Ar+ lasers. The He-Ne laser transmission at fixed input intensity was found to increase temporally within a time scale of twelve hours. The origin of this temporal change of transmission is discussed. The third order nonlinear susceptibilities (chi (exp(3))) by four-wave mixing were measured for films of different thickness. The saturation intensity of MFPC, and its absorption cross section, at 633 nm from a He-Ne laser, are reported. An optical bistability was recorded using a He-Ne laser. An AND logic gate was also demonstrated in the system. These phenomena in the system are attributed to refractive index modulation by thermal excitations.

  15. A Metal-Free, Nonconjugated Polymer for Solar Photocatalysis.

    PubMed

    Irigoyen-Campuzano, Rafael; González-Béjar, María; Pino, Eduardo; Proal-Nájera, Jose B; Pérez-Prieto, Julia

    2017-02-24

    Heterogeneous catalysts that can absorb light over the solar range are ideal for green photocatalysis. Recently, attention has been directed towards the generation of novel solar-light photocatalysts, in particular, metal-free polymers. Herein, it is demonstrated that a metal-free, nonconjugated, anthraquinone-based copolymer (poly[1,4-diamine-9,10-dioxoanthracene-alt-(benzene-1,4-dioic acid)] (COP)) with a strong absorption in the visible region is effective as a sunlight heterogeneous photocatalyst. As a proof of concept, it has been used to mineralize 2,5-dichlorophenol (2,5-DCP) in water under air and sunlight irradiation. The photocatalytic efficiency of COP compares well with that of TiO2 -P25 when the reaction is carried out in a solar photoreactor in acid medium. Steady-state and time-resolved (absorption and emission) studies performed on COP suspended in 6:4 DMF/H2 O have provided valuable information about the COP species generated under different pH conditions. Steady-state absorption and fluorescence data are consistent with the existence of a tautomeric equilibrium between the 9,10-keto and 1,10-iminoketo quinoid forms for the anthraquinone in the ground state. Moreover, in basic media, transient absorption measurements showed the presence of two bands ascribed to the tautomeric triplet excited states, whereas only one of the triplets was observed in acid medium. A mechanism for the photocatalyzed degradation of 2,5-DCP by COP is proposed on the basis of these observations. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Reusable Launch Vehicle Technology Program

    NASA Technical Reports Server (NTRS)

    Freeman, Delma C., Jr.; Talay, Theodore A.; Austin, R. Eugene

    1996-01-01

    Industry/NASA Reusable Launch Vehicle (RLV) Technology Program efforts are underway to design, test, and develop technologies and concepts for viable commercial launch systems that also satisfy national needs at acceptable recurring costs. Significant progress has been made in understanding the technical challenges of fully reusable launch systems and the accompanying management and operational approaches for achieving a low-cost program. This paper reviews the current status of the Reusable Launch Vehicle Technology Program including the DC-XA, X-33 and X-34 flight systems and associated technology programs. It addresses the specific technologies being tested that address the technical and operability challenges of reusable launch systems including reusable cryogenic propellant tanks, composite structures, thermal protection systems, improved propulsion, and subsystem operability enhancements. The recently concluded DC-XA test program demonstrated some of these technologies in ground and flight tests. Contracts were awarded recently for both the X-33 and X-34 flight demonstrator systems. The Orbital Sciences Corporation X-34 flight test vehicle will demonstrate an air-launched reusable vehicle capable of flight to speeds of Mach 8. The Lockheed-Martin X-33 flight test vehicle will expand the test envelope for critical technologies to flight speeds of Mach 15. A propulsion program to test the X-33 linear aerospike rocket engine using a NASA SR-71 high speed aircraft as a test bed is also discussed. The paper also describes the management and operational approaches that address the challenge of new cost-effective, reusable launch vehicle systems.

  17. An SSE approach to reusability

    NASA Technical Reports Server (NTRS)

    Badal, David L.

    1989-01-01

    The SSE project has engineering analysis and design efforts under way for the development of the SSE reusability library management system. An ad hoc committee on reuse has been meeting for several months identifying design considerations and learning about Ruben Prieto-Diaz faceted classification, CAMP domain analysis, SPC activities, SEI activities, and SPS activities. A standard format was developed for the Ada prologue for reusable components (both specification and body). The SSE reusability process can be viewed as a transformation process with minimized losses and difficulties.

  18. Reusable captive blind fastener

    NASA Technical Reports Server (NTRS)

    Peterson, S. A. (Inventor)

    1981-01-01

    A one piece reusable fastener capable of joining materials together from one side (blind backside) comprises a screw driven pin ending in a wedge-shaped expander cone. The cone cooperates within a slotted collar end which has a number of tangs on a cylindrical body. The fastener is set by inserting it through aligned holes in the workpieces to be joined. Turning the pin in one direction draws the cone into the collar, deforming the tangs radially outward to mate with tapered back-tapered hold in the workpiece, thus fastening the two pieces together. Reversing the direction of the pin withdraws the cone from the collar, and allows the tangs to resume their contracted configuration without withdrawing the fastener from the insertion hole. The fastener is capable of joining materials together from only one side with substantial strength in tension and shear over many resue attachment cycles, with no special operations on the main assembly parts other than the tapering of the back end of the insertion hole.

  19. Reusable Launch Vehicle Technology Program

    NASA Technical Reports Server (NTRS)

    Freeman, Delma C., Jr.; Talay, Theodore A.; Austin, R. Eugene

    1997-01-01

    Industry/NASA reusable launch vehicle (RLV) technology program efforts are underway to design, test, and develop technologies and concepts for viable commercial launch systems that also satisfy national needs at acceptable recurring costs. Significant progress has been made in understanding the technical challenges of fully reusable launch systems and the accompanying management and operational approaches for achieving a low cost program. This paper reviews the current status of the RLV technology program including the DC-XA, X-33 and X-34 flight systems and associated technology programs. It addresses the specific technologies being tested that address the technical and operability challenges of reusable launch systems including reusable cryogenic propellant tanks, composite structures, thermal protection systems, improved propulsion and subsystem operability enhancements. The recently concluded DC-XA test program demonstrated some of these technologies in ground and flight test. Contracts were awarded recently for both the X-33 and X-34 flight demonstrator systems. The Orbital Sciences Corporation X-34 flight test vehicle will demonstrate an air-launched reusable vehicle capable of flight to speeds of Mach 8. The Lockheed-Martin X-33 flight test vehicle will expand the test envelope for critical technologies to flight speeds of Mach 15. A propulsion program to test the X-33 linear aerospike rocket engine using a NASA SR-71 high speed aircraft as a test bed is also discussed. The paper also describes the management and operational approaches that address the challenge of new cost effective, reusable launch vehicle systems.

  20. Reusable launch vehicle technology program

    NASA Astrophysics Data System (ADS)

    Freeman, Delma C.; Talay, Theodore A.; Austin, R. Eugene

    Industry/NASA reusable launch vehicle (RLV) technology program efforts are underway to design, test, and develop technologies and concepts for viable commercial launch systems that also satisfy national needs at acceptable recurring costs. Significant progress has been made in understanding the technical challenges of fully reusable launch systems and the accompanying management and operational approaches for achieving a low-cost program. This paper reviews the current status of the RLV technology program including the DC-XA, X-33 and X-34 flight systems and associated technology programs. It addresses the specific technologies being tested that address the technical and operability challenges of reusable launch systems including reusable cryogenic propellant tanks, composite structures, thermal protection systems, improved propulsion, and subsystem operability enhancements. The recently concluded DC-XA test program demonstrated some of these technologies in ground and flight tests. Contracts were awarded recently for both the X-33 and X-34 flight demonstrator systems. The Orbital Sciences Corporation X-34 flight test vehicle will demonstrate an air-launched reusable vehicle capable of flight to speeds of Mach 8. The Lockheed-Martin X-33 flight test vehicle will expand the test envelope for critical technologies to flight speeds of Mach 15. A propulsion program to test the X-33 linear aerospike rocket engine using a NASA SR-71 high speed aircraft as a test bed is also discussed. The paper also describes the management and operational approaches that address the challenge of new cost-effective, reusable launch vehicle systems.

  1. A precious-metal free micro fuel cell accumulator

    NASA Astrophysics Data System (ADS)

    Bretthauer, C.; Müller, C.; Reinecke, H.

    2011-05-01

    In recent years, integrated fuel cell (FC) type primary and secondary batteries attracted a great deal of attention as integrated on-chip power sources due to their high theoretical power densities. Unfortunately, the costs of these devices have been rather high. This is partially due to the involved clean-room processes, but also due to the fact that these devices generally rely on expensive precious-metals such as Pd and Pt. Therefore we developed a novel integrated FC type accumulator that is based on non-precious-metals only. The key component of the presented accumulator is its alkaline polymer electrolyte membrane that allows not only the usage of a low-cost AB5 type hydrogen storage electrode, but also the usage of La0.6Ca0.4CoO3 as a precious-metal free bifunctional catalyst for the air-breathing electrode. Additionally the presented design requires only comparatively few cleanroom processes which further reduces the overall production costs. Although abdicating precious-metals, the presented accumulator shows an open circuit voltage of 0.81 V and a maximum power density of 0.66 mW cm-2 which is comparable or even superior to former precious-metal based cells.

  2. Investigation of Metal Free Naphthalocyanine Vapor Deposited on Au(111)

    SciTech Connect

    Wiggins, Bryan C.; Hipps, Kerry W.

    2014-02-27

    Naphthalocyanines (Ncs) are promising candidates for future components in electronic devices and applications. To maximize the efficiency of Nc devices, it is critical to understand their structural and electronic properties and how these are impacted by deposition methods. The formation of a metal free naphthalocyanine (H2Nc) self-assembled monolayer on a Au(111) crystal was investigated by scanning tunneling microscopy under ultra-high-vacuum conditions at room temperature. A rigorous purification and processing procedure was developed to produce high purity, low defect, and well-ordered monolayers. High-resolution STM images reveal epitaxial growth of H2Nc on Au(111) with the observed structure having a molecular spacing of 1.6 ± 0.05 nm, with molecules orientated slightly off (roughly 2.5°) the low density packing direction of Au(111). A commensurate structure having 4 molecules per unit cell and unit cell parameters of A = 3.25 ± 0.05 nm, B = 3.17 ± 0.05 nm, and α = 87.5 ± 2° is proposed. Orbital-mediated tunneling spectroscopy was used to examine the electronic properties of individual molecules within the thin film. The first ionization potential and electron affinity of H2Nc adsorbed on Au(111) were measured to be -0.68 ± 0.03 and 1.12 ± 0.02 eV, relative to the Fermi energy.

  3. Metal-Free Sensitizers for Dye-Sensitized Solar Cells.

    PubMed

    Chaurasia, Sumit; Lin, Jiann T

    2016-06-01

    This review focuses on our work on metal-free sensitizers for dye-sensitized solar cells (DSSCs). Sensitizers based on D-A'-π-A architecture (D is a donor, A is an acceptor, A' is an electron-deficient entity) exhibit better light harvesting than D-π-A-type sensitizers. However, appropriate molecular design is needed to avoid excessive aggregation of negative charge at the electron-deficient entity upon photoexcitation. Rigidified aromatics, including aromatic segments comprising fused electron-excessive and -deficient units in the spacer, allow effective electronic communication, and good photoinduced charge transfer leads to excellent cell performance. Sensitizers with two anchors/acceptors, D(-π-A)2 , can more efficiently harvest light, inject electrons, and suppress dark current compared with congeners with a single anchor. Appropriate incorporation of heteroaromatic units in the spacer is beneficial to DSSC performance. High-performance, aqueous-based DSSCs can be achieved with a dual redox couple comprising imidazolium iodide and 2,2,6,6-tetramethylpiperidin-N-oxyl, and/or using dyes of improved wettability through the incorporation of a triethylene oxide methyl ether chain.

  4. Metal-Free and Noble Metal-Free Heteroatom-Doped Nanostructured Carbons as Prospective Sustainable Electrocatalysts.

    PubMed

    Asefa, Tewodros

    2016-09-20

    The large-scale deployment of many types of fuel cells and electrolyzers is currently constrained by the lack of sustainable and efficient catalysts that can replace the less earth-abundant, noble metal-based catalysts, which are commonly used in these renewable energy systems. This burgeoning issue has led to explosive research efforts worldwide to find alternative, metal-free and noble metal-free catalysts that are composed of inexpensive and earth-abundant elements. Hence, the recent discoveries that doping carbon nanomaterials with heteroatoms (such as N, S, B, etc.) can give sustainable materials with good electrocatalytic activity for reactions carried out in fuel cells and electrolyzers have been not only quite exciting but also very promising to address these challenging issues. Interestingly, even though they contain no metals or involve only the inexpensive, more earth-abundant ones, the catalytic activity of some of these materials fares well with those of the commercially used noble metal-based electrocatalysts, such as Pt/C. However, research efforts to improve the catalytic activity, selectivity, and stability of some of these materials for various reactions are still necessary and thus continuing. While some of these efforts have focused on finding synthetic methods that can tune the structures and compositions of already known materials and thereby improve their catalytic properties (activity, selectivity, stability, etc.), others have focused on developing entirely new materials that can exhibit better or superior catalytic properties. In these efforts, additional considerations are also being paid to find facile synthetic routes or renewable and inexpensive precursors that can lead to such types of catalysts in order to make the entire process highly sustainable and widely applicable. In this Account, notable heteroatom-doped carbon catalysts that have been developed for reactions in fuel cells and water electrolyzers, the various synthetic

  5. Technology demonstration for reusable launchers

    NASA Astrophysics Data System (ADS)

    Baiocco, P.; Bonnal, Ch.

    2016-03-01

    Reusable launchers have been studied under CNES contracts for more than 30 years, with early concepts such as STS-2000 or Oriflamme, more recently with very significant efforts devoted to Liquid Fly Back Boosters as with the Bargouzin project led with Tsniimash, TSTO with the Everest concept studied by Airbus-DS as prime contractor or the RFS Reusable First Stage concept of a large first stage associated to a cryotechnic second stage. These investigations, summarized in the first part of the paper, enabled CNES to identify clearly the technology requirements associated to reusability, as well as cost efficiency through detailed non-recurring costs and mission costs analysis. In parallel, CNES set in place development logic for sub-systems and equipment based on demonstrators, hardware test benches enabling maturation of technologies up to a TRL such that an actual development can be decided with limited risk. This philosophy has been applied so far to a large number of cases, such as TPTech and TPX for Hydrogen turbo pump, GGPX as demonstrator of innovative gas generator, HX demonstrator of modern cryotechnic upper stage with a dozen of different objectives (Thermal Protection, 20K Helium storage, measurements …). This virtuous approach, "learn as you test", is currently applied in the phased approach towards scaled down reusable booster stage, whose possibility to be used as first stage of a microlaunch vehicle is under investigation. The selected technologies allow paving the way towards reusable booster stages for Ariane 6 evolutions or main reusable stage for a further generation of heavy launchers. The paper describes the logic behind this project, together with the demonstration objectives set for the various sub-systems as well as operations.

  6. System For Retrieving Reusable Software

    NASA Technical Reports Server (NTRS)

    Van Warren, Lloyd; Beckman, Brian C.

    1993-01-01

    Encyclopedia of Software Components (ESC) is information-retrieval system of computer hardware and software providing access to generic reusable software tools and parts. Core of ESC is central tool base, which is repository of reusable software. It receives queries and submissions from user through local browser subsystem and receives authorized updates from maintenance subsystem. Sends retrievals to local browser subsystem and user's submissions to maintenance subsystem. Future versions will provide for advanced media, including voice and video, and will link system to database-management system. Programmers will not only retrieve software, but also modify, execute, and cross-link with other software.

  7. NUCLEOSYNTHESIS AND EVOLUTION OF MASSIVE METAL-FREE STARS

    SciTech Connect

    Heger, Alexander; Woosley, S. E. E-mail: woosley@ucolick.or

    2010-11-20

    The evolution and explosion of metal-free stars with masses 10-100 M{sub sun} are followed, and their nucleosynthetic yields, light curves, and remnant masses determined. Such stars would have been the first to form after the big bang and may have left a distinctive imprint on the composition of the early universe. When the supernova yields are integrated over a Salpeter initial mass function (IMF), the resulting elemental abundance pattern is qualitatively solar, but with marked deficiencies of odd-Z elements with 7 {<=} Z {<=} 13. Neglecting the contribution of the neutrino wind from the neutron stars that they form, no appreciable abundances are made for elements heavier than germanium. The computed pattern compares favorably with what has been observed in metal-deficient stars with [Z] {approx}< -3. The amount of ionizing radiation from this generation of stars is {approx}2.16 MeV per baryon (4.15 B per M{sub sun}; where 1 B = 1 Bethe = 10{sup 51} erg) for a Salpeter IMF, and may have played a role in reionizing the universe. Neglecting rotation, most of the stars end their lives as blue supergiants and form supernovae with distinctive light curves resembling SN 1987A, but some produce primary nitrogen due to dredge-up and become red supergiants. These make brighter supernovae like typical Type IIp's. For the lower mass supernovae considered, the distribution of remnant masses clusters around typical modern neutron star masses, but above 20-30 M{sub sun}, with the value depending on explosion energy, black holes are copiously formed by fallback, with a maximum hole mass of {approx}40 M{sub sun}. A novel automated fitting algorithm is developed for determining optimal combinations of explosion energy, mixing, and IMF in the large model database to agree with specified data sets. The model is applied to the low-metallicity sample of Cayrel et al. and the two ultra-iron-poor stars HE0107-5240 and HE1327-2326. Best agreement with these very low metallicity stars is

  8. A metal-free organic-inorganic aqueous flow battery.

    PubMed

    Huskinson, Brian; Marshak, Michael P; Suh, Changwon; Er, Süleyman; Gerhardt, Michael R; Galvin, Cooper J; Chen, Xudong; Aspuru-Guzik, Alán; Gordon, Roy G; Aziz, Michael J

    2014-01-09

    As the fraction of electricity generation from intermittent renewable sources--such as solar or wind--grows, the ability to store large amounts of electrical energy is of increasing importance. Solid-electrode batteries maintain discharge at peak power for far too short a time to fully regulate wind or solar power output. In contrast, flow batteries can independently scale the power (electrode area) and energy (arbitrarily large storage volume) components of the system by maintaining all of the electro-active species in fluid form. Wide-scale utilization of flow batteries is, however, limited by the abundance and cost of these materials, particularly those using redox-active metals and precious-metal electrocatalysts. Here we describe a class of energy storage materials that exploits the favourable chemical and electrochemical properties of a family of molecules known as quinones. The example we demonstrate is a metal-free flow battery based on the redox chemistry of 9,10-anthraquinone-2,7-disulphonic acid (AQDS). AQDS undergoes extremely rapid and reversible two-electron two-proton reduction on a glassy carbon electrode in sulphuric acid. An aqueous flow battery with inexpensive carbon electrodes, combining the quinone/hydroquinone couple with the Br2/Br(-) redox couple, yields a peak galvanic power density exceeding 0.6 W cm(-2) at 1.3 A cm(-2). Cycling of this quinone-bromide flow battery showed >99 per cent storage capacity retention per cycle. The organic anthraquinone species can be synthesized from inexpensive commodity chemicals. This organic approach permits tuning of important properties such as the reduction potential and solubility by adding functional groups: for example, we demonstrate that the addition of two hydroxy groups to AQDS increases the open circuit potential of the cell by 11% and we describe a pathway for further increases in cell voltage. The use of π-aromatic redox-active organic molecules instead of redox-active metals

  9. A metal-free organic-inorganic aqueous flow battery

    NASA Astrophysics Data System (ADS)

    Huskinson, Brian; Marshak, Michael P.; Suh, Changwon; Er, Süleyman; Gerhardt, Michael R.; Galvin, Cooper J.; Chen, Xudong; Aspuru-Guzik, Alán; Gordon, Roy G.; Aziz, Michael J.

    2014-01-01

    As the fraction of electricity generation from intermittent renewable sources--such as solar or wind--grows, the ability to store large amounts of electrical energy is of increasing importance. Solid-electrode batteries maintain discharge at peak power for far too short a time to fully regulate wind or solar power output. In contrast, flow batteries can independently scale the power (electrode area) and energy (arbitrarily large storage volume) components of the system by maintaining all of the electro-active species in fluid form. Wide-scale utilization of flow batteries is, however, limited by the abundance and cost of these materials, particularly those using redox-active metals and precious-metal electrocatalysts. Here we describe a class of energy storage materials that exploits the favourable chemical and electrochemical properties of a family of molecules known as quinones. The example we demonstrate is a metal-free flow battery based on the redox chemistry of 9,10-anthraquinone-2,7-disulphonic acid (AQDS). AQDS undergoes extremely rapid and reversible two-electron two-proton reduction on a glassy carbon electrode in sulphuric acid. An aqueous flow battery with inexpensive carbon electrodes, combining the quinone/hydroquinone couple with the Br2/Br- redox couple, yields a peak galvanic power density exceeding 0.6Wcm-2 at 1.3Acm-2. Cycling of this quinone-bromide flow battery showed >99 per cent storage capacity retention per cycle. The organic anthraquinone species can be synthesized from inexpensive commodity chemicals. This organic approach permits tuning of important properties such as the reduction potential and solubility by adding functional groups: for example, we demonstrate that the addition of two hydroxy groups to AQDS increases the open circuit potential of the cell by 11% and we describe a pathway for further increases in cell voltage. The use of π-aromatic redox-active organic molecules instead of redox-active metals represents a new and

  10. Metal Free Azide-Alkyne Click Reaction: Role of Substituents and Heavy Atom Tunneling.

    PubMed

    Karmakar, Sharmistha; Datta, Ayan

    2015-09-03

    Metal free click reactions provide an excellent noninvasive tool to modify and understand the processes in biological systems. Release of ring strain in cyclooctynes on reaction with azides on the formation of triazoles results in small activation energies for various intermolecular Huisgen reactions (1-9). Substitution of difluoro groups at the α, α' position of the cyclooctyne ring enhances the rates of cycloadditions by 10 and 20 times for methyl azide and benzyl azide respectively at room temperature. The computed rate enhancement on difluoro substitution using direct dynamical calculations using the canonical variational transition state theory (CVT/CAG) with small curvature tunneling (SCT) corrections are in excellent agreement with the experimental results. For the intramolecular click reaction (10) notwithstanding its much higher activation energy, quantum mechanical tunneling (QMT) enhances the rate of cycloaddition significantly and increases the N(14)/N(15) primary kinetic isotope effect at 298 K. QMT is shown to be rather efficient in 10 due to a thin barrier of ∼2.4 Å. The present study shows that tunneling effects can be significant for intramolecular click reactions.

  11. Effect of metal-free porphyrins on the thermal-oxidative breakdown of biocompatible polymers

    NASA Astrophysics Data System (ADS)

    Zarkhina, T. S.; Aksenova, N. A.; Solov'eva, A. B.

    2017-06-01

    The inhibitory effect of metal-free porphyrins on the thermal-oxidative breakdown of several biocompatible polymers is observed for the first time. Differential thermal analysis shows that the thermal stability of poly(ethylene oxide) and triblock copolymers of ethylene oxide and propylene oxide increases by 80-100 K, compared to the initial breakdown temperatures of these polymers in the presence of metal-free porphyrins (up to 3 wt %).

  12. Reusable Material for Drop Tower

    DTIC Science & Technology

    2011-08-01

    UNCLASSIFIED: Distribution A. Approved for public release. REUSABLE MATERIAL FOR DROP TOWER A thesis written at TANK AUTOMOTIVE RESEARCH AND...ABSTRACT This thesis represents the capstone of my five years combined academic work at Kettering University and job experience at Tank Automotive ...NUMBER OF PAGES 57 19a. NAME OF RESPONSIBLE PERSON a. REPORT unclassified b. ABSTRACT unclassified c. THIS PAGE unclassified Standard Form

  13. Reusable rocket engine optical condition monitoring

    NASA Technical Reports Server (NTRS)

    Wyett, L.; Maram, J.; Barkhoudarian, S.; Reinert, J.

    1987-01-01

    Plume emission spectrometry and optical leak detection are described as two new applications of optical techniques to reusable rocket engine condition monitoring. Plume spectrometry has been used with laboratory flames and reusable rocket engines to characterize both the nominal combustion spectra and anomalous spectra of contaminants burning in these plumes. Holographic interferometry has been used to identify leaks and quantify leak rates from reusable rocket engine joints and welds.

  14. Nitrogen-doped graphene as efficient metal-free electrocatalyst for oxygen reduction in fuel cells.

    PubMed

    Qu, Liangti; Liu, Yong; Baek, Jong-Beom; Dai, Liming

    2010-03-23

    Nitrogen-doped graphene (N-graphene) was synthesized by chemical vapor deposition of methane in the presence of ammonia. The resultant N-graphene was demonstrated to act as a metal-free electrode with a much better electrocatalytic activity, long-term operation stability, and tolerance to crossover effect than platinum for oxygen reduction via a four-electron pathway in alkaline fuel cells. To the best of our knowledge, this is the first report on the use of graphene and its derivatives as metal-free catalysts for oxygen reduction. The important role of N-doping to oxygen reduction reaction (ORR) can be applied to various carbon materials for the development of other metal-free efficient ORR catalysts for fuel cell applications, even new catalytic materials for applications beyond fuel cells.

  15. Reusable launch vehicle development research

    NASA Technical Reports Server (NTRS)

    1995-01-01

    NASA has generated a program approach for a SSTO reusable launch vehicle technology (RLV) development which includes a follow-on to the Ballistic Missile Defense Organization's (BMDO) successful DC-X program, the DC-XA (Advanced). Also, a separate sub-scale flight demonstrator, designated the X-33, will be built and flight tested along with numerous ground based technologies programs. For this to be a successful effort, a balance between technical, schedule, and budgetary risks must be attained. The adoption of BMDO's 'fast track' management practices will be a key element in the eventual success of NASA's effort.

  16. Use of steric encumbrance to develop conjugated nanoporous polymers for metal-free catalytic hydrogenation

    DOE PAGES

    Tian, Chengcheng; Zhu, Xiang; Abney, Carter W.; ...

    2016-09-08

    The design and synthesis of metal-free heterogeneous catalysts for efficient hydrogenation remains a great challenge. Here we report a novel approach to create conjugated nanoporous polymers with efficient hydrogenation activities toward unsaturated ketones by leveraging the innate steric encumbrance. The steric bulk of the framework as well as the local sterics of the Lewis basic sites within the polymeric skeleton result in the generation of the putative catalyst. Lastly, this approach opens up new possibilities for the development of innovative metal-free heterogeneous catalysts.

  17. Use of steric encumbrance to develop conjugated nanoporous polymers for metal-free catalytic hydrogenation

    SciTech Connect

    Tian, Chengcheng; Zhu, Xiang; Abney, Carter W.; Tian, Ziqi; Jiang, De-en; Han, Kee Sung; Mahurin, Shannon M.; Washton, Nancy M.; Dai, Sheng

    2016-01-01

    The design and synthesis of metal-free heterogeneous catalysts for efficient hydrogenation remains a great challenge. Here we report a novel approach to create conjugated nanoporous polymers with efficient hydrogenation activities toward unsaturated ketones by leveraging the innate steric encumbrance. The steric bulk of the framework as well as the local sterics of the Lewis basic sites within the polymeric skeleton result in the generation of the putative catalyst. This approach opens up new possibilities for the development of innovative metal-free heterogeneous catalysts.

  18. Aquarius, a reusable water-based interplanetary human spaceflight transport

    NASA Astrophysics Data System (ADS)

    Adamo, Daniel R.; Logan, James S.

    2016-11-01

    Attributes of a reusable interplanetary human spaceflight transport are proposed and applied to example transits between the Earth/Moon system and Deimos, the outer moon of Mars. Because the transport is 54% water by mass at an interplanetary departure, it is christened Aquarius. In addition to supporting crew hydration/hygiene, water aboard Aquarius serves as propellant and as enhanced crew habitat radiation shielding during interplanetary transit. Key infrastructure and technology supporting Aquarius operations include pre-emplaced consumables and subsurface habitat at Deimos with crew radiation shielding equivalent to sea level on Earth, resupply in a selenocentric distant retrograde orbit, and nuclear thermal propulsion.

  19. Methodology for Assessing Reusability of Spaceflight Hardware

    NASA Technical Reports Server (NTRS)

    Childress-Thompson, Rhonda; Thomas, L. Dale; Farrington, Phillip

    2017-01-01

    In 2011 the Space Shuttle, the only Reusable Launch Vehicle (RLV) in the world, returned to earth for the final time. Upon retirement of the Space Shuttle, the United States (U.S.) no longer possessed a reusable vehicle or the capability to send American astronauts to space. With the National Aeronautics and Space Administration (NASA) out of the RLV business and now only pursuing Expendable Launch Vehicles (ELV), not only did companies within the U.S. start to actively pursue the development of either RLVs or reusable components, but entities around the world began to venture into the reusable market. For example, SpaceX and Blue Origin are developing reusable vehicles and engines. The Indian Space Research Organization is developing a reusable space plane and Airbus is exploring the possibility of reusing its first stage engines and avionics housed in the flyback propulsion unit referred to as the Advanced Expendable Launcher with Innovative engine Economy (Adeline). Even United Launch Alliance (ULA) has announced plans for eventually replacing the Atlas and Delta expendable rockets with a family of RLVs called Vulcan. Reuse can be categorized as either fully reusable, the situation in which the entire vehicle is recovered, or partially reusable such as the National Space Transportation System (NSTS) where only the Space Shuttle, Space Shuttle Main Engines (SSME), and Solid Rocket Boosters (SRB) are reused. With this influx of renewed interest in reusability for space applications, it is imperative that a systematic approach be developed for assessing the reusability of spaceflight hardware. The partially reusable NSTS offered many opportunities to glean lessons learned; however, when it came to efficient operability for reuse the Space Shuttle and its associated hardware fell short primarily because of its two to four-month turnaround time. Although there have been several attempts at designing RLVs in the past with the X-33, Venture Star and Delta Clipper

  20. Metal-Free Nitrile Diboration through Activation by an Electron-Rich Diborane.

    PubMed

    Frick, Markus; Kaifer, Elisabeth; Himmel, Hans-Jörg

    2017-09-11

    Diboration of unsaturated organic compounds is an extremely useful reaction in synthetic chemistry. Herein, we report the first diboration of a nitrile by an electron-rich diborane, mediated by an electrophilic borane. The reaction is metal-free, and all of the reagents are readily available. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Metal-free catalysis of nitrogen-doped nanocarbons for the ammoxidation of alcohols to nitriles.

    PubMed

    Shang, Sensen; Dai, Wen; Wang, Lianyue; Lv, Ying; Gao, Shuang

    2017-01-17

    Here meso-N/C-900 derived from polypyridyl ligand DAA has been developed as a metal-free catalyst, for the first time, exhibiting good performance in catalytic ammoxidation of alcohols to nitriles. Systematic characterization suggests that the accessible mesopores and the effective pyridinic/pyrrolic-N are responsible for the unprecedented performance.

  2. Diversity-oriented synthesis of chromenes via metal-free domino reactions from ketones and phenols.

    PubMed

    Xue, Wei-Jian; Li, Qi; Gao, Fang-fang; Zhu, Yan-ping; Wang, Jun-gang; Zhang, Wei; Wu, An-Xin

    2012-08-13

    Functionalized chromenes have been synthesized via highly selective metal-free domino reactions from ketones and phenols. 2H-Chromenes, 4H-chromenes, spiran and benzocyclopentane can be respectively prepared starting from the corresponding cyclic ketones, aryl methyl ketones, acetone, and 3-pentanone.

  3. A metal-free general procedure for oxidation of secondary amines to nitrones.

    PubMed

    Gella, Carolina; Ferrer, Eric; Alibés, Ramon; Busqué, Félíx; de March, Pedro; Figueredo, Marta; Font, Josep

    2009-08-21

    An efficient and metal-free protocol for direct oxidation of secondary amines to nitrones has been developed, using Oxone in a biphasic basic medium as the sole oxidant. The method is general and tolerant with other functional groups or existing stereogenic centers, providing rapid access to enantiomerically pure compounds in good yields.

  4. The Reusable Astronomy Portal (TRAP)

    NASA Astrophysics Data System (ADS)

    Donaldson, T.; Rogers, A.; Wallace, G.

    2012-09-01

    The Reusable Astronomy Portal (TRAP) aims to provide a common platform for rapidly deploying Astronomy Archives to the web. TRAP is currently under development for both the VAO Data Discovery Portal and the MAST Multi-Mission Portal (Figure 1). TRAP consists of 2 major software packages: the TRAP Client and the TRAP Server. The TRAP framework allows developers to deploy the Server, connect to data resources, then focus on building custom tools for the Client. TRAP is built upon proven industry technologies including the Ext/JS JavaScript Component Library, Mono.NET Web Services, and JSON message based APIs. The multi-layered architecture of TRAP decouples each layer: Client, Service and Data Access, enabling each to evolve independently over time. Although currently deployed to provide astronomy science data access, the TRAP architecture is flexible enough to thrive in any distributed data environment.

  5. Reusable ultralight personnel carrier (RUPC)

    NASA Technical Reports Server (NTRS)

    Clark, B. C., III; Mccandless, B., II

    1992-01-01

    Attention is given to a personnel-carrying space vehicle concept developed to minimize the cost of access to LEO. The RUPC could provide alternate access to Space Station Freedom (SSF) for six passengers per flight. It can also bring and return small amounts of cargo, up to and including one SSF double rack. These capabilities are ideal for utilization flights during man-tended operations at SSF and for crew rotation during permanently manned periods. The RUPC is a reusable conical reentry vehicle and disposable adapter with propulsion and power subsystems. Avionics subsystem benefit from advanced low-power high-performance microelectronics developed for both the civilian and military space sectors. The RUPC core cabin concept has growth potential for other applications, including assured crew return, ground-launched crew rescue, delivery and retrieval of SSF cargo, and crew cabin for flights to the moon.

  6. Selective synthesis of thioethers in the presence of a transition-metal-free solid Lewis acid.

    PubMed

    Santoro, Federica; Mariani, Matteo; Zaccheria, Federica; Psaro, Rinaldo; Ravasio, Nicoletta

    2016-01-01

    The synthesis of thioethers starting from alcohols and thiols in the presence of amorphous solid acid catalysts is reported. A silica alumina catalyst with a very low content in alumina gave excellent results in terms of both activity and selectivity also under solvent-free conditions. The reaction rate follows the electron density of the carbinol atom in the substrate alcohol and yields up to 99% and can be obtained for a wide range of substrates under mild reaction conditions.

  7. Chemo- and Stereoselective Transition-Metal-Free Amination of Amides with Azides

    PubMed Central

    2016-01-01

    The synthesis of α-amino carbonyl/carboxyl compounds is a contemporary challenge in organic synthesis. Herein, we present a stereoselective α-amination of amides employing simple azides that proceeds under mild conditions with release of nitrogen gas. The amide is used as the limiting reagent, and through simple variation of the azide pattern, various differently substituted aminated products can be obtained. The reaction is fully chemoselective for amides even in the presence of esters or ketones and lends itself to preparation of optically enriched products. PMID:27350334

  8. Transition-metal-free acid-mediated synthesis of aryl sulfides from thiols and thioethers.

    PubMed

    Wagner, Anna M; Sanford, Melanie S

    2014-03-07

    The preparation of diaryl and alkyl aryl sulfides via acid-mediated coupling of thiols and thioethers with diaryliodonium salts is reported. The scope, limitations, and mechanism of the transformation are discussed.

  9. Transition-metal-free Sonogashira-type cross-coupling of alkynes with fluoroarenes.

    PubMed

    Jin, Guanyi; Zhang, Xuxue; Cao, Song

    2013-06-21

    A novel, inexpensive, and efficient palladium-, copper-, ligand-, and amine-free Sonogashira-type cross-coupling reaction of terminal alkynes with unreactive aryl fluorides in the presence of sodium, sodium methoxide, and calcium hydroxide under the assistance of a Grignard reagent was developed. A plausible mechanism was also suggested.

  10. Selective synthesis of thioethers in the presence of a transition-metal-free solid Lewis acid

    PubMed Central

    Santoro, Federica; Mariani, Matteo; Zaccheria, Federica; Psaro, Rinaldo

    2016-01-01

    The synthesis of thioethers starting from alcohols and thiols in the presence of amorphous solid acid catalysts is reported. A silica alumina catalyst with a very low content in alumina gave excellent results in terms of both activity and selectivity also under solvent-free conditions. The reaction rate follows the electron density of the carbinol atom in the substrate alcohol and yields up to 99% and can be obtained for a wide range of substrates under mild reaction conditions. PMID:28144333

  11. Fully reusable launch vehicle with airbreathing booster

    NASA Astrophysics Data System (ADS)

    Huang, Z.

    1983-10-01

    The performance of a two-stage, fully reusable scramjet-Shuttle launch vehicle is examined analytically. The first stage of the hybrid vehicle would be a hydrocarbon/hydrogen fueled air breathing hypersonic aircraft. The winged booster, in one configuration, would be equipped with both turbojets and scramjets, and the Orbiter would be a scaled-up version of the present STS Orbiter. The nominal mission would involve placing a 65,000 lb payload into a 92.5 x 185 km orbit. The size of the manned first stage is dictated by the ventricle gross weight, density, and contents, with the fuel carried in integrated tanks. A delta planform is presented, with an elliptical cone forebody, an elliptical cross-section afterbody, and a smooth transition surface from the end of the forebody to the straightline leading edge. Formulations are defined for the wing loading, gross density, fatness ratio, and breadpoint ratio, as well as for the propulsion, aerodynamics, and trajectories.

  12. Modified multi-wall carbon nanotubes as metal free catalyst for application in H2 production from methanolysis of NaBH4

    NASA Astrophysics Data System (ADS)

    Sahiner, Nurettin

    2017-10-01

    Multi-walled carbon nanotubes (MWCNT) are modified by acid treatments to obtain MWCNT-COOHs and used as metal free catalyst directly in H2 generation from the methanolysis of sodium borohydride (NaBH4). The chemically modified MWCNT-COOHs are characterized with Fourier Transform Infrared Spectroscopy (FT-IR) and zeta potential measurements. The H2 generation reactions are proceeded at different reaction conditions to determine the optimum reaction parameters such as the concentration of NaBH4 and temperature, the reusability of catalyst, and the regeneration of catalyst. The MWCNT-COOHs are found to be very effective catalyst in comparison to the metal nanoparticle catalyzed H2 generation reactions from the methanolysis of NaBH4. Thus, hydrogen generation rate (HGR) is calculated as 8766 ± 477 mL H2 g-1 min-1 for 500 mM NaBH4 in 20 mL methanol in presence of 50 mg MWCNT-COOH. Furthermore, the activation energy (Ea) for the methanolysis of NaBH4 in presence of MWCNT-COOHs is computed as 20.1 ± 1.4 kJ mol-1, comparable with most of the reported metal nanoparticle based catalyst in the literature.

  13. Enhanced visible-light response of metal-free doped bulk h-BN as potential efficient photocatalyst: a computational study.

    PubMed

    Wang, Fang; Cao, Yuehan; Wei, Shiqian; Zhou, Ying

    2017-01-01

    We have provided a straightforward route to screen a series of metal-free doped bulk h-BN as potential visible-light photocatalysts via the first-principle computations. Various nonmetal dopants are considered including Si, P, C, S, Cl, O, and F atoms according to increasing electronegativity. The results show that the introduction of nonmetals leads to small lattice distortions but significant modifications of band structures, electron transition paths and chemical bonding interactions. Generally, all doped h-BN except Si doping have an active response to the visible-light, and dopants with higher electronegativity can significantly narrow the band gaps, which could induce easier optical transition under visible-light excitation. Based on the electronic structures and absorption spectra, three different mechanisms of enhanced visible-light response for the doping effect are proposed. It is expected that F, Cl, and S-doped h-BN could be used as potential efficient visible-light driven photocatalysts. This study could aid in the design of novel efficient h-BN photocatalysts. Graphical Abstract The mechanisms of the enhanced visible-light response of metal-free doped bulk h-BN.

  14. Metal-Free C–H Alkyliminylation and Acylation of Alkenes with Secondary Amides

    NASA Astrophysics Data System (ADS)

    Huang, Pei-Qiang; Huang, Ying-Hong; Geng, Hui; Ye, Jian-Liang

    2016-06-01

    Carbon–carbon bond formation by metal-free cross-coupling of two reactants with low reactivity represents a challenge in organic synthesis. Secondary amides and alkenes are two classes of bench-stable compounds. The low electrophilicity of the former and low nucleophilicity of the latter make the direct coupling of these two partners challenging yet highly desirable. We report herein an unprecedented intermolecular reaction of secondary amides with alkenes to afford α,β-unsaturated ketimines or enones, which are versatile intermediates for organic synthesis and are prevalent in bioactive compounds and functional materials. Our strategy relies on the chemoselective activation of the secondary amide with trifluoromethanesulfonic anhydride (Tf2O)/2-fluoropyridine to generate a highly reactive nitrilium intermediate, which reacts efficiently with alkenes. This metal-free synthesis is characterized by its mild reaction conditions, excellent functional group tolerance and chemoselectivity, allowing the preparation of multi-functionalized compounds without using protecting groups.

  15. Aryl Transfer Selectivity in Metal-Free Reactions of Unsymmetrical Diaryliodonium Salts.

    PubMed

    Stuart, David R

    2017-08-09

    Aromatic rings are found in a wide variety of products, including pharmaceuticals, agrochemicals, and functional materials. Diaryliodonium salts are new reagents used to transfer aryl groups under both metal-free and metal-catalyzed reactions and thereby synthesize arene-containing compounds. This minireview focuses on recent studies in selective aryl transfer reactions from unsymmetrical diaryliodonium salts under metal-free conditions. Reactions reported from 2007 to 2017, which represents a period of significant growth in diaryliodonium salt chemistry, are presented and organized by the type of reactive intermediate formed in the reaction. Specifically, reactions involving λ(3) -iodane, λ(3) -iodane radical anions, aryl radicals, and arynes are discussed. Chemoselectivity trends in aryl transfer are compared and contrasted across reaction intermediates and translation to potential auxiliaries are posited. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Metal-free carbon nanotubes: synthesis, and enhanced intrinsic microwave absorption properties

    NASA Astrophysics Data System (ADS)

    Qi, Xiaosi; Xu, Jianle; Hu, Qi; Deng, Yu; Xie, Ren; Jiang, Yang; Zhong, Wei; Du, Youwei

    2016-06-01

    In order to clearly understand the intrinsic microwave absorption properties of carbon nanomaterials, we proposed an efficient strategy to synthesize high purity metal-free carbon nanotubes (CNTs) over water-soluble K2CO3 particles through chemical vapor decomposition and water-washing process. The comparison results indicated the leftover catalyst caused negative effects in intrinsic microwave absorption properties of CNTs, while an enhanced microwave absorption performance could be observed over the metal-free CNT sample. Moreover, the results indicated that the microwave absorption properties could be tuned by the CNT content. Therefore, we provided a simple route to investigate the intrinsic properties of CNTs and a possible enhanced microwave absorbing mechanism.

  17. Metal-Free C–H Alkyliminylation and Acylation of Alkenes with Secondary Amides

    PubMed Central

    Huang, Pei-Qiang; Huang, Ying-Hong; Geng, Hui; Ye, Jian-Liang

    2016-01-01

    Carbon–carbon bond formation by metal-free cross-coupling of two reactants with low reactivity represents a challenge in organic synthesis. Secondary amides and alkenes are two classes of bench-stable compounds. The low electrophilicity of the former and low nucleophilicity of the latter make the direct coupling of these two partners challenging yet highly desirable. We report herein an unprecedented intermolecular reaction of secondary amides with alkenes to afford α,β-unsaturated ketimines or enones, which are versatile intermediates for organic synthesis and are prevalent in bioactive compounds and functional materials. Our strategy relies on the chemoselective activation of the secondary amide with trifluoromethanesulfonic anhydride (Tf2O)/2-fluoropyridine to generate a highly reactive nitrilium intermediate, which reacts efficiently with alkenes. This metal-free synthesis is characterized by its mild reaction conditions, excellent functional group tolerance and chemoselectivity, allowing the preparation of multi-functionalized compounds without using protecting groups. PMID:27356173

  18. Metal-free carbon nanotubes: synthesis, and enhanced intrinsic microwave absorption properties

    PubMed Central

    Qi, Xiaosi; Xu, Jianle; Hu, Qi; Deng, Yu; Xie, Ren; Jiang, Yang; Zhong, Wei; Du, Youwei

    2016-01-01

    In order to clearly understand the intrinsic microwave absorption properties of carbon nanomaterials, we proposed an efficient strategy to synthesize high purity metal-free carbon nanotubes (CNTs) over water-soluble K2CO3 particles through chemical vapor decomposition and water-washing process. The comparison results indicated the leftover catalyst caused negative effects in intrinsic microwave absorption properties of CNTs, while an enhanced microwave absorption performance could be observed over the metal-free CNT sample. Moreover, the results indicated that the microwave absorption properties could be tuned by the CNT content. Therefore, we provided a simple route to investigate the intrinsic properties of CNTs and a possible enhanced microwave absorbing mechanism. PMID:27324290

  19. Reusable Surface Insulation (RSI) Material Samples

    NASA Technical Reports Server (NTRS)

    Banas, R. P.

    1977-01-01

    Test specimen data sheets are presented for 48 high temperature and 40 low temperature reusable surface insulation tiles. Tabular data show dimensions, density, coating weight, and final tile weight. Codes indicate basic material, surface coating, and hydrophobic treatment.

  20. A Framework for Assessing the Reusability of Hardware (Reusable Rocket Engines)

    NASA Technical Reports Server (NTRS)

    Childress-Thompson, Rhonda; Thomas, Dale; Farrington, Philip

    2016-01-01

    Within the past few years, there has been a renewed interest in reusability as it applies to space flight hardware. Commercial companies such as Space Exploration Technologies Corporation (SpaceX), Blue Origin, and United Launch Alliance (ULA) are pursuing reusable hardware. Even foreign companies are pursuing this option. The Indian Space Research Organization (ISRO) launched a reusable space plane technology demonstrator and Airbus Defense and Space is planning to recover the main engines and avionics from its Advanced Expendable Launcher with Innovative engine Economy [1] [2]. To date, the Space Shuttle remains as the only Reusable Launch (RLV) to have flown repeated missions and the Space Shutte Main Engine (SSME) is the only demonstrated reusable engine. Whether the hardware being considered for reuse is a launch vehicle (fully reusable), a first stage (partially reusable), or a booster engine (single component), the overall governing process is the same; it must be recovered and recertified for flight. Therefore, there is a need to identify the key factors in determining the reusability of flight hardware. This paper begins with defining reusability to set the context, addresses the significance of reuse, and discusses areas that limit successful implementation. Finally, this research identifies the factors that should be considered when incorporating reuse.

  1. Metal-free intermolecular formal cycloadditions enable an orthogonal access to nitrogen heterocycles

    PubMed Central

    Xie, Lan-Gui; Niyomchon, Supaporn; Mota, Antonio J.; González, Leticia; Maulide, Nuno

    2016-01-01

    Nitrogen-containing heteroaromatic cores are ubiquitous building blocks in organic chemistry. Herein, we present a family of metal-free intermolecular formal cycloaddition reactions that enable highly selective and orthogonal access to isoquinolines and pyrimidines at will. Applications of the products are complemented by a density functional theory mechanistic analysis that pinpoints the crucial factors responsible for the selectivity observed, including stoichiometry and the nature of the heteroalkyne. PMID:26975182

  2. Metal-Free Oxidation of Glycerol over Nitrogen-Containing Carbon Nanotubes.

    PubMed

    Gupta, Neeraj; Khavryuchenko, Oleksiy; Villa, Alberto; Su, Dangsheng

    2017-08-10

    Nitrogen rich carbon nanotubes have been used as a metal free catalyst for the conversion of glycerol into dihydroxyacetone using tert-butyl hydroperoxide as an oxidant. Pyridine nitrogen groups embedded in a carbon matrix are identified as active sites for the reaction. Computational studies have demonstrated that oxidation of pyridine groups to pyridine oxime followed by hydrogen abstraction from secondary alcohol is likely responsible for the oxidation process. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Seven-membered rings through metal-free rearrangement mediated by hypervalent iodine.

    PubMed

    Silva, Siguara Bastos Lemos; Torre, Adriana Della; de Carvalho, João Ernesto; Ruiz, Ana Lúcia Tasca Gois; Silva, Luiz F

    2015-01-15

    A versatile and metal-free approach for the synthesis of carbocycles and of heterocycles bearing seven- and eight-membered rings is described. The strategy is based on ring expansion of 1-vinylcycloalkanols (or the corresponding silyl or methyl ether) mediated by the hypervalent iodine reagent HTIB (PhI(OH)OTs). Reaction conditions can be easily adjusted to give ring expansion products bearing different functional groups. A route to medium-ring lactones was also developed.

  4. A pre-lithiation method for sulfur cathode used for future lithium metal free full battery

    NASA Astrophysics Data System (ADS)

    Wu, Yunwen; Yokoshima, Tokihiko; Nara, Hiroki; Momma, Toshiyuki; Osaka, Tetsuya

    2017-02-01

    Lithium metal free sulfur battery paired by lithium sulfide (Li2S) is a hot point in recent years because of its potential for relatively high capacity and its safety advantage. Due to the insulating nature and high sensitivity to moisture of Li2S, it calls for new way to introduce Li ion into S cathode besides the method of directly using the Li2S powder for the battery pre-lithiation. Herein, we proposed a pre-lithiation method to lithiate the polypyrrole (PPy)/S/Ketjenblack (KB) electrode into PPy/Li2S/KB cathode at room temperature. By this process, the fully lithiated PPy/Li2S/KB cathode showed facilitated charge transfer than the original PPy/S/KB cathode, leading to better cycling performance at high C-rates and disappearance of over potential phenomenon. In this work, the ion-selective PPy layer has been introduced on the cathode surface by an electrodeposition method, which can suppress the polysulfide dissolution from the cathode source. The lithium metal free full battery coupled by the prepared Li2S/KB cathode and graphite anode exhibited excellent cycling performance. Hence, we believe this comprehensive fabrication approach of Li2S cathode will pave a way for the application of new type lithium metal free secondary battery.

  5. Surface modification of nanodiamond through metal free atom transfer radical polymerization

    NASA Astrophysics Data System (ADS)

    Zeng, Guangjian; Liu, Meiying; Shi, Kexin; Heng, Chunning; Mao, Liucheng; Wan, Qing; Huang, Hongye; Deng, Fengjie; Zhang, Xiaoyong; Wei, Yen

    2016-12-01

    Surface modification of nanodiamond (ND) with poly(2-methacryloyloxyethyl phosphorylcholine) [poly(MPC)] has been achieved by using metal free surface initiated atom transfer radical polymerization (SI-ATRP). The ATRP initiator was first immobilized on the surface of ND through direct esterification reaction between hydroxyl group of ND and 2-bromoisobutyryl bromide. The initiator could be employed to obtain ND-poly(MPC) nanocomposites through SI-ATRP using an organic catalyst. The final functional materials were characterized by 1H nuclear magnetic resonance, transmission electron microscopy, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy and thermo gravimetric analysis in detailed. All of these characterization results demonstrated that ND-poly(MPC) have been successfully obtained via metal free photo-initiated SI-ATRP. The ND-poly(MPC) nanocomposites shown enhanced dispersibility in various solvents as well as excellent biocompatibility. As compared with traditional ATRP, the metal free ATRP is rather simple and effective. More importantly, this preparation method avoided the negative influence of metal catalysts. Therefore, the method described in this work should be a promising strategy for fabrication of polymeric nanocomposites with great potential for different applications especially in biomedical fields.

  6. MOF-Derived Noble Metal Free Catalysts for Electrochemical Water Splitting.

    PubMed

    Tao, Zixu; Wang, Teng; Wang, Xiaojuan; Zheng, Jie; Li, Xingguo

    2016-12-28

    Noble metal free electrocatalysts for water splitting are key to low-cost, sustainable hydrogen production. In this work, we demonstrate that metal-organic frameworks (MOFs) can be controllably converted into catalysts for the oxygen evolution reaction (OER) or the hydrogen evolution reaction (HER). The OER catalyst is composed of FeNi alloy nanoparticles encapsulated in N-doped carbon nanotubes, which is obtained by thermal decomposition of a trimetallic (Zn(2+), Fe(2+), and Ni(2+)) zeolitic imidazolate framework (ZIF). It reaches 10 mA cm(-2) at the overpotential of 300 mV with a low Tafel slope of 47.7 mV dec(-1). The HER catalyst consists of Ni nanoparticles coated with a thin layer of N-doped carbon. It is obtained by thermal decomposition of a Ni-MOF in NH3. It shows low overpotential of only 77 mV at 20 mA cm(-2) with low Tafel slope of 68 mV dec(-1). The above noble metal free OER and HER electrocatalysts are applied in an alkaline electrolyzer driven by a commercial polycrystalline solar cell. It achieves electrolysis efficiency of 64.4% at 65 mA cm(-2) under sun irradiation of 50 mW cm(-2). This practical application shows the promising prospect of low-cost and high-efficiency sustainable hydrogen production from combination of solar cells with high-performance noble metal free electrocatalysts.

  7. Reusable, tamper-indicating seal

    DOEpatents

    Ryan, Michael J.

    1978-01-01

    A reusable, tamper-indicating seal comprises a drum confined within a fixed body and rotatable in one direction therewithin, the top of the drum constituting a tray carrying a large number of small balls of several different colors. The fixed body contains parallel holes for looping a seal wire therethrough. The base of the drums carries cams adapted to coact with cam followers to lock the wire within the seal at one angular position of the drum. A channel in the fixed body -- visible from outside the seal -- adjacent the tray constitutes a segregated location for a small plurality of the colored balls. A spring in the tray forces colored balls into the segregated location at one angular position of the drum, further rotation securing the balls in position and the wires in the seal. A wedge-shaped plough removes the balls from the segregated location, at a different angular position of the drum, the wire being unlocked at the same position. A new pattern of colored balls will appear in the segregated location when the seal is relocked.

  8. Reusable experiment controllers, case studies

    NASA Astrophysics Data System (ADS)

    Buckley, Brian A.; Gaasbeck, Jim Van

    1996-03-01

    Congress has given NASA and the science community a reality check. The tight and ever shrinking budgets are trimming the fat from many space science programs. No longer can a Principal Investigator (PI) afford to waste development dollars on re-inventing spacecraft controllers, experiment/payload controllers, ground control systems, or test sets. Inheritance of the Ground Support Equipment (GSE) from one program to another is not a significant re-use of technology to develop a science mission in these times. Reduction of operational staff and highly autonomous experiments are needed to reduce the sustaining cost of a mission. The re-use of an infrastructure from one program to another is needed to truly attain the cost and time savings required. Interface and Control Systems, Inc. (ICS) has a long history of re-usable software. Navy, Air Force, and NASA programs have benefited from the re-use of a common control system from program to program. Several standardization efforts in the AIAA have adopted the Spacecraft Command Language (SCL) architecture as a point solution to satisfy requirements for re-use and autonomy. The Environmental Research Institute of Michigan (ERIM) has been a long-standing customer of ICS and are working on their 4th generation system using SCL. Much of the hardware and software infrastructure has been re-used from mission to mission with little cost for re-hosting a new experiment. The same software infrastructure has successfully been used on Clementine, and an end-to-end system is being deployed for the Far Ultraviolet Spectroscopic Explorer (FUSE) for Johns Hopkins University. A case study of the ERIM programs, Clementine and FUSE will be detailed in this paper.

  9. B4CN3 and B3CN4 monolayers as the promising candidates for metal-free spintronic materials

    NASA Astrophysics Data System (ADS)

    Pan, Hongzhe; Sun, Yuanyuan; Zheng, Yongping; Tang, Nujiang; Du, Youwei

    2016-09-01

    The search for candidates of spintronic materials, especially among the two-dimensional (2D) materials, has attracted tremendous attentions over the past decades. By using a particle swarm optimization structure searching method combined with density functional calculations, two kinds of boron carbonitride monolayer structures (B4CN3 and B3CN4) are proposed and confirmed to be dynamically and kinetically stable. Intriguingly, we demonstrate that the magnetic ground states of the two B x C y N z systems are ferromagnetic ordering with a high Curie temperature of respectively 337 K for B4CN3 and 309 K for B3CN4. Furthermore, based on their respective band structures, the B4CN3 is found to be a bipolar magnetic semiconductor (BMS), while the B3CN4 is identified to be a type of spin gapless semiconductor (SGS), both of which are potential spintronic materials. In particular, carrier doping in the B4CN3 can induce a transition from BMS to half-metal, and its spin polarization direction is switchable depending on the doped carrier type. The BMS property of B4CN3 is very robust under an external strain or even a strong electric field. By contrast, as a SGS, the electronic structure of B3CN4 is relatively sensitive to external influences. Our findings successfully disclose two promising materials toward 2D metal-free spintronic applications.

  10. From melamine sponge towards 3D sulfur-doping carbon nitride as metal-free electrocatalysts for oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Xu, Jingjing; Li, Bin; Li, Songmei; Liu, Jianhua

    2017-07-01

    Development of new and efficient metal-free electrocatalysts for replacing Pt to improve the sluggish kinetics of oxygen reduction reaction (ORR) is of great importance to emerging renewable energy technologies such as metal-air batteries and polymer electrolyte fuel cells. Herein, 3D sulfur-doping carbon nitride (S-CN) as a novel metal-free ORR electrocatalyst was synthesized by exploiting commercial melamine sponge as raw material. The sulfur atoms were doping on CN networks uniformly through numerous S-C bonds which can provide additional active sites. And it was found that the S-CN exhibited high catalytic activity for ORR in term of more positive onset potential, higher electron transfer number and higher cathodic density. This work provides a novel choice of metal-free ORR electrocatalysts and highlights the importance of sulfur-doping CN in metal-free ORR electrocatalysts.

  11. Transitions.

    ERIC Educational Resources Information Center

    Agnew, Jeanne L.; Choike, James R.

    1987-01-01

    Mathematical observations are made about some continuous curves, called transitions, encountered in well-known experiences. The transition parabola, the transition spiral, and the sidestep maneuver are presented. (MNS)

  12. Synthesis of cycloalkyl substituted purine nucleosides via a metal-free radical route.

    PubMed

    Wang, Dong-Chao; Xia, Ran; Xie, Ming-Sheng; Qu, Gui-Rong; Guo, Hai-Ming

    2016-05-04

    An efficient route to synthesize cycloalkyl substituted purine nucleosides was developed. This metal-free C-H activation was accomplished by a tBuOOtBu initiated radical reaction. By adjusting the amount of tBuOOtBu and reaction time, the selective synthesis of C6-monocycloalkyl or C6,C8-dicycloalkyl substituted purine nucleosides could be realized. Furthermore, uracil and related nucleosides were also suitable substrates, giving the C5-cyclohexyl substituted uracil derivatives in good yields with excellent regioselectivities.

  13. Thermal Methane Activation by the Metal-Free Cluster Cation [Si2 O4 ](.)

    PubMed

    Sun, Xiaoyan; Zhou, Shaodong; Schlangen, Maria; Schwarz, Helmut

    2017-01-31

    The thermal reaction of methane with the metal-free cluster cation [Si2 O4 ](.+) has been examined by using Fourier transform-ion cyclotron resonance (FT-ICR) mass spectrometry. In addition to generating a methyl radical via hydrogen-atom abstraction, [Si2 O4 ](.+) can selectively oxidize methane to formaldehyde. The mechanisms of these rather efficient reactions have been elucidated by high-level quantum-chemical calculations. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Transitions.

    ERIC Educational Resources Information Center

    Nathanson, Jeanne H., Ed.

    1993-01-01

    This theme issue on transitions for individuals with disabilities contains nine papers discussing transition programs and issues. "Transition Issues for the 1990s," by Michael J. Ward and William D. Halloran, discusses self-determination, school responsibility for transition, continued educational engagement of at-risk students, and service…

  15. CD-XA Reusable Launch Vehicle (RLV)

    NASA Technical Reports Server (NTRS)

    1995-01-01

    This is the McDornell Douglas CD-XA Reusable Launch Vehicle (RLV) concept. The Delta Clipper-Experimental (DC-X) was originally developed by McDonnell Douglas for the DOD. The DC-XA is a single-stage-to-orbit, vertical takeoff/vertical landing, launch vehicle concept, whose development is geared to significantly reduce launch cost and provided a test bed for NASA Reusable Launch Vehicle (RLV) technology as the Delta Clipper-Experimental Advanced (DC-XA). The program was discontinued in 2003.

  16. Reusable thermal protection system development: A prospective

    NASA Astrophysics Data System (ADS)

    Goldstein, Howard

    1992-10-01

    The state of the art in passive reusable thermal protection system materials is described. Development of the Space Shuttle Orbiter, which was the first reusable vehicle, is discussed. The thermal protection materials and given concepts and some of the shuttle development and manufacturing problems are described. Evolution of a family of grid and flexible ceramic external insulation materials from the initial shuttle concept in the early 1970's to the present time is described. The important properties and their evolution are documented. Application of these materials to vehicles currently being developed and plans for research to meet the space programs future needs are summarized.

  17. Reusable Agena study. Volume 2: Technical

    NASA Technical Reports Server (NTRS)

    Carter, W. K.; Piper, J. E.; Douglass, D. A.; Waller, E. W.; Hopkins, C. V.; Fitzgerald, E. T.; Sagawa, S. S.; Carter, S. A.; Jensen, H. L.

    1974-01-01

    The application of the existing Agena vehicle as a reusable upper stage for the space shuttle is discussed. The primary objective of the study is to define those changes to the Agena required for it to function in the reusable mode in the 100 percent capture of the NASA-DOD mission model. This 100 percent capture is achieved without use of kick motors or stages by simply increasing the Agena propellant load by using optional strap-on-tanks. The required shuttle support equipment, launch and flight operations techniques, development program, and cost package are also defined.

  18. Comparison to the scanning electron microscope of professional dental hygiene methods on metal-free layered structures and metal-free monolithic structures processed by different polymerization cycles.

    PubMed

    Ermetici, M; Segù, M; Butera, A

    2014-06-01

    Aim of the study was to find effective instrumental methodologies and procedures for scaling and deplaquing without compromising the structure of metal-free, monolithic lithium disilicate and layered zirconia prosthetics. Of 14 decontaminated, extracted teeth in good anatomical condition, 7 veneers lithium disilicate monolithic and 7 layered zirconia crowns were prepared for testing and divided into 6 treatment groups. Each group was composed of a veneer and a crown. The division of the groups was carried out according to the type of treatment performed- instrumental carbon fiber and steel tips, prophylaxis paste with high and low RDA (Relative dentin abrasion), bicarbonate powder. Samples were examined and observed through a scanning electron microscope (SEM). Afterwards a detailed comparison of the images of treated and untreated samples was performed. The images were at the same magnification, thus showing the differences in the treated samples. The monolithic lithium disilicate presents minor damage to the surface but no excessive changes to the structure in general post treatment. The layered zirconia resulted in notable damage with evident abrasions on the layered ceramic structure after the use of ultrasound with a steel tip and air flow with bicarbonate. Carbon fibre tips and prophylaxis paste containing perlite and low RDA did not create notable changes to the properties of the materials in question. The results of the disilicate monolithic appear to show it to be a much more resistant material compared to layered zirconia in ceramic. Its resistance is demonstrated by the lack of notable damage in all the treatment groups.

  19. Noble metal-free bifunctional oxygen evolution and oxygen reduction acidic media electro-catalysts

    PubMed Central

    Patel, Prasad Prakash; Datta, Moni Kanchan; Velikokhatnyi, Oleg I.; Kuruba, Ramalinga; Damodaran, Krishnan; Jampani, Prashanth; Gattu, Bharat; Shanthi, Pavithra Murugavel; Damle, Sameer S.; Kumta, Prashant N.

    2016-01-01

    Identification of low cost, highly active, durable completely noble metal-free electro-catalyst for oxygen reduction reaction (ORR) in proton exchange membrane (PEM) fuel cells, oxygen evolution reaction (OER) in PEM based water electrolysis and metal air batteries remains one of the major unfulfilled scientific and technological challenges of PEM based acid mediated electro-catalysts. In contrast, several non-noble metals based electro-catalysts have been identified for alkaline and neutral medium water electrolysis and fuel cells. Herein we report for the very first time, F doped Cu1.5Mn1.5O4, identified by exploiting theoretical first principles calculations for ORR and OER in PEM based systems. The identified novel noble metal-free electro-catalyst showed similar onset potential (1.43 V for OER and 1 V for ORR vs RHE) to that of IrO2 and Pt/C, respectively. The system also displayed excellent electrochemical activity comparable to IrO2 for OER and Pt/C for ORR, respectively, along with remarkable long term stability for 6000 cycles in acidic media validating theory, while also displaying superior methanol tolerance and yielding recommended power densities in full cell configurations. PMID:27380719

  20. Effects of Computer-Aided Manufacturing Technology on Precision of Clinical Metal-Free Restorations

    PubMed Central

    Lee, Ki-Hong; Yeo, In-Sung; Wu, Benjamin M.; Yang, Jae-Ho; Han, Jung-Suk; Kim, Sung-Hun; Yi, Yang-Jin; Kwon, Taek-Ka

    2015-01-01

    Purpose. The purpose of this study was to investigate the marginal fit of metal-free crowns made by three different computer-aided design/computer-aided manufacturing (CAD/CAM) systems. Materials and Methods. The maxillary left first premolar of a dentiform was prepared for all-ceramic crown restoration. Thirty all-ceramic premolar crowns were made, ten each manufactured by the Lava system, Cercon, and Cerec. Ten metal ceramic gold (MCG) crowns served as control. The marginal gap of each sample was measured under a stereoscopic microscope at 75x magnification after cementation. One-way ANOVA and the Duncan's post hoc test were used for data analysis at the significance level of 0.05. Results. The mean (standard deviation) marginal gaps were 70.5 (34.4) μm for the MCG crowns, 87.2 (22.8) μm for Lava, 58.5 (17.6) μm for Cercon, and 72.3 (30.8) μm for Cerec. There were no significant differences in the marginal fit among the groups except that the Cercon crowns had significantly smaller marginal gaps than the Lava crowns (P < 0.001).  Conclusions. Within the limitation of this study, all the metal-free restorations made by the digital CAD/CAM systems had clinically acceptable marginal accuracy. PMID:26557681

  1. Metal-free photochemical silylations and transfer hydrogenations of benzenoid hydrocarbons and graphene

    NASA Astrophysics Data System (ADS)

    Papadakis, Raffaello; Li, Hu; Bergman, Joakim; Lundstedt, Anna; Jorner, Kjell; Ayub, Rabia; Haldar, Soumyajyoti; Jahn, Burkhard O.; Denisova, Aleksandra; Zietz, Burkhard; Lindh, Roland; Sanyal, Biplab; Grennberg, Helena; Leifer, Klaus; Ottosson, Henrik

    2016-10-01

    The first hydrogenation step of benzene, which is endergonic in the electronic ground state (S0), becomes exergonic in the first triplet state (T1). This is in line with Baird's rule, which tells that benzene is antiaromatic and destabilized in its T1 state and also in its first singlet excited state (S1), opposite to S0, where it is aromatic and remarkably unreactive. Here we utilized this feature to show that benzene and several polycyclic aromatic hydrocarbons (PAHs) to various extents undergo metal-free photochemical (hydro)silylations and transfer-hydrogenations at mild conditions, with the highest yield for naphthalene (photosilylation: 21%). Quantum chemical computations reveal that T1-state benzene is excellent at H-atom abstraction, while cyclooctatetraene, aromatic in the T1 and S1 states according to Baird's rule, is unreactive. Remarkably, also CVD-graphene on SiO2 is efficiently transfer-photohydrogenated using formic acid/water mixtures together with white light or solar irradiation under metal-free conditions.

  2. NIR Absorbing Metal-Free Organic, Porphyrin, and Phthalocyanine Dyes for Panchromatic DSCs.

    PubMed

    Brogdon, Phillip; Cheema, Hammad; Delcamp, Jared Heath

    2017-09-19

    Dye-sensitized solar cells (DSCs) are a promising source of renewable energy. However, power conversion efficiency (PCE) of devices has been limited largely by the difficulty of producing electricity using photons from the near-infrared (NIR) spectral region. Metal-free organic sensitizers frequently employ strong electron donating or withdrawing moieties to tune the optical band gap to allow the absorption of lower energy wavelengths in charge transfer systems while porphyrins and phthalocyanines use substituents to shift the Soret and Q bands toward lower energy absorption. Very few devices employing precious metal free dyes have been able to achieve panchromatic, NIR photon conversion for electricity generation at wavelengths >750 nm despite a tremendous number of sensitizers published over last 25 years. This minireview seeks to compile a summary of these sensitizers to encourage assimilation, analysis and development of efficient future NIR sensitizers. Herein, we discuss common synthetic strategies, optical properties and electronic properties of the most successful panchromatic organic sensitizers in this regard. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Metal-free photochemical silylations and transfer hydrogenations of benzenoid hydrocarbons and graphene

    PubMed Central

    Papadakis, Raffaello; Li, Hu; Bergman, Joakim; Lundstedt, Anna; Jorner, Kjell; Ayub, Rabia; Haldar, Soumyajyoti; Jahn, Burkhard O.; Denisova, Aleksandra; Zietz, Burkhard; Lindh, Roland; Sanyal, Biplab; Grennberg, Helena; Leifer, Klaus; Ottosson, Henrik

    2016-01-01

    The first hydrogenation step of benzene, which is endergonic in the electronic ground state (S0), becomes exergonic in the first triplet state (T1). This is in line with Baird's rule, which tells that benzene is antiaromatic and destabilized in its T1 state and also in its first singlet excited state (S1), opposite to S0, where it is aromatic and remarkably unreactive. Here we utilized this feature to show that benzene and several polycyclic aromatic hydrocarbons (PAHs) to various extents undergo metal-free photochemical (hydro)silylations and transfer-hydrogenations at mild conditions, with the highest yield for naphthalene (photosilylation: 21%). Quantum chemical computations reveal that T1-state benzene is excellent at H-atom abstraction, while cyclooctatetraene, aromatic in the T1 and S1 states according to Baird's rule, is unreactive. Remarkably, also CVD-graphene on SiO2 is efficiently transfer-photohydrogenated using formic acid/water mixtures together with white light or solar irradiation under metal-free conditions. PMID:27708336

  4. The electrochemical and spectroelectrochemical properties of metal free and metallophthalocyanines containing triazole/piperazine units

    NASA Astrophysics Data System (ADS)

    Demirbaş, Ümit; Akyüz, Duygu; Mermer, Arif; Akçay, Hakkı Türker; Demirbaş, Neslihan; Koca, Atıf; Kantekin, Halit

    2016-01-01

    The synthesis and characterization of novel peripherally tetra [1,2,4]-triazole substituted metal-free phthalocyanine and its metal complexes (Zn(II), Ni(II), Pb(II), Cu(II) and Fe(II)) and the investigation of electrochemical and spectroelectrochemical properties of metal-free, Zn(II), Pb(II), Fe(II) phthalocyanines were performed for the first time in this study. Electrochemical characterizations of the complexes were performed with voltammetric and in situ spectroelectrochemical measurements. Voltammetric responses of the complexes supported the proposed structures, since complexes bearing redox inactive Pc ring metal centers just gave Pc based electron transfer reactions, while iron phthalocyanine went to metal based electron transfer reaction in addition to the Pc based ones. Electron withdrawing nature of [1,2,4]-triazole substituents shifted the redox processes toward the positive potentials. All complexes were electropolymerized during the oxidation reactions in dichloromethane (DCM) solvent. Types of the metal center of the complexes altered the electropolymerization reactions of the complexes. Spectra and colors of the electrogenerated redox species of the complexes were also determined with in situ spectroelectrochemical and in situ electrocolorimetric measurements.

  5. Metal-Free cAMP-Dependent Protein Kinase Can Catalyze Phosphoryl Transfer

    PubMed Central

    2015-01-01

    X-ray structures of several ternary product complexes of the catalytic subunit of cAMP-dependent protein kinase (PKAc) have been determined with no bound metal ions and with Na+ or K+ coordinated at two metal-binding sites. The metal-free PKAc and the enzyme with alkali metals were able to facilitate the phosphoryl transfer reaction. In all studied complexes, the ATP and the substrate peptide (SP20) were modified into the products ADP and the phosphorylated peptide. The products of the phosphotransfer reaction were also found when ATP-γS, a nonhydrolyzable ATP analogue, reacted with SP20 in the PKAc active site containing no metals. Single turnover enzyme kinetics measurements utilizing 32P-labeled ATP confirmed the phosphotransferase activity of the enzyme in the absence of metal ions and in the presence of alkali metals. In addition, the structure of the apo-PKAc binary complex with SP20 suggests that the sequence of binding events may become ordered in a metal-free environment, with SP20 binding first to prime the enzyme for subsequent ATP binding. Comparison of these structures reveals conformational and hydrogen bonding changes that might be important for the mechanism of catalysis. PMID:24786636

  6. Noble metal-free bifunctional oxygen evolution and oxygen reduction acidic media electro-catalysts

    NASA Astrophysics Data System (ADS)

    Patel, Prasad Prakash; Datta, Moni Kanchan; Velikokhatnyi, Oleg I.; Kuruba, Ramalinga; Damodaran, Krishnan; Jampani, Prashanth; Gattu, Bharat; Shanthi, Pavithra Murugavel; Damle, Sameer S.; Kumta, Prashant N.

    2016-07-01

    Identification of low cost, highly active, durable completely noble metal-free electro-catalyst for oxygen reduction reaction (ORR) in proton exchange membrane (PEM) fuel cells, oxygen evolution reaction (OER) in PEM based water electrolysis and metal air batteries remains one of the major unfulfilled scientific and technological challenges of PEM based acid mediated electro-catalysts. In contrast, several non-noble metals based electro-catalysts have been identified for alkaline and neutral medium water electrolysis and fuel cells. Herein we report for the very first time, F doped Cu1.5Mn1.5O4, identified by exploiting theoretical first principles calculations for ORR and OER in PEM based systems. The identified novel noble metal-free electro-catalyst showed similar onset potential (1.43 V for OER and 1 V for ORR vs RHE) to that of IrO2 and Pt/C, respectively. The system also displayed excellent electrochemical activity comparable to IrO2 for OER and Pt/C for ORR, respectively, along with remarkable long term stability for 6000 cycles in acidic media validating theory, while also displaying superior methanol tolerance and yielding recommended power densities in full cell configurations.

  7. Heavy-Metal-Free Fluorescent ZnTe/ZnSe Nanodumbbells.

    PubMed

    Ji, Botao; Panfil, Yossef E; Banin, Uri

    2017-07-25

    For visible range emitting particles, which are relevant for display and additional applications, Cd-chalcogenide nanocrystals have reached the highest degree of control and performance. Considering potential toxicity and regulatory limitations, there is a challenge to successfully develop Cd-free emitting nanocrystals and, in particular, heterostructures with desirable properties. Herein, we report a colloidal synthesis of fluorescent heavy-metal-free Zn-chalcogenide semiconductor nanodumbbells (NDBs), in which ZnSe tips were selectively grown on the apexes of ZnTe rods, as evidenced by a variety of methods. The fluorescence of the NDBs can be tuned between ∼500 and 585 nm by changing the ZnSe tip size. The emission quantum yield can be greatly increased through chloride surface treatment and reaches more than 30%. Simulations within an effective-mass-based model show that the hole wave function is spread over the ZnTe nanorods, while the electron wave function is localized on the ZnSe tips. Quantitative agreement for the red-shifted emission wavelength is obtained between the simulations and the experiments. Additionally, the changes in radiative lifetimes correlate well with the calculated decrease in electron-hole overlap upon growth of larger ZnSe tips. The heavy-metal-free ZnTe/ZnSe NDBs may be relevant for optoelectronic applications such as displays or light-emitting diodes.

  8. Injectable dextran hydrogels fabricated by metal-free click chemistry for cartilage tissue engineering.

    PubMed

    Wang, Xiaoyu; Li, Zihan; Shi, Ting; Zhao, Peng; An, Kangkang; Lin, Chao; Liu, Hongwei

    2017-04-01

    Injectable dextran-based hydrogels were prepared for the first time by bioorthogonal click chemistry for cartilage tissue engineering. Click-crosslinked injectable hydrogels based on cyto-compatible dextran (Mw=10kDa) were successfully fabricated under physiological conditions by metal-free alkyne-azide cycloaddition (click) reaction between azadibenzocyclooctyne-modified dextran (Dex-ADIBO) and azide-modified dextran (Dex-N3). Gelation time of these dextran hydrogels could be regulated in the range of approximately 1.1 to 10.2min, depending on the polymer concentrations (5% or 10%) and ADIBO substitution degree (DS, 5 or 10) of Dex-ADIBO. Rheological analysis indicated that the dextran hydrogels were elastic and had storage moduli from 2.1 to 6.0kPa with increasing DS of ADIBO from 5 to 10. The in vitro tests revealed that the dextran hydrogel crosslinked from Dex-ADIBO DS 10 and Dex-N3 DS 10 at a polymer concentration of 10% could support high viability of individual rabbit chondrocytes and the chondrocyte spheroids encapsulated in the hydrogel over 21days. Individual chondrocytes and chondrocyte spheroids in the hydrogel could produce cartilage matrices such as collagen and glycosaminoglycans. However, the chondrocyte spheroids produced a higher content of matrices than individual chondrocytes. This study indicates that metal-free click chemistry is effective to produce injectable dextran hydrogels for cartilage tissue engineering. Copyright © 2016 Elsevier B.V. All rights reserved.

  9. Room temperature phosphorescence of metal-free organic materials in amorphous polymer matrices.

    PubMed

    Lee, Dongwook; Bolton, Onas; Kim, Byoung Choul; Youk, Ji Ho; Takayama, Shuichi; Kim, Jinsang

    2013-04-24

    Developing metal-free organic phosphorescent materials is promising but challenging because achieving emissive triplet relaxation that outcompetes the vibrational loss of triplets, a key process to achieving phosphorescence, is difficult without heavy metal atoms. While recent studies reveal that bright room temperature phosphorescence can be realized in purely organic crystalline materials through directed halogen bonding, these organic phosphors still have limitations to practical applications due to the stringent requirement of high quality crystal formation. Here we report bright room temperature phosphorescence by embedding a purely organic phosphor into an amorphous glassy polymer matrix. Our study implies that the reduced beta (β)-relaxation of isotactic PMMA most efficiently suppresses vibrational triplet decay and allows the embedded organic phosphors to achieve a bright 7.5% phosphorescence quantum yield. We also demonstrate a microfluidic device integrated with a novel temperature sensor based on the metal-free purely organic phosphors in the temperature-sensitive polymer matrix. This unique system has many advantages: (i) simple device structures without feeding additional temperature sensing agents, (ii) bright phosphorescence emission, (iii) a reversible thermal response, and (iv) tunable temperature sensing ranges by using different polymers.

  10. Metal-free photochemical silylations and transfer hydrogenations of benzenoid hydrocarbons and graphene.

    PubMed

    Papadakis, Raffaello; Li, Hu; Bergman, Joakim; Lundstedt, Anna; Jorner, Kjell; Ayub, Rabia; Haldar, Soumyajyoti; Jahn, Burkhard O; Denisova, Aleksandra; Zietz, Burkhard; Lindh, Roland; Sanyal, Biplab; Grennberg, Helena; Leifer, Klaus; Ottosson, Henrik

    2016-10-06

    The first hydrogenation step of benzene, which is endergonic in the electronic ground state (S0), becomes exergonic in the first triplet state (T1). This is in line with Baird's rule, which tells that benzene is antiaromatic and destabilized in its T1 state and also in its first singlet excited state (S1), opposite to S0, where it is aromatic and remarkably unreactive. Here we utilized this feature to show that benzene and several polycyclic aromatic hydrocarbons (PAHs) to various extents undergo metal-free photochemical (hydro)silylations and transfer-hydrogenations at mild conditions, with the highest yield for naphthalene (photosilylation: 21%). Quantum chemical computations reveal that T1-state benzene is excellent at H-atom abstraction, while cyclooctatetraene, aromatic in the T1 and S1 states according to Baird's rule, is unreactive. Remarkably, also CVD-graphene on SiO2 is efficiently transfer-photohydrogenated using formic acid/water mixtures together with white light or solar irradiation under metal-free conditions.

  11. Metal-free cAMP-dependent protein kinase can catalyze phosphoryl transfer.

    PubMed

    Gerlits, Oksana; Das, Amit; Keshwani, Malik M; Taylor, Susan; Waltman, Mary Jo; Langan, Paul; Heller, William T; Kovalevsky, Andrey

    2014-05-20

    X-ray structures of several ternary product complexes of the catalytic subunit of cAMP-dependent protein kinase (PKAc) have been determined with no bound metal ions and with Na(+) or K(+) coordinated at two metal-binding sites. The metal-free PKAc and the enzyme with alkali metals were able to facilitate the phosphoryl transfer reaction. In all studied complexes, the ATP and the substrate peptide (SP20) were modified into the products ADP and the phosphorylated peptide. The products of the phosphotransfer reaction were also found when ATP-γS, a nonhydrolyzable ATP analogue, reacted with SP20 in the PKAc active site containing no metals. Single turnover enzyme kinetics measurements utilizing (32)P-labeled ATP confirmed the phosphotransferase activity of the enzyme in the absence of metal ions and in the presence of alkali metals. In addition, the structure of the apo-PKAc binary complex with SP20 suggests that the sequence of binding events may become ordered in a metal-free environment, with SP20 binding first to prime the enzyme for subsequent ATP binding. Comparison of these structures reveals conformational and hydrogen bonding changes that might be important for the mechanism of catalysis.

  12. Noble metal-free bifunctional oxygen evolution and oxygen reduction acidic media electro-catalysts

    SciTech Connect

    Patel, Prasad Prakash; Datta, Moni Kanchan; Velikokhatnyi, Oleg I.; Kuruba, Ramalinga; Damodaran, Krishnan; Jampani, Prashanth; Gattu, Bharat; Shanthi, Pavithra Murugavel; Damle, Sameer S.; Kumta, Prashant N.

    2016-07-06

    We report that identification of low cost, highly active, durable completely noble metal-free electro-catalyst for oxygen reduction reaction (ORR) in proton exchange membrane (PEM) fuel cells, oxygen evolution reaction (OER) in PEM based water electrolysis and metal air batteries remains one of the major unfulfilled scientific and technological challenges of PEM based acid mediated electro-catalysts. In contrast, several non-noble metals based electro-catalysts have been identified for alkaline and neutral medium water electrolysis and fuel cells. Furthermore, we report for the very first time, F doped Cu1.5Mn1.5O4, identified by exploiting theoretical first principles calculations for ORR and OER in PEM based systems. The identified novel noble metal-free electro-catalyst showed similar onset potential (1.43 V for OER and 1 V for ORR vs RHE) to that of IrO2 and Pt/C, respectively. The system also displayed excellent electrochemical activity comparable to IrO2 for OER and Pt/C for ORR, respectively, along with remarkable long term stability for 6000 cycles in acidic media validating theory, while also displaying superior methanol tolerance and yielding recommended power densities in full cell configurations.

  13. Noble metal-free bifunctional oxygen evolution and oxygen reduction acidic media electro-catalysts

    DOE PAGES

    Patel, Prasad Prakash; Datta, Moni Kanchan; Velikokhatnyi, Oleg I.; ...

    2016-07-06

    We report that identification of low cost, highly active, durable completely noble metal-free electro-catalyst for oxygen reduction reaction (ORR) in proton exchange membrane (PEM) fuel cells, oxygen evolution reaction (OER) in PEM based water electrolysis and metal air batteries remains one of the major unfulfilled scientific and technological challenges of PEM based acid mediated electro-catalysts. In contrast, several non-noble metals based electro-catalysts have been identified for alkaline and neutral medium water electrolysis and fuel cells. Furthermore, we report for the very first time, F doped Cu1.5Mn1.5O4, identified by exploiting theoretical first principles calculations for ORR and OER in PEM basedmore » systems. The identified novel noble metal-free electro-catalyst showed similar onset potential (1.43 V for OER and 1 V for ORR vs RHE) to that of IrO2 and Pt/C, respectively. The system also displayed excellent electrochemical activity comparable to IrO2 for OER and Pt/C for ORR, respectively, along with remarkable long term stability for 6000 cycles in acidic media validating theory, while also displaying superior methanol tolerance and yielding recommended power densities in full cell configurations.« less

  14. System specification for the reusable reentry satellite

    NASA Technical Reports Server (NTRS)

    1991-01-01

    The RRS design shall provide a relatively inexpensive method of access to micro and fractional gravity space environments for an extended period of time, with eventual intact recovery on the surface of the Earth. This specification establishes the performance, design, development, and test requirements for the Reusable Reentry Satellite (RRS) system.

  15. FEEDBACK SCORING SYSTEMS FOR REUSABLE KINDERGARTEN WORKBOOKS.

    ERIC Educational Resources Information Center

    GACH, PENELOPE J.; AND OTHERS

    THE DEVELOPMENT OF ECONOMICAL FEEDBACK SCORING SYSTEMS FOR REUSABLE KINDERGARTEN WORKBOOKS IS DESCRIBED. THREE PROTOTYPE SYSTEMS WERE DEVELOPED--(1) A METAL FOIL ACTIVATING AN ELECTRICAL PROBE, (2) A METAL FOIL REACTING WITH A MAGNETIC PROBE, AND (3) INVISIBLE FLUORESCENT INK REVEALED BY THE APPLICATION OF LONGWAVE ULTRAVIOLET LIGHT. (MS)

  16. The Venture Star Reusable Launch Vehicle

    NASA Technical Reports Server (NTRS)

    1996-01-01

    In this artist's concept, the X-33 Venture Star, a Reusable Launch Vehicle (RLV), manufactured by Lockheed Martin Skunk Works, is shown in orbit with a deployed payload. The Venture Star was one of the earliest versions of the RLV's developed to replace the aging shuttle fleet. The X-33 program was cancelled in 2001.

  17. X-33 Venture Star - Reusable Launch Vehicle

    NASA Technical Reports Server (NTRS)

    1996-01-01

    In this artist's concept, the X-33 Venture Star, a Reusable Launch Vehicle (RLV), manufactured by Lockheed Martin Skunk Works, is shown in orbit with a deployed payload. The Venture Star was one of the earliest versions of the RLV's developed to replace the aging shuttle fleet. The X-33 program was cancelled in 2001.

  18. Reusable surface insulation materials research and development

    NASA Technical Reports Server (NTRS)

    Goldstein, H. E.; Buckley, J. D.; King, H. M.; Probst, H. B.; Spiker, I. K.

    1972-01-01

    Reusable surface insulation is considered a prime candidate for heat shielding large areas of the space shuttle vehicle. The composition and fabrication of RSI materials are discussed, followed by evolution of RSI and current problems, physical and thermal properties, arc plasma test data and results, and material improvement research. Finally, a summary of RSI technology status is presented.

  19. Reusable Reentry Satellite (RRS): Launch tradeoff study

    NASA Technical Reports Server (NTRS)

    1990-01-01

    A goal of the Phase B study is to define the launch system interfaces for the reusable reentry satellite (RRS) program. The focus of the launch tradeoff study, documented in this report, is to determine which expendable launch vehicles (ELV's) are best suited for the RRS application by understanding the impact of all viable launch systems on RRS design and operation.

  20. Key technology for reusable rocket engine turbopump

    NASA Astrophysics Data System (ADS)

    Okayasu, A.; Ohta, T.; Kamijyo, A.; Yamada, H.

    2002-03-01

    Recently, there has been an increased need for evolved space transportation and the research of reusable rocket which enable low cost and high reliability and is generating a lot of interest all over the world. In the USA, the development of reusable launch vehicle "Venture Star" which will be used instead of space shuttle is planned and its half scale model "X-33" was developed for the first flight in 1999. In Japan, there has been agreement on the main points to develop the rocket type RLV based on the technology of H-IIA, HOPE-X before developing space plane type RLV. The planned reusable rocket engine was LOX/LH2 as propellant, has 100- 200 ton thrust and has a throttling capability. In addition, long life and high reliability are required for the engine system including LOX/LH2 turbopump. The paper introduces some key technologies for the reusable turbopump which IHI is promoting for research and development with NAL and Tohoku University.

  1. Development Status of Reusable Rocket Engine

    NASA Astrophysics Data System (ADS)

    Yoshida, Makoto; Takada, Satoshi; Naruo, Yoshihiro; Niu, Kenichi

    A 30-kN rocket engine, a pilot engine, is being developed in Japan. Development of this pilot engine has been initiated in relation to a reusable sounding rocket, which is also being developed in Japan. This rocket takes off vertically, reaches an altitude of 100 km, lands vertically at the launch site, and is launched again within several days. Due to advantage of reusability, successful development of this rocket will mean that observation missions can be carried out more frequently and economically. In order to realize this rocket concept, the engines installed on the rocket should be characterized by reusability, long life, deep throttling and health monitoring, features which have not yet been established in Japanese rocket engines. To solve the engineering factors entitled by those features, a new design methodology, advanced engine simulations and engineering testing are being focused on in the pilot engine development stage. Especially in engineering testing, limit condition data is acquired to facilitate development of new diagnostic techniques, which can be applied by utilizing the mobility of small-size hardware. In this paper, the development status of the pilot engine is described, including fundamental design and engineering tests of the turbopump bearing and seal, turbine rig, injector and combustion chamber, and operation and maintenance concepts for one hundred flights by a reusable rocket are examined.

  2. Creating Reusable Educational Components: Lessons from DLESE.

    ERIC Educational Resources Information Center

    Sumner, Tamara; Dawe, Melissa; Devaul, Holly

    2002-01-01

    Studies the reuse of educational materials in the context of the Digital Library for Earth System Education (DLESE). Suggests that the 'findability' and reusability of community-created digital educational resources is highly dependent on the presentational and structural design of the resources themselves. Includes 15 references. (Author/YDS)

  3. Reusable cryogenic liquid rocket propellant tank

    NASA Astrophysics Data System (ADS)

    Freeman, William T.; MacConochie, Ian O.; Breiner, Charles A.; Bryan, Charles F., Jr.

    1993-07-01

    A reusable liquid rocket propellant tank is provided. The tank consists of a composite outer shell, a foam-filled honeycomb sandwich insulation layer bonded to the inner surface of the composite shell and a collapsible inner lining which may be removed from the outer shell for inspection and replacement.

  4. 14 CFR 437.67 - Tracking a reusable suborbital rocket.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... 14 Aeronautics and Space 4 2012-01-01 2012-01-01 false Tracking a reusable suborbital rocket. 437... a reusable suborbital rocket. A permittee must— (a) During permitted flight, measure in real time the position and velocity of its reusable suborbital rocket; and (b) Provide position and velocity...

  5. 14 CFR 437.67 - Tracking a reusable suborbital rocket.

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ... 14 Aeronautics and Space 4 2014-01-01 2014-01-01 false Tracking a reusable suborbital rocket. 437... a reusable suborbital rocket. A permittee must— (a) During permitted flight, measure in real time the position and velocity of its reusable suborbital rocket; and (b) Provide position and velocity...

  6. 14 CFR 437.67 - Tracking a reusable suborbital rocket.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 14 Aeronautics and Space 4 2010-01-01 2010-01-01 false Tracking a reusable suborbital rocket. 437... a reusable suborbital rocket. A permittee must— (a) During permitted flight, measure in real time the position and velocity of its reusable suborbital rocket; and (b) Provide position and velocity...

  7. 14 CFR 437.67 - Tracking a reusable suborbital rocket.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... 14 Aeronautics and Space 4 2013-01-01 2013-01-01 false Tracking a reusable suborbital rocket. 437... a reusable suborbital rocket. A permittee must— (a) During permitted flight, measure in real time the position and velocity of its reusable suborbital rocket; and (b) Provide position and velocity...

  8. 14 CFR 437.67 - Tracking a reusable suborbital rocket.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... 14 Aeronautics and Space 4 2011-01-01 2011-01-01 false Tracking a reusable suborbital rocket. 437... a reusable suborbital rocket. A permittee must— (a) During permitted flight, measure in real time the position and velocity of its reusable suborbital rocket; and (b) Provide position and velocity...

  9. Reusable Space Vehicle Ground Operations Baseline Conceptual Model

    DTIC Science & Technology

    2004-03-01

    REUSABLE SPACE VEHICLE GROUND OPERATIONS BASELINE CONCEPTUAL MODEL THESIS DENNIS R...United States Air Force, Department of Defense, or the United States Government. AFIT/GLM/ENS/04-12 REUSABLE SPACE VEHICLE GROUND...for the next launch. v AFIT/GLM/ENS/04-12 REUSABLE SPACE VEHICLE GROUND OPERATIONS BASELINE CONCEPTUAL MODEL DENNIS R. MAYNARD

  10. 76 FR 45268 - Reprocessing of Reusable Medical Devices

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-07-28

    ... HUMAN SERVICES Food and Drug Administration Reprocessing of Reusable Medical Devices AGENCY: Food and... Administration (FDA) is considering factors affecting the reprocessing of reusable medical devices, including reprocessing quality, device design as it relates to the reprocessing of reusable medical devices, reprocessing...

  11. Transitions.

    ERIC Educational Resources Information Center

    Field, David; And Others

    1992-01-01

    Includes four articles: "Career Aspirations" (Field); "Making the Transition to a New Curriculum" (Baker, Householder); "How about a 'Work to School' Transition?" (Glasberg); and "Technological Improvisation: Bringing CNC to Woodworking" (Charles, McDuffie). (SK)

  12. Characterizing the conformational dynamics of metal-free PsaA using molecular dynamics simulations and electron paramagnetic resonance spectroscopy.

    PubMed

    Deplazes, Evelyne; Begg, Stephanie L; van Wonderen, Jessica H; Campbell, Rebecca; Kobe, Bostjan; Paton, James C; MacMillan, Fraser; McDevitt, Christopher A; O'Mara, Megan L

    2015-12-01

    Prokaryotic metal-ion receptor proteins, or solute-binding proteins, facilitate the acquisition of metal ions from the extracellular environment. Pneumococcal surface antigen A (PsaA) is the primary Mn(2+)-recruiting protein of the human pathogen Streptococcus pneumoniae and is essential for its in vivo colonization and virulence. The recently reported high-resolution structures of metal-free and metal-bound PsaA have provided the first insights into the mechanism of PsaA-facilitated metal binding. However, the conformational dynamics of metal-free PsaA in solution remain unknown. Here, we use continuous wave electron paramagnetic resonance (EPR) spectroscopy and molecular dynamics (MD) simulations to study the relative flexibility of the structural domains in metal-free PsaA and its distribution of conformations in solution. The results show that the crystal structure of metal-free PsaA is a good representation of the dominant conformation in solution, but the protein also samples structurally distinct conformations that are not captured by the crystal structure. Further, these results suggest that the metal binding site is both larger and more solvent exposed than indicated by the metal-free crystal structure. Collectively, this study provides atomic-resolution insight into the conformational dynamics of PsaA prior to metal binding and lays the groundwork for future EPR and MD based studies of PsaA in solution. Copyright © 2015 Elsevier B.V. All rights reserved.

  13. Metal-free organic sensitizers for use in water-splitting dye-sensitized photoelectrochemical cells

    PubMed Central

    Swierk, John R.; Méndez-Hernández, Dalvin D.; McCool, Nicholas S.; Liddell, Paul; Terazono, Yuichi; Pahk, Ian; Tomlin, John J.; Oster, Nolan V.; Moore, Thomas A.; Moore, Ana L.; Gust, Devens; Mallouk, Thomas E.

    2015-01-01

    Solar fuel generation requires the efficient capture and conversion of visible light. In both natural and artificial systems, molecular sensitizers can be tuned to capture, convert, and transfer visible light energy. We demonstrate that a series of metal-free porphyrins can drive photoelectrochemical water splitting under broadband and red light (λ > 590 nm) illumination in a dye-sensitized TiO2 solar cell. We report the synthesis, spectral, and electrochemical properties of the sensitizers. Despite slow recombination of photoinjected electrons with oxidized porphyrins, photocurrents are low because of low injection yields and slow electron self-exchange between oxidized porphyrins. The free-base porphyrins are stable under conditions of water photoelectrolysis and in some cases photovoltages in excess of 1 V are observed. PMID:25583488

  14. Metal-Free Oxidative C-C Bond Formation through C-H Bond Functionalization.

    PubMed

    Narayan, Rishikesh; Matcha, Kiran; Antonchick, Andrey P

    2015-10-12

    The formation of C-C bonds embodies the core of organic chemistry because of its fundamental application in generation of molecular diversity and complexity. C-C bond-forming reactions are well-known challenges. To achieve this goal through direct functionalization of C-H bonds in both of the coupling partners represents the state-of-the-art in organic synthesis. Oxidative C-C bond formation obviates the need for prefunctionalization of both substrates. This Minireview is dedicated to the field of C-C bond-forming reactions through direct C-H bond functionalization under completely metal-free oxidative conditions. Selected important developments in this area have been summarized with representative examples and discussions on their reaction mechanisms. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Metal-Free Trifluoromethylation of Aromatic and Heteroaromatic Aldehydes and Ketones

    PubMed Central

    2015-01-01

    The ability to convert simple and common substrates into fluoroalkyl derivatives under mild conditions remains an important goal for medicinal and agricultural chemists. One representative example of a desirable transformation involves the conversion of aromatic and heteroaromatic ketones and aldehydes into aryl and heteroaryl β,β,β-trifluoroethylarenes and -heteroarenes. The traditional approach for this net transformation involves stoichiometric metals and/or multistep reaction sequences that consume excessive time, material, and labor resources while providing low yields of products. To complement these traditional strategies, we report a one-pot metal-free decarboxylative procedure for accessing β,β,β-trifluoroethylarenes and -heteroarenes from readily available ketones and aldehydes. This method features several benefits, including ease of operation, readily available reagents, mild reaction conditions, high functional-group compatibility, and scalability. PMID:25001876

  16. Water-gas-shift over metal-free nanocrystalline ceria: An experimental and theoretical study

    DOE PAGES

    Guild, Curtis J.; Vovchok, Dimitriy; Kriz, David A.; ...

    2017-01-23

    A tandem experimental and theoretical investigation of a mesoporous ceria catalyst reveals the properties of the metal oxide are conducive for activity typically ascribed to metals, suggesting reduced Ce3+ and oxygen vacancies are responsible for the inherent bi-functionality of CO oxidation and dissociation of water required for facilitating the production of H2. The degree of reduction of the ceria, specifically the (1 0 0) face, is found to significantly influence the binding of reagents, suggesting reduced surfaces harbor the necessary reactive sites. The metal-free catalysis of the reaction is significant for catalyst design considerations, and the suite of in situmore » analyses provides a comprehensive study of the dynamic nature of the high surface area catalyst system. Finally, this study postulates feasible improvements in catalytic activity may redirect the purpose of the water-gas shift reaction from CO purification to primary hydrogen production.« less

  17. Metal-free melem/g-C3N4 hybrid photocatalysts for water treatment.

    PubMed

    Liu, Shizhen; Sun, Hongqi; O'Donnell, Kane; Ang, H M; Tade, Moses O; Wang, Shaobin

    2016-02-15

    In this study, graphitic carbon nitride was engineered to produce metal-free melem/g-C3N4 hybrid photocatalysts through a hydrothermal technique. It was revealed that the hydrothermal treatment of g-C3N4 could produce a hybrid structure of "thorn ball" liked melem on g-C3N4 layer at a high temperature, and was able to modify the photoelectronic properties of g-C3N4. The spectroscopic measurements implied that a melem/g-C3N4 hybrid has better light absorption and lower electron/hole recombination than pristine g-C3N4. Therefore, the melem/g-C3N4 photocatalysts can decompose methylene blue solution under artificial sunlight with a higher rate and also present good stability.

  18. Hydrogen Sulfide Induced Carbon Dioxide Activation by Metal-Free Dual Catalysis.

    PubMed

    Kumar, Manoj; Francisco, Joseph S

    2016-03-18

    The role of metal free dual catalysis in the hydrogen sulfide (H2S)-induced activation of carbon dioxide (CO2) and subsequent decomposition of resulting monothiolcarbonic acid in the gas phase has been explored. The results suggest that substituted amines and monocarboxylic type organic or inorganic acids via dual activation mechanisms promote both activation and decomposition reactions, implying that the judicious selection of a dual catalyst is crucial to the efficient C-S bond formation via CO2 activation. Considering that our results also suggest a new mechanism for the formation of carbonyl sulfide from CO2 and H2S, these new insights may help in better understanding the coupling between the carbon and sulfur cycles in the atmospheres of Earth and Venus.

  19. Metal-free hybrids of graphitic carbon nitride and nanodiamonds for photoelectrochemical and photocatalytic applications.

    PubMed

    Zhou, Li; Zhang, Huayang; Guo, Xiaochen; Sun, Hongqi; Liu, Shaomin; Tade, Moses O; Wang, Shaobin

    2017-05-01

    Graphitic carbon nitride (g-C3N4) has been considered as a metal-free, cost-effective, eco-friendly and efficient catalyst for various photoelectrochemical applications. However, compared to conventional metal-based photocatalysts, its photocatalytic activity is still low because of the low mobility of carriers restricted by the polymer nature. Herein, a series of hybrids of g-C3N4 (GCN) and nanodiamonds (NDs) were synthesized using a solvothermal method. The photoelectrochemical performance and photocatalytic efficiency of the GCN/NDs were investigated by means of the generation of photocurrent and photodegradation of methylene blue (MB) solutions under UV-visible light irradiations. In this study, the sample of GCN/ND-33% derived from 0.1g GCN and 0.05g NDs displayed the highest photocatalytic activity and the strongest photocurrent density. The mechanism of enhanced photoelectrochemical and photocatalytic performances was also discussed.

  20. Metal-Free Nitrogen-Doped Mesoporous Carbon for Electroreduction of CO2 to Ethanol.

    PubMed

    Song, Yanfang; Chen, Wei; Zhao, Chengcheng; Li, Shenggang; Wei, Wei; Sun, Yuhan

    2017-08-28

    CO2 electroreduction is a promising technique for satisfying both renewable energy storage and a negative carbon cycle. However, it remains a challenge to convert CO2 into C2 products with high efficiency and selectivity. Herein, we report a nitrogen-doped ordered cylindrical mesoporous carbon as a robust metal-free catalyst for CO2 electroreduction, enabling the efficient production of ethanol with nearly 100 % selectivity and high faradaic efficiency of 77 % at -0.56 V versus the reversible hydrogen electrode. Experiments and density functional theory calculations demonstrate that the synergetic effect of the nitrogen heteroatoms and the cylindrical channel configurations facilitate the dimerization of key CO* intermediates and the subsequent proton-electron transfers, resulting in superior electrocatalytic performance for synthesizing ethanol from CO2 . © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Metal-free organic sensitizers for use in water-splitting dye-sensitized photoelectrochemical cells

    DOE PAGES

    Swierk, John R.; Méndez-Hernández, Dalvin D.; McCool, Nicholas S.; ...

    2015-01-12

    Solar fuel generation requires the efficient capture and conversion of visible light. In both natural and artificial systems, molecular sensitizers can be tuned to capture, convert, and transfer visible light energy. We demonstrate that a series of metal-free porphyrins can drive photoelectrochemical water splitting under broadband and red light (λ > 590 nm) illumination in a dye-sensitized TiO2 solar cell. Here, we report the synthesis, spectral, and electrochemical properties of the sensitizers. Despite slow recombination of photoinjected electrons with oxidized porphyrins, photocurrents are low because of low injection yields and slow electron self-exchange between oxidized porphyrins. As a result, themore » free-base porphyrins are stable under conditions of water photoelectrolysis and in some cases photovoltages in excess of 1 V are observed.« less

  2. Metal-free electrocatalytic hydrogen oxidation using frustrated Lewis pairs and carbon-based Lewis acids.

    PubMed

    Lawrence, Elliot J; Clark, Ewan R; Curless, Liam D; Courtney, James M; Blagg, Robin J; Ingleson, Michael J; Wildgoose, Gregory G

    2016-04-21

    Whilst hydrogen is a potentially clean fuel for energy storage and utilisation technologies, its conversion to electricity comes at a high energetic cost. This demands the use of rare and expensive precious metal electrocatalysts. Electrochemical-frustrated Lewis pairs offer a metal-free, CO tolerant pathway to the electrocatalysis of hydrogen oxidation. They function by combining the hydrogen-activating ability of frustrated Lewis pairs (FLPs) with electrochemical oxidation of the resultant hydride. Here we present an electrochemical-FLP approach that utilises two different Lewis acids - a carbon-based N-methylacridinium cation that possesses excellent electrochemical attributes, and a borane that exhibits fast hydrogen cleavage kinetics and functions as a "hydride shuttle". This synergistic interaction provides a system that is electrocatalytic with respect to the carbon-based Lewis acid, decreases the required potential for hydrogen oxidation by 1 V, and can be recycled multiple times.

  3. Metal-free flat lens using negative refraction by nonlinear four-wave mixing.

    PubMed

    Cao, Jianjun; Zheng, Yuanlin; Feng, Yaming; Chen, Xianfeng; Wan, Wenjie

    2014-11-21

    A perfect lens with unlimited resolution has always posed a challenge to both theoretical and experimental physicists. Recent developments in optical metamaterials promise an attractive approach towards perfect lenses using negative refraction to overcome the diffraction limit, improving resolution. However, those artificially engineered metamaterials are usually accompanied by high losses from metals and are extremely difficult to fabricate. An alternative proposal using negative refraction by four-wave mixing has attracted much interest recently, though most existing experiments still require metals and none of them have been implemented for an optical lens. Here, we experimentally demonstrate a metal-free flat lens for the first time using negative refraction by degenerate four-wave mixing with a thin glass slide. We realize an optical lensing effect utilizing a nonlinear refraction law, which may have potential applications in microscopy.

  4. In-plane graphene/boron-nitride heterostructures as an efficient metal-free electrocatalyst for the oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Sun, Qiao; Sun, Caixia; Du, Aijun; Dou, Shixue; Li, Zhen

    2016-07-01

    Exploiting metal-free catalysts for the oxygen reduction reaction (ORR) and understanding their catalytic mechanisms are vital for the development of fuel cells (FCs). Our study has demonstrated that in-plane heterostructures of graphene and boron nitride (G/BN) can serve as an efficient metal-free catalyst for the ORR, in which the C-N interfaces of G/BN heterostructures act as reactive sites. The formation of water at the heterointerface is both energetically and kinetically favorable via a four-electron pathway. Moreover, the water formed can be easily released from the heterointerface, and the catalytically active sites can be regenerated for the next cycle. Since G/BN heterostructures with controlled domain sizes have been successfully synthesized in recent reports (e.g. Nat. Nanotechnol., 2013, 8, 119), our results highlight the great potential of such heterostructures as a promising metal-free catalyst for the ORR in FCs.Exploiting metal-free catalysts for the oxygen reduction reaction (ORR) and understanding their catalytic mechanisms are vital for the development of fuel cells (FCs). Our study has demonstrated that in-plane heterostructures of graphene and boron nitride (G/BN) can serve as an efficient metal-free catalyst for the ORR, in which the C-N interfaces of G/BN heterostructures act as reactive sites. The formation of water at the heterointerface is both energetically and kinetically favorable via a four-electron pathway. Moreover, the water formed can be easily released from the heterointerface, and the catalytically active sites can be regenerated for the next cycle. Since G/BN heterostructures with controlled domain sizes have been successfully synthesized in recent reports (e.g. Nat. Nanotechnol., 2013, 8, 119), our results highlight the great potential of such heterostructures as a promising metal-free catalyst for the ORR in FCs. Electronic supplementary information (ESI) available. See DOI: 10.1039/c6nr03288e

  5. Heterogeneous Metal-Free Hydrogenation over Defect-Laden Hexagonal Boron Nitride

    DOE PAGES

    Nash, David J.; Restrepo, David T.; Parra, Natalia S.; ...

    2016-12-21

    Catalytic hydrogenation is an important process used for the production of everything from foods to fuels. Current heterogeneous implementations of this process utilize metals as the active species. Until recently, catalytic heterogeneous hydrogenation over a metal-free solid was unknown; implementation of such a system would eliminate the health, environmental, and economic concerns associated with metal-based catalysts. We report good hydrogenation rates and yields for a metal-free heterogeneous hydrogenation catalyst as well as its unique hydrogenation mechanism. We achieved catalytic hydrogenation of olefins over defect-laden h-BN (dh-BN) in a reactor designed to maximize the defects in h-BN sheets. Good yields (>90%)more » and turnover frequencies (6 × 10–5–4 × 10–3) were obtained for the hydrogenation of propene, cyclohexene, 1,1-diphenylethene, (E)- and (Z)-1,2-diphenylethene, octadecene, and benzylideneacetophenone. Temperature-programmed desorption of ethene over processed h-BN indicates the formation of a highly defective structure. Solid-state NMR (SSNMR) measurements of dh-BN with high and low propene surface coverages show four different binding modes. The introduction of defects into h-BN creates regions of electronic deficiency and excess. Density functional theory calculations show that both the alkene and hydrogen-bond order are reduced over four specific defects: boron substitution for nitrogen (BN), vacancies (VB and VN), and Stone–Wales defects. SSNMR and binding-energy calculations show that VN are most likely the catalytically active sites. Our work shows that catalytic sites can be introduced into a material previously thought to be catalytically inactive through the production of defects.« less

  6. A metal-free N-annulated thienocyclopentaperylene dye: power conversion efficiency of 12% for dye-sensitized solar cells.

    PubMed

    Yao, Zhaoyang; Zhang, Min; Li, Renzhi; Yang, Lin; Qiao, Yongna; Wang, Peng

    2015-05-11

    Reported are two highly efficient metal-free perylene dyes featuring N-annulated thienobenzoperylene (NTBP) and N-annulated thienocyclopentaperylene (NTCP), which are coplanar polycyclic aromatic hydrocarbons. Without the use of any coadsorbate, the metal-free organic dye derived from the NTCP segment was used for a dye-sensitized solar cell which attained a power conversion efficiency of 12% under an irradiance of 100 mW cm(-2), simulated air mass global (AM1.5G) sunlight. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. A Framework for Assessing the Reusability of Hardware (Reusable Rocket Engines)

    NASA Technical Reports Server (NTRS)

    Childress-Thompson, Rhonda; Farrington, Philip; Thomas, Dale

    2016-01-01

    Within the space flight community, reusability has taken center stage as the new buzzword. In order for reusable hardware to be competitive with its expendable counterpart, two major elements must be closely scrutinized. First, recovery and refurbishment costs must be lower than the development and acquisition costs. Additionally, the reliability for reused hardware must remain the same (or nearly the same) as "first use" hardware. Therefore, it is imperative that a systematic approach be established to enhance the development of reusable systems. However, before the decision can be made on whether it is more beneficial to reuse hardware or to replace it, the parameters that are needed to deem hardware worthy of reuse must be identified. For reusable hardware to be successful, the factors that must be considered are reliability (integrity, life, number of uses), operability (maintenance, accessibility), and cost (procurement, retrieval, refurbishment). These three factors are essential to the successful implementation of reusability while enabling the ability to meet performance goals. Past and present strategies and attempts at reuse within the space industry will be examined to identify important attributes of reusability that can be used to evaluate hardware when contemplating reusable versus expendable options. This paper will examine why reuse must be stated as an initial requirement rather than included as an afterthought in the final design. Late in the process, changes in the overall objective/purpose of components typically have adverse effects that potentially negate the benefits. A methodology for assessing the viability of reusing hardware will be presented by using the Space Shuttle Main Engine (SSME) to validate the approach. Because reliability, operability, and costs are key drivers in making this critical decision, they will be used to assess requirements for reuse as applied to components of the SSME.

  8. A Framework for Assessing the Reusability of Hardware (Reusable Rocket Engines)

    NASA Technical Reports Server (NTRS)

    Childress-Thompson, Rhonda; Thomas, Dale; Farrington, Phillip

    2016-01-01

    Within the space flight community, reusability has taken center stage as the new buzzword. In order for reusable hardware to be competitive with its expendable counterpart, two major elements must be closely scrutinized. First, recovery and refurbishment costs must be lower than the development and acquisition costs. Additionally, the reliability for reused hardware must remain the same (or nearly the same) as "first use" hardware. Therefore, it is imperative that a systematic approach be established to enhance the development of reusable systems. However, before the decision can be made on whether it is more beneficial to reuse hardware or to replace it, the parameters that are needed to deem hardware worthy of reuse must be identified. For reusable hardware to be successful, the factors that must be considered are reliability (integrity, life, number of uses), operability (maintenance, accessibility), and cost (procurement, retrieval, refurbishment). These three factors are essential to the successful implementation of reusability while enabling the ability to meet performance goals. Past and present strategies and attempts at reuse within the space industry will be examined to identify important attributes of reusability that can be used to evaluate hardware when contemplating reusable versus expendable options. This paper will examine why reuse must be stated as an initial requirement rather than included as an afterthought in the final design. Late in the process, changes in the overall objective/purpose of components typically have adverse effects that potentially negate the benefits. A methodology for assessing the viability of reusing hardware will be presented by using the Space Shuttle Main Engine (SSME) to validate the approach. Because reliability, operability, and costs are key drivers in making this critical decision, they will be used to assess requirements for reuse as applied to components of the SSME.

  9. Reusable space systems (Eugen Saenger Lecture, 1987)

    NASA Technical Reports Server (NTRS)

    Fletcher, J. C.

    1988-01-01

    The history and current status of reusable launch vehicle (RLV) development are surveyed, with emphases on the contributions of Eugen Saenger and ongoing NASA projects. Topics addressed include the capabilities and achievements of the Space Shuttle, the need to maintain a fleet with both ELVs and RLVs to meet different mission requirements, the X-30 testbed aircraft for the National Aerospace Plane program, current design concepts for Shuttle II (a 1000-ton fully reusable two-stage rocket-powered spacecraft capable of carrying 11,000 kg to Space Station orbit), proposals for dual-fuel-propulsion SSTO RLVs, and the Space Station Orbital Maneuvering Vehicle and Orbital Transfer Vehicle. The importance of RLVs and of international cooperation in establishing the LEO infrastructure needed for planetary exploration missions is stressed.

  10. Reusable space systems (Eugen Saenger Lecture, 1987)

    NASA Technical Reports Server (NTRS)

    Fletcher, J. C.

    1988-01-01

    The history and current status of reusable launch vehicle (RLV) development are surveyed, with emphases on the contributions of Eugen Saenger and ongoing NASA projects. Topics addressed include the capabilities and achievements of the Space Shuttle, the need to maintain a fleet with both ELVs and RLVs to meet different mission requirements, the X-30 testbed aircraft for the National Aerospace Plane program, current design concepts for Shuttle II (a 1000-ton fully reusable two-stage rocket-powered spacecraft capable of carrying 11,000 kg to Space Station orbit), proposals for dual-fuel-propulsion SSTO RLVs, and the Space Station Orbital Maneuvering Vehicle and Orbital Transfer Vehicle. The importance of RLVs and of international cooperation in establishing the LEO infrastructure needed for planetary exploration missions is stressed.

  11. Transition.

    ERIC Educational Resources Information Center

    Thompson, Sandy, Ed.; And Others

    1990-01-01

    This "feature issue" focuses on transition from school to adult life for persons with disabilities. Included are "success stories," brief program descriptions, and a list of resources. Individual articles include the following titles and authors: "Transition: An Energizing Concept" (Paul Bates); "Transition…

  12. Improvement of reusable surface insulation material

    NASA Technical Reports Server (NTRS)

    1972-01-01

    The results are presented of a program to improve the reusable surface insulation (RSI) system through the improvement of the LI-1500 material properties and the simplification of the RSI system. The improvements made include: 2500 F-capability RSI systems, water-impervious surface coatings, establishment of a high-emittance coating constituent, development of a secondary water-reduction system, and achievement of a lower density (9 pcf) RSI material.

  13. The Venture Star Reusable Launch Vehicle

    NASA Technical Reports Server (NTRS)

    1997-01-01

    This artist's concept is of the X-33 Advanced Technology Demonstrator, a subscale prototype Reusable Launch Vehicle (RLV), in its 1997 configuration. Named the Venture Star, this vehicle manufactured by Lockheed Martin Skunk Works, is shown in orbit with a deployed payload. The Venture Star was one of the earliest versions of the RLV's developed in attempt to replace the aging shuttle fleet. The X-33 program has been discontinued.

  14. The reusable launch vehicle technology program

    NASA Astrophysics Data System (ADS)

    Cook, S.

    Today's launch systems have major shortcomings that will increase in significance in the future, and thus are principal drivers for seeking major improvements in space transportation. They are too costly; insufficiently reliable, safe, and operable; and increasingly losing market share to international competition. For the United States to continue its leadership in the human exploration and wide ranging utilization of space, the first order of business must be to achieve low cost, reliable transportatin to Earth orbit. NASA's Access to Space Study, in 1993, recommended the development of a fully reusable single-stage-to-orbit (SSTO) rocket vehicle as an Agency goal. The goal of the Reusable Launch Vehicle (RLV) technology program is to mature the technologies essential for a next-generation reusable launch system capable of reliably serving National space transportation needs at substantially reduced costs. The primary objectives of the RLV technology program are to (1) mature the technologies required for the next-generation system, (2) demonstrate the capability to achieve low development and operational cost, and rapid launch turnaround times and (3) reduce business and technical risks to encourage significant private investment in the commercial development and operation of the next-generation system. Developing and demonstrating the technologies required for a Single Stage to Orbit (SSTO) rocket is a focus of the program becuase past studies indicate that it has the best potential for achieving the lowest space access cost while acting as an RLV technology driver (since it also encompasses the technology requirements of reusable rocket vehicles in general).

  15. Self-unloading, reusable, lunar lander project

    NASA Technical Reports Server (NTRS)

    Arseculeratne, Ruwan; Cavazos, Melissa; Euker, John; Ghavidel, Fred; Hinkel, Todd J.; Hitzfelder, John; Leitner, Jesse; Nevik, James; Paynter, Scott; Zolondek, Allen

    1990-01-01

    In the early 21st century, NASA will return to the Moon and establish a permanent base. To achieve this goal safely and economically, B&T Engineering has designed an unmanned, reusable, self-unloading lunar lander. The lander is designed to deliver 15,000 kg payloads from an orbit transfer vehicle (OTV) in a low lunar polar orbit and an altitude of 200 km to any location on the lunar surface.

  16. 24 Inch Reusable Solid Rocket Motor Test

    NASA Technical Reports Server (NTRS)

    2002-01-01

    A scaled-down 24-inch version of the Space Shuttle's Reusable Solid Rocket Motor was successfully fired for 21 seconds at a Marshall Space Flight Center (MSFC) Test Stand. The motor was tested to ensure a replacement material called Lycocel would meet the criteria set by the Shuttle's Solid Motor Project Office. The current material is a heat-resistant, rayon-based, carbon-cloth phenolic used as an insulating material for the motor's nozzle. Lycocel, a brand name for Tencel, is a cousin to rayon and is an exceptionally strong fiber made of wood pulp produced by a special 'solvent-spirning' process using a nontoxic solvent. It will also be impregnated with a phenolic resin. This new material is expected to perform better under the high temperatures experienced during launch. The next step will be to test the material on a 48-inch solid rocket motor. The test, which replicates launch conditions, is part of Shuttle's ongoing verification of components, materials, and manufacturing processes required by MSFC, which oversees the Reusable Solid Rocket Motor project. Manufactured by the ATK Thiokol Propulsion Division in Promontory, California, the Reusable Solid Rocket Motor measures 126 feet (38.4 meters) long and 12 feet (3.6 meters) in diameter. It is the largest solid rocket motor ever flown and the first designed for reuse. During its two-minute burn at liftoff, each motor generates an average thrust of 2.6 million pounds (1.2 million kilograms).

  17. Inventory management of reusable surgical supplies.

    PubMed

    Diamant, Adam; Milner, Joseph; Quereshy, Fayez; Xu, Bo

    2017-03-08

    We investigate the inventory management practices for reusable surgical instruments that must be sterilized between uses. We study a hospital that outsources their sterilization services and model the inventory process as a discrete-time Markov chain. We present two base-stock inventory models, one that considers stockout-based substitution and one that does not. We derive the optimal base-stock level for the number of reusable instruments to hold in inventory, the expected service level, and investigate the implied cost of a stockout. We apply our theoretical results to a dataset collected from a surgical unit at a large tertiary care hospital specializing in colorectal operations. We demonstrate how to implement our model when determining base-stock levels for future capacity expansion and when considering alternative stockout protocols. Our analysis suggests that the hospital can reduce the number of reusable instrument sets held in inventory if on-site sterilization techniques (e.g., flash sterilization) are employed. Our results will guide future procurement decisions for surgical units based on costs and desired service levels.

  18. Reusable fuel test assembly for the FFTF

    SciTech Connect

    Pitner, A.L.; Dittmer, J.O. )

    1992-01-01

    A fuel test assembly that provides re-irradiation capability after interim discharge and reconstitution of the test pin bundle has been developed for use in the Fast Flux Test Facility (FFTF). This test vehicle permits irradiation test data to be obtained at multiple exposures on a few select test pins without the substantial expense of fabricating individual test assemblies as would otherwise be required. A variety of test pin types can be loaded in the reusable test assembly. A reusable test vehicle for irradiation testing in the FFTF has long been desired, but a number of obstacles previously prevented the implementation of such an experimental rig. The MFF-8A test assembly employs a 169-pin bundle using HT-9 alloy for duct and cladding material. The standard driver pins in the fuel bundle are sodium-bonded metal fuel (U-10 wt% Zr). Thirty-seven positions in the bundle are replaceable pin positions. Standard MFF-8A driver pins can be loaded in any test pin location to fill the bundle if necessary. Application of the MFF-8A reusable test assembly in the FFTF constitutes a considerable cost-saving measure with regard to irradiation testing. Only a few well-characterized test pins need be fabricated to conduct a test program rather than constructing entire test assemblies.

  19. Metal-free transannulation reaction of indoles with nitrostyrenes: a simple practical synthesis of 3-substituted 2-quinolones†

    PubMed Central

    Aksenov, Alexander V.; Smirnov, Alexander N.; Aksenov, Nicolai A.; Aksenova, Inna V.; Frolova, Liliya V.; Kornienko, Alexander; Magedov, Igor V.; Rubin, Michael

    2016-01-01

    3-Substituted 2-quinolones are obtained via a novel, metal-free transannulation reaction of 2-substituted indoles with 2-nitroalkenes in polyphosphoric acid. The reaction can be used in conjunction with the Fisher indole synthesis offering a practical three-component heteroannulation methodology to produce 2-quinolones from arylhydrazines, 2-nitroalkenes and acetophenone. PMID:23999797

  20. Metal-free transannulation reaction of indoles with nitrostyrenes: a simple practical synthesis of 3-substituted 2-quinolones.

    PubMed

    Aksenov, Alexander V; Smirnov, Alexander N; Aksenov, Nicolai A; Aksenova, Inna V; Frolova, Liliya V; Kornienko, Alexander; Magedov, Igor V; Rubin, Michael

    2013-10-18

    3-Substituted 2-quinolones are obtained via a novel, metal-free transannulation reaction of 2-substituted indoles with 2-nitroalkenes in polyphosphoric acid. The reaction can be used in conjunction with the Fisher indole synthesis offering a practical three-component heteroannulation methodology to produce 2-quinolones from arylhydrazines, 2-nitroalkenes and acetophenone.

  1. Amorphous carbon enriched with pyridinic nitrogen as an efficient metal-free electrocatalyst for oxygen reduction reaction.

    PubMed

    Chen, Jingyan; Wang, Xin; Cui, Xiaoqiang; Yang, Guangmin; Zheng, Weitao

    2014-01-18

    An amorphous metal-free N-doped carbon film prepared by sputtering and annealing exhibits comparable electrocatalytic activity and superior stability and methanol tolerance to the commercial Pt/C catalyst via a four-electron pathway for oxygen reduction reaction (ORR). Pyridinic nitrogen in films plays a key role in electrocatalytic activity for ORR.

  2. A Direct Metal-Free Decarboxylative Sulfono Functionalization (DSF) of Cinnamic Acids to α,β-Unsaturated Phenyl Sulfones.

    PubMed

    Singh, Rahul; Allam, Bharat Kumar; Singh, Neetu; Kumari, Kumkum; Singh, Satish Kumar; Singh, Krishna Nand

    2015-06-05

    A metal-free room temperature decarboxylative cross-coupling between cinnamic acids and arylsulfonyl hydrazides has been realized for the first time for the synthesis of (E)-vinyl sulfones. The scope and versatility of the reaction has been demonstrated by the regio- and stereoselective synthesis of 22 derivatives with diverse structural features.

  3. Metal-free oxidative hydroxyalkylarylation of activated alkenes by direct sp3 C-H functionalization of alcohols.

    PubMed

    Meng, Yuan; Guo, Li-Na; Wang, Hua; Duan, Xin-Hua

    2013-09-04

    A metal-free tandem radical addition/cyclization reaction of activated alkenes and alcohols has been developed. The process provides an efficient and atom economical access to various valuable hydroxyl-containing oxindoles through the direct sp(3) C-H functionalization of alcohols.

  4. Acetic acid promoted metal-free aerobic carbon-carbon bond forming reactions at α-position of tertiary amines.

    PubMed

    Ueda, Hirofumi; Yoshida, Kei; Tokuyama, Hidetoshi

    2014-08-15

    The oxidative functionalization of the benzylic C-H bonds in tetrahydroisoquinolines and tetrahydro-β-carboline derivatives was investigated. C-C bond forming reactions proceeded with a range of nucleophiles (nitroalkane, enol silyl ether, indole, allylstannane, and tetrabutylammonium cyanide) under metal-free conditions and an oxygen atmosphere. Acetic acid caused a significant acceleration effect.

  5. Metal-free C-N- and N-N-bond formation: synthesis of 1,2,3-triazoles from ketones, N-tosylhydrazines, and amines in one pot.

    PubMed

    Chen, Zhengkai; Yan, Qiangqiang; Liu, Zhanxiang; Zhang, Yuhong

    2014-12-22

    A novel synthetic approach toward 1,4-disubstituted 1,2,3-triazoles by C-N- and N-N-bond formation has been established under transition-metal-free conditions. Complete control of the regioselectivity was successfully achieved. Commercially available anilines, ketones, and N-tosylhydrazine were treated with molecular iodine in one pot to allow the regioselective generation of 1,4-disubstituted 1,2,3-triazoles in high yields without the use of azides. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Anion reduction dominated cathodic limit of metal-free ionic liquid: experimental and theoretical proofs.

    PubMed

    Lo, Nai-Chang; Chen, Hsing-Yin; Chuang, Wan-Jung; Lu, Chi-Yu; Chen, Ping-Yu; Chen, Po-Yu

    2013-11-07

    The cathodic limit of the electrochemical window in the second-generation ionic liquids (composed of air- and water-stable metal-free cations and anions) is traditionally believed to be determined by the reduction of the cation. More and more exceptions, however, were found in various ionic liquids. In this study, the cathodic limit of the electrochemical window in 1-butyl-1-methylpyrrolidinium salicylate ionic liquid (BMP-SAL IL) was studied. It has been found that the cathodic limit of BMP-SAL is determined by the reduction of SAL(-) anion rather than the reduction of BMP(+) cation. The cyclic voltammetric behavior, NMR spectra, and MALDI-TOF MS spectra of BMP-SAL recorded before and after the IL was electrolyzed at the cathodic limit provide sufficient evidence that the major reaction at the cathodic limit of BMP-SAL is the reduction of SAL(-) anion. The theoretical calculations support the experimental data, and the results indicate that anion reduction dominated cathodic limit should be a common phenomenon in ionic liquids.

  7. Platinum Group Metal-free Catalysts for Hydrogen Evolution Reaction in Microbial Electrolysis Cells.

    PubMed

    Yuan, Heyang; He, Zhen

    2017-07-01

    Hydrogen gas is a green energy carrier with great environmental benefits. Microbial electrolysis cells (MECs) can convert low-grade organic matter to hydrogen gas with low energy consumption and have gained a growing interest in the past decade. Cathode catalysts for the hydrogen evolution reaction (HER) present a major challenge for the development and future applications of MECs. An ideal cathode catalyst should be catalytically active, simple to synthesize, durable in a complex environment, and cost-effective. A variety of noble-metal free catalysts have been developed and investigated for HER in MECs, including Nickel and its alloys, MoS2 , carbon-based catalysts and biocatalysts. MECs in turn can serve as a research platform to study the durability of the HER catalysts. This personal account has reviewed, analyzed, and discussed those catalysts with an emphasis on synthesis and modification, system performance and potential for practical applications. It is expected to provide insights into the development of HER catalysts towards MEC applications. © 2017 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Electron doped C2N monolayer as efficient noble metal-free catalysts for CO oxidation

    NASA Astrophysics Data System (ADS)

    Chakrabarty, Soubhik; Das, Tisita; Banerjee, Paramita; Thapa, Ranjit; Das, G. P.

    2017-10-01

    Using state-of-the-art density functional theory (DFT) based approach; we investigated the catalytic activity of electron doped C2N monolayer (O → N) for CO oxidation. Large surface-to-volume ratio and uniformly distributed holes of recently synthesized planar 2D C2N have made it a potential candidate as noble metal-free catalyst. However, pristine C2N monolayer is chemically inert and hinders the adsorption of O2 and CO molecule on it. Oxygen doping in C2N brings additional electrons to the system and introduces donor state below EF. Thus the reactivity of O-doped C2N (2OC2N) monolayer gets significantly enhanced, thereby opening up the possibility of its usage as a catalyst. This reactive 2OC2N surface adsorbs an incoming O2 molecule along with the elongation of Osbnd O bond, making it chemically active. Presence of this pre-adsorbed active O2 greatly impedes the adsorption of another incoming CO, favoring Eiley-Rideal (ER) mechanism for CO oxidation.

  9. A Class of High Performance Metal-Free Oxygen Reduction Electrocatalysts based on Cheap Carbon Blacks

    PubMed Central

    Sun, Xiujuan; Song, Ping; Zhang, Yuwei; Liu, Changpeng; Xu, Weilin; Xing, Wei

    2013-01-01

    For the goal of practical industrial development of fuel cells, cheap, sustainable and high performance electrocatalysts for oxygen reduction reactions (ORR) which rival those based on platinum (Pt) and other rare materials are highly desirable. In this work, we report a class of cheap and high-performance metal-free oxygen reduction electrocatalysts obtained by co-doping carbon blacks with nitrogen and fluorine (CB-NF).The CB-NF electrocatalysts are highly active and exhibit long-term operation stability and tolerance to poisons during oxygen reduction process in alkaline medium. The alkaline direct methanol fuel cell with the best CB-NF as cathode (3 mg/cm2) outperforms the one with commercial platinum-based cathode (3 mg Pt/cm2). To the best of our knowledge, these are among the most efficient non-Pt based electrocatalysts. Since carbon blacks are 10,000 times cheaper than Pt, these CB-NF electrocatalysts possess the best price/performance ratio for ORR, and are the most promising alternatives to Pt-based ones to date. PMID:23974295

  10. Highly stable precious metal-free cathode catalyst for fuel cell application

    NASA Astrophysics Data System (ADS)

    Serov, Alexey; Workman, Michael J.; Artyushkova, Kateryna; Atanassov, Plamen; McCool, Geoffrey; McKinney, Sam; Romero, Henry; Halevi, Barr; Stephenson, Thomas

    2016-09-01

    A platinum group metal-free (PGM-free) oxygen reduction reaction (ORR) catalyst engineered for stability has been synthesized using the sacrificial support method (SSM). This catalyst was comprehensively characterized by physiochemical analyses and tested for performance and durability in fuel cell membrane electrode assemblies (MEAs). This catalyst, belonging to the family of Fe-N-C materials, is easily scalable and can be manufactured in batches up to 200 g. The fuel cell durability tests were performed in a single cell configuration at realistic operating conditions of 0.65 V, 1.25 atmgauge air, and 90% RH for 100 h. In-depth characterization of surface chemistry and morphology of the catalyst layer before and after durability tests were performed. The failure modes of the PGM-free electrodes were derived from structure-to-property correlations. It is suggested that under constant voltage operation, the performance loss results from degradation of the electrode pore structure, while under carbon corrosion accelerated test protocols the failure mode is catalyst corrosion.

  11. Activity targets for nanostructured platinum-group-metal-free catalysts in hydroxide exchange membrane fuel cells.

    PubMed

    Setzler, Brian P; Zhuang, Zhongbin; Wittkopf, Jarrid A; Yan, Yushan

    2016-12-06

    Fuel cells are the zero-emission automotive power source that best preserves the advantages of gasoline automobiles: low upfront cost, long driving range and fast refuelling. To make fuel-cell cars a reality, the US Department of Energy has set a fuel cell system cost target of US$30 kW(-1) in the long-term, which equates to US$2,400 per vehicle, excluding several major powertrain components (in comparison, a basic, but complete, internal combustion engine system costs approximately US$3,000). To date, most research for automotive applications has focused on proton exchange membrane fuel cells (PEMFCs), because these systems have demonstrated the highest power density. Recently, however, an alternative technology, hydroxide exchange membrane fuel cells (HEMFCs), has gained significant attention, because of the possibility to use stable platinum-group-metal-free catalysts, with inherent, long-term cost advantages. In this Perspective, we discuss the cost profile of PEMFCs and the advantages offered by HEMFCs. In particular, we discuss catalyst development needs for HEMFCs and set catalyst activity targets to achieve performance parity with state-of-the-art automotive PEMFCs. Meeting these targets requires careful optimization of nanostructures to pack high surface areas into a small volume, while maintaining high area-specific activity and favourable pore-transport properties.

  12. Activity targets for nanostructured platinum-group-metal-free catalysts in hydroxide exchange membrane fuel cells

    NASA Astrophysics Data System (ADS)

    Setzler, Brian P.; Zhuang, Zhongbin; Wittkopf, Jarrid A.; Yan, Yushan

    2016-12-01

    Fuel cells are the zero-emission automotive power source that best preserves the advantages of gasoline automobiles: low upfront cost, long driving range and fast refuelling. To make fuel-cell cars a reality, the US Department of Energy has set a fuel cell system cost target of US$30 kW-1 in the long-term, which equates to US$2,400 per vehicle, excluding several major powertrain components (in comparison, a basic, but complete, internal combustion engine system costs approximately US$3,000). To date, most research for automotive applications has focused on proton exchange membrane fuel cells (PEMFCs), because these systems have demonstrated the highest power density. Recently, however, an alternative technology, hydroxide exchange membrane fuel cells (HEMFCs), has gained significant attention, because of the possibility to use stable platinum-group-metal-free catalysts, with inherent, long-term cost advantages. In this Perspective, we discuss the cost profile of PEMFCs and the advantages offered by HEMFCs. In particular, we discuss catalyst development needs for HEMFCs and set catalyst activity targets to achieve performance parity with state-of-the-art automotive PEMFCs. Meeting these targets requires careful optimization of nanostructures to pack high surface areas into a small volume, while maintaining high area-specific activity and favourable pore-transport properties.

  13. Metal-free DNA linearized nuclease based on PASP-polyamine conjugates.

    PubMed

    Li, Chao; Zhao, Fangfang; Huang, Yunan; Liu, Xueyuan; Liu, Yan; Qiao, Renzhong; Zhao, Yufen

    2012-09-19

    Genome manipulation controlled by small metal complexes has attracted extensive interest because of their potential application in the fields of molecular biotechnology and drug development. However, their medicinal application is still limited due to the distinct toxicity of the free radicals generated by partial metal complexes based on oxidative cleaving processes. Thus, it is still a challenge for us to use metal free agent to cleave DNA. In this work, we showed that a family of polyamine-grafted PASP (poly(aspartic acid)) conjugates is able to rapidly induce DNA cleavage in the absence of metal ions, and obtain a high-yield linearization product via a hydrolytic path. From the results of detailed control experiments, it was revealed that the formation of polyamine cation/phosphate anion pair and free ungrafted nucleophilic groups would be the key factors to improve DNA linearization. Constructing polyamine conjugates based on short peptide such as polyamine-grafted PASP, as achieved here, could provide an attractive strategy for developing mild and efficient artificial nucleases as well as researching catalytic mechanisms on DNA chemistry.

  14. Synthesis of Stacked-Cup Carbon Nanotubes in a Metal Free Low Temperature System

    NASA Technical Reports Server (NTRS)

    Kimura, Yuki; Nuth, Joseph A.; Johnson, Natasha M.; Farmer, Kevin D.; Roberts, Kenneth P.; Hussaini, Syed R.

    2011-01-01

    Stacked-cup carbon nanotubes were formed by either Fischer-Tropsch type or Haber Bosch type reactions in a metal free system. Graphite particles were used as the catalyst. The samples were heated at 600 C in a gas mixture of CO 75 Torr, N2 75 Torr and H2 550 Torr for three days. Trans mission electron microscope analysis of the catalyst surface at the completion of the experiment recognized the growth of nanotubes. They were 10-50 nm in diameter and approximately 1 micrometer in length. They had a hollow channel of 5-20 nm in the center. The nanotubes may have grown on graphite surfaces by the CO disproportionation reaction and the surface tension of the carbon nucleus may have determined the diameter. Although, generally, the diameter of a carbon nanotube depends on the size of the cataly1ic particles, the diameter of the nanotubes on graphite particles was independent of the particle size and significantly confined within a narrow range compared with that produced using catalytic amorphous iron-silicate nanoparticles. Therefore, they must have an unknown formation process that is different than the generally accepted mechanism.

  15. Wear of posterior metal-free polymer crowns after 2 years.

    PubMed

    Ohlmann, B; Trame, J-P; Dreyhaupt, J; Gabbert, O; Koob, A; Rammelsberg, P

    2008-10-01

    The objective of this study was to evaluate the clinical wear behaviour of posterior, metal-free polymer crowns and to compare it with that of metal-ceramic crowns. After randomization, a total of 120 single crowns were set in posterior teeth. These 120 crowns were divided into three groups: 40 polymer crowns with a glass-fibre framework (group 1), 40 polymer crowns without framework stabilization (group 2) and 40 metal-ceramic crowns (control group). Wear was measured by use of gypsum replicas and a 3D laser scanner at baseline and after 2 years. Statistical analysis was performed by use of a mixed-effects regression model. The mean total wear of posterior single crowns was -19.0 mum (+/- 18.5 microm) in group 1, -24.3 microm (+/- 31.5 microm) in group 2 and -7.0 microm (+/- 8.8 microm) in the control group. Statistical analysis revealed the mean total wear of the polymer crowns in groups 1 (P < or = 0.01) and 2 (P < or = 0.01) was significantly greater than in the control group. No significant difference was detected between groups 1 and 2 (P = 0.58). Age, gender and opposing teeth had no significant effect on wear behaviour.

  16. Highly reusable space transportation system study

    NASA Astrophysics Data System (ADS)

    Haney, J. W.

    1997-01-01

    To significantly increase demand for launch services by stimulating existing and planned markets as well as enabling new markets, the cost to orbit needs to be reduced a factor of ten below projected Reusable Launch Vehicle (RLV) goals. This will place the recurring operations cost around 200 per payload pound to low earth orbit (LEO). Methods for reducing the cost include: increasing relative vehicle performance, increasing vehicle reusability, and decreasing recurring operations. A study was conducted for NASA in support of its Highly Reusable Space Transportation (HRST) initiative to identify for further assessment and development, those launch strategies that hold the greatest potential with respect to meeting this goal. During this study a number of candidate strategies were evaluated associated with access to space. Both technical and cost trades were performed, and concluded that there are two airbreathing propulsion concepts utilizing launch assist that appear promising in achieving the HRST-cost goals. These concepts employ both turbine based combine cycle (TBCC) and rocket based combine cycle (RBCC) propulsion systems. The launch assist selected uses electromagnetic propulsion and a guideway to provide both delta velocity and altitude. A first order investigation of system level requirements associated with HRST launch assist for a magnetically launched vehicle including guideway concept and requirements as well as magnetic levitation and propulsion concepts and requirements were also conducted. This study concluded that the HRST goals of total recurring operations cost of 200 per payload pound to Low Earth Orbit based on a ten year operational period were feasible if the required technology was matured. The most promising concept to achieve these goals is based on a RBCC powered vehicle with electromagnetic launch assist.

  17. Military applications of reusable launch vehicles (RLVs)

    NASA Astrophysics Data System (ADS)

    Sponable, Jess M.

    1996-03-01

    With the development and operational fielding of fully reusable launch vehicles (RLVs) becoming imminent, coupled with the ``end of the Cold War'' and fractionalization of the former ``bi-polar'' world into a ``multi-polar'' one, the need and potential for military versions of RLVs are being recognized by the military strategic planner. Recognizing the instability of the world order, especially with the potential for terrorism from all quarters, planning for the development of systems capable of defending our critical space based assests is becoming more essential. This paper presents some of the potential military applications of RLVs to support the Nation's defense and security interests world-wide.

  18. Reusable crucible for containing corrosive liquids

    DOEpatents

    de Pruneda, Jean A. H.

    1995-01-01

    A reusable, non-wetting, corrosion-resistant material suitable for containment of corrosive liquids is formed of a tantalum or tantalum alloy substrate that is permeated with carbon atoms. The substrate is carburized to form surface layers of TaC and Ta.sub.2 C, and then is heated at high temperature under vacuum until the carbon atoms in the carbide layers diffuse throughout the substrate to form a solid solution of carbon atoms randomly interspersed in the tantalum or tantalum alloy lattice.

  19. Reusable crucible for containing corrosive liquids

    DOEpatents

    Pruneda, J.A.H. de.

    1995-01-24

    A reusable, non-wetting, corrosion-resistant material suitable for containment of corrosive liquids is formed of a tantalum or tantalum alloy substrate that is permeated with carbon atoms. The substrate is carburized to form surface layers of TaC and Ta[sub 2]C, and then is heated at high temperature under vacuum until the carbon atoms in the carbide layers diffuse throughout the substrate to form a solid solution of carbon atoms randomly interspersed in the tantalum or tantalum alloy lattice. 10 figures.

  20. Reusable launch vehicle facts and fantasies

    NASA Astrophysics Data System (ADS)

    Kaplan, Marshall H.

    2002-01-01

    Many people refuse to address many of the realities of reusable launch vehicle systems, technologies, operations and economics. Basic principles of physics, space flight operations, and business limitations are applied to the creation of a practical vision of future expectations. While reusable launcher concepts have been proposed for several decades, serious review of potential designs began in the mid-1990s, when NASA decided that a Space Shuttle replacement had to be pursued. A great deal of excitement and interest was quickly generated by the prospect of ``orders-of-magnitude'' reduction in launch costs. The potential for a vastly expanded space program motivated the entire space community. By the late-1990s, and after over one billion dollars were spent on the technology development and privately-funded concepts, it had become clear that there would be no new, near-term operational reusable vehicle. Many factors contributed to a very expensive and disappointing effort to create a new generation of launch vehicles. It began with overly optimistic projections of technology advancements and the belief that a greatly increased demand for satellite launches would be realized early in the 21st century. Contractors contributed to the perception of quickly reachable technology and business goals, thus, accelerating the enthusiasm and helping to create a ``gold rush'' euphoria. Cost, schedule and performance margins were all highly optimistic. Several entrepreneurs launched start up companies to take advantage of the excitement and the availability of investor capital. Millions were raised from private investors and venture capitalists, based on little more than flashy presentations and animations. Well over $500 million were raised by little-known start up groups to create reusable systems, which might complete for the coming market in launch services. By 1999, it was clear that market projections, made just two years earlier, were not going to be realized. Investors

  1. Simulated meteoroid penetration of reusable surface insulation

    NASA Technical Reports Server (NTRS)

    Lehman, J. K.; Christensen, H. E.

    1973-01-01

    Meteoroid impact simulation test results on insulation tiles were used to determine penetration resistance of reusable surface insulation attached to simulated shuttle structures. The probability of no meteoroid damage to a typical shuttle orbiter was determined. Specimens were plasma jet tested to determine effects of various size meteoroid cavities on their thermal performance. None of the tiles failed catastrophically, but large, egg-shaped craters did result from meteoroid penetration. The metallic side of a specimen that was completely penetrated showed a petalled hole typical for thin gage shielded structures.

  2. Influence of gamma ray irradiation and annealing temperature on the optical constants and spectral dispersion parameters of metal-free and zinc tetraphenylporphyrin thin films: A comparative study.

    PubMed

    Zeyada, H M; Makhlouf, M M; El-Nahass, M M

    2015-09-05

    In this work, we report on the effect of γ-ray irradiation and annealing temperature on the optical properties of metal-free tetraphenylporphyrin, H2TPP, and zinc tetraphenylporphyrin, ZnTPP, thin films. Thin films of H2TPP and ZnTPP were successfully prepared by the thermal evaporation technique. The optical properties of H2TPP and ZnTPP films were investigated using spectrophotometric measurements of the transmittance and reflectance at normal incidence of light in the wavelength range from 200 to 2500 nm. The absorption spectra of H2TPP showed four absorption bands, namely the Q, B, N and M bands. The effect of inserting Zn atom into the cavity of porphyrin macrocycle in ZnTPP molecule distorted the Q and B bands, reduced the width of absorption region and influenced the optical constants and dispersion parameters. In all conditions, the type of electron transition is indirect allowed transition. Anomalous dispersion is observed in the absorption region but normal dispersion occurs in the transparent region of spectra. We adopted multi-oscillator model and the single oscillator model to interpret the anomalous and normal dispersion, respectively. We have found that the annealing temperature has mostly the opposite effect of γ-ray irradiation on absorption and dispersion characteristics of these films. Copyright © 2015 Elsevier B.V. All rights reserved.

  3. Influence of gamma ray irradiation and annealing temperature on the optical constants and spectral dispersion parameters of metal-free and zinc tetraphenylporphyrin thin films: A comparative study

    NASA Astrophysics Data System (ADS)

    Zeyada, H. M.; Makhlouf, M. M.; El-Nahass, M. M.

    2015-09-01

    In this work, we report on the effect of γ-ray irradiation and annealing temperature on the optical properties of metal-free tetraphenylporphyrin, H2TPP, and zinc tetraphenylporphyrin, ZnTPP, thin films. Thin films of H2TPP and ZnTPP were successfully prepared by the thermal evaporation technique. The optical properties of H2TPP and ZnTPP films were investigated using spectrophotometric measurements of the transmittance and reflectance at normal incidence of light in the wavelength range from 200 to 2500 nm. The absorption spectra of H2TPP showed four absorption bands, namely the Q, B, N and M bands. The effect of inserting Zn atom into the cavity of porphyrin macrocycle in ZnTPP molecule distorted the Q and B bands, reduced the width of absorption region and influenced the optical constants and dispersion parameters. In all conditions, the type of electron transition is indirect allowed transition. Anomalous dispersion is observed in the absorption region but normal dispersion occurs in the transparent region of spectra. We adopted multi-oscillator model and the single oscillator model to interpret the anomalous and normal dispersion, respectively. We have found that the annealing temperature has mostly the opposite effect of γ-ray irradiation on absorption and dispersion characteristics of these films.

  4. Architecture and systems design of a reusable Martian twin rotor tailsitter

    NASA Astrophysics Data System (ADS)

    Forshaw, Jason L.; Lappas, Vaios J.

    2012-11-01

    A rapidly developing field is that of tailsitters, aircraft capable of transitioning between horizontal and vertical flight, a premise that supports a diverse range of applications. Tailsitters can effortlessly land and hover at will, yet can also move at high speed between destinations making them ideal in undertaking 'multiple missions to land at multiple destinations far apart'. This paper considers how the concept of twin helicopter rotor tailsitters, such as QinetiQ's Eye-OnTM, can be adapted for use in a Martian environment. The mission architecture and system requirements for both reusable and single-use tailsitters are considered and 12 disparate subsystems or fields (including propulsion, power and aerodynamics) are designed using a high-level systems approach. The resulting tailsitter is capable of covering 100km and 450km in reusable and single-use architectures respectively. A docking station is also designed utilising a four stage process for deployment of the tailsitter.

  5. Parameter Validation for Evaluation of Spaceflight Hardware Reusability

    NASA Technical Reports Server (NTRS)

    Childress-Thompson, Rhonda; Thomas, L. Dale; Farrington, Phillip

    2017-01-01

    Within recent years, there has been an influx of companies around the world pursuing reusable systems for space flight. Much like NASA, many of these new entrants are learning that reusable systems are complex and difficult to acheive. For instance, in its first attempts to retrieve spaceflight hardware for future reuse, SpaceX unsuccessfully tried to land on a barge at sea, resulting in a crash-landing. As this new generation of launch developers continues to develop concepts for reusable systems, having a systematic approach for determining the most effective systems for reuse is paramount. Three factors that influence the effective implementation of reusability are cost, operability and reliability. Therefore, a method that integrates these factors into the decision-making process must be utilized to adequately determine whether hardware used in space flight should be reused or discarded. Previous research has identified seven features that contribute to the successful implementation of reusability for space flight applications, defined reusability for space flight applications, highlighted the importance of reusability, and presented areas that hinder successful implementation of reusability. The next step is to ensure that the list of reusability parameters previously identified is comprehensive, and any duplication is either removed or consolidated. The characteristics to judge the seven features as good indicators for successful reuse are identified and then assessed using multiattribute decision making. Next, discriminators in the form of metrics or descriptors are assigned to each parameter. This paper explains the approach used to evaluate these parameters, define the Measures of Effectiveness (MOE) for reusability, and quantify these parameters. Using the MOEs, each parameter is assessed for its contribution to the reusability of the hardware. Potential data sources needed to validate the approach will be identified.

  6. Graphdiyne as a metal-free catalyst for low-temperature CO oxidation.

    PubMed

    Wu, Ping; Du, Pan; Zhang, Hui; Cai, Chenxin

    2014-03-28

    The oxidation of CO has attracted great interest in recent years because of its important role in enhancing the catalyst durability in fuel cells and in solving the growing environmental problems caused by CO emission. The usually used noble metal nanocatalysts are costly and require high reaction temperature for efficient operation. We report here a density functional theory (DFT) study of low-temperature CO oxidation catalyzed by graphdiyne, which is a new two-dimensional periodic carbon allotrope with a one-atom-thick sheet of carbon building of sp- and sp(2)-hybridized carbon atoms and has been shown in our recent work to have high catalytic activity for oxygen reduction reactions (ORRs). We studied the adsorption properties of CO and O2 on graphdiyne, simulated the reaction mechanism of CO oxidation involving graphdiyne, and analyzed electronic structures at each step of reaction progress. The simulation results indicate that the adsorption of O2 prevails over CO adsorption on the graphdiyne sheet; the reaction of CO oxidation by adsorbed O2 on graphdiyne proceeds via the Eley-Rideal (ER) mechanism with a decrease in the energy of the system and the energy barrier as low as 0.18 eV in the rate-limiting step. The oxidation reaction includes the breakage of the O-O bond in the adsorbed O2, formation of the metastable carbonate-like intermediate state, and the creation of CO2 molecules. The results presented here demonstrate that graphdiyne is a good, low-cost, and metal-free catalyst for low-temperature CO oxidation, can be used to solve problems caused by environmental CO emission and has a high ability of CO tolerance by its removal through oxidation in fuel cells.

  7. Enhancement of the electrical characteristics of metal-free phthalocyanine films using cold isostatic pressing

    SciTech Connect

    Matsushima, Toshinori E-mail: adachi@cstf.kyushu-u.ac.jp; Adachi, Chihaya E-mail: adachi@cstf.kyushu-u.ac.jp; Esaki, Yu

    2014-12-15

    Spatial gaps between grains and other grains, substrates, or electrodes in organic electronic devices are one of the causes of the reduction in the electrical characteristics. In this study, we demonstrate that cold isostatic pressing (CIP) is an effective method to crush the gaps and enhance the electrical characteristics. CIP of metal-free phthalocyanine (H{sub 2}PC) films induced a decrease in the film thickness by 34%–40% because of the gap crush. The connection of smaller grains into a larger grain and planarization of the film surface were also observed in the CIP film. The crystal axes of the H{sub 2}PC crystallites were rearranged from the a-axis to the c-axis of the α-phase crystal structure in a direction perpendicular to the substrate by CIP, indicating favorable hole injection and transport in this direction because of a better overlap of π orbitals. Thermally stimulated current measurements showed that deep hole traps disappeared and the total hole-trap density decreased after CIP. These CIP-induced changes of the film thicknesses, crystal axes and the hole traps lead to a marked increase in the hole mobility of the H{sub 2}PC films from 2.0 × 10{sup −7} to 4.0 × 10{sup −4} cm{sup 2}/V s by 2000 times in the perpendicular direction. We believe that these findings are important for unveiling the underlying carrier injection and transport mechanisms of organic films and for enhancing the performance of future organic electronic devices.

  8. CMB signatures of metal-free star formation and Planck 2015 polarization data

    NASA Astrophysics Data System (ADS)

    Miranda, Vinicius; Lidz, Adam; Heinrich, Chen He; Hu, Wayne

    2017-06-01

    Standard analyses of the reionization history of the Universe from Planck cosmic microwave background (CMB) polarization measurements consider only the overall optical depth to electron scattering (τ), and further assume a step-like reionization history. However, the polarization data contain information beyond the overall optical depth, and the assumption of a step-like function may miss high redshift contributions to the optical depth and leads to biased τ constraints. Accounting for its full reionization information content, we reconsider the interpretation of Planck 2015 Low-Frequency Instrument (LFI) polarization data using simple, yet physically motivated reionization models. We show that these measurements still, in fact, allow a non-negligible contribution from metal-free (Pop-III) stars forming in mini-haloes of mass M ˜ 105-106 M⊙ at z ≳ 15, provided this mode of star formation is fairly inefficient. We find that an early, self-regulated phase of Pop-III star formation with a gradual, plateau feature in the ionization history provides a good match to the Planck LFI measurements. In this case, as much as 20 per cent of the volume of the Universe is ionized by z ˜ 20. Although preferred when the full information content of the data is incorporated, this model would spuriously be disfavoured in the standard analysis. This preference is driven mostly by excess power from E-mode polarization at multipoles of 10 ≲ ℓ ≲ 20, which may reflect remaining systematic errors in the data, a statistical fluctuation or signatures of the first stars. Measurements from the Planck High-Frequency Instrument should be able to confirm or refute this hint and future cosmic-variance-limited E-mode polarization surveys can provide substantially more information on these signatures.

  9. Facile and Gram-scale Synthesis of Metal-free Catalysts: Toward Realistic Applications for Fuel Cells

    PubMed Central

    Kim, Ok-Hee; Cho, Yong-Hun; Chung, Dong Young; Kim, Min Jeong; Yoo, Ji Mun; Park, Ji Eun; Choe, Heeman; Sung, Yung-Eun

    2015-01-01

    Although numerous reports on nonprecious metal catalysts for replacing expensive Pt-based catalysts have been published, few of these studies have demonstrated their practical application in fuel cells. In this work, we report graphitic carbon nitride and carbon nanofiber hybrid materials synthesized by a facile and gram-scale method via liquid-based reactions, without the use of toxic materials or a high pressure-high temperature reactor, for use as fuel cell cathodes. The resulting materials exhibited remarkable methanol tolerance, selectivity, and stability even without a metal dopant. Furthermore, these completely metal-free catalysts exhibited outstanding performance as cathode materials in an actual fuel cell device: a membrane electrode assembly with both acidic and alkaline polymer electrolytes. The fabrication method and remarkable performance of the single cell produced in this study represent progressive steps toward the realistic application of metal-free cathode electrocatalysts in fuel cells. PMID:25728910

  10. Facile and gram-scale synthesis of metal-free catalysts: toward realistic applications for fuel cells.

    PubMed

    Kim, Ok-Hee; Cho, Yong-Hun; Chung, Dong Young; Kim, Min Jeong; Yoo, Ji Mun; Park, Ji Eun; Choe, Heeman; Sung, Yung-Eun

    2015-03-02

    Although numerous reports on nonprecious metal catalysts for replacing expensive Pt-based catalysts have been published, few of these studies have demonstrated their practical application in fuel cells. In this work, we report graphitic carbon nitride and carbon nanofiber hybrid materials synthesized by a facile and gram-scale method via liquid-based reactions, without the use of toxic materials or a high pressure-high temperature reactor, for use as fuel cell cathodes. The resulting materials exhibited remarkable methanol tolerance, selectivity, and stability even without a metal dopant. Furthermore, these completely metal-free catalysts exhibited outstanding performance as cathode materials in an actual fuel cell device: a membrane electrode assembly with both acidic and alkaline polymer electrolytes. The fabrication method and remarkable performance of the single cell produced in this study represent progressive steps toward the realistic application of metal-free cathode electrocatalysts in fuel cells.

  11. Facile and Gram-scale Synthesis of Metal-free Catalysts: Toward Realistic Applications for Fuel Cells

    NASA Astrophysics Data System (ADS)

    Kim, Ok-Hee; Cho, Yong-Hun; Chung, Dong Young; Kim, Min Jeong; Yoo, Ji Mun; Park, Ji Eun; Choe, Heeman; Sung, Yung-Eun

    2015-03-01

    Although numerous reports on nonprecious metal catalysts for replacing expensive Pt-based catalysts have been published, few of these studies have demonstrated their practical application in fuel cells. In this work, we report graphitic carbon nitride and carbon nanofiber hybrid materials synthesized by a facile and gram-scale method via liquid-based reactions, without the use of toxic materials or a high pressure-high temperature reactor, for use as fuel cell cathodes. The resulting materials exhibited remarkable methanol tolerance, selectivity, and stability even without a metal dopant. Furthermore, these completely metal-free catalysts exhibited outstanding performance as cathode materials in an actual fuel cell device: a membrane electrode assembly with both acidic and alkaline polymer electrolytes. The fabrication method and remarkable performance of the single cell produced in this study represent progressive steps toward the realistic application of metal-free cathode electrocatalysts in fuel cells.

  12. Metal free nitrogen doped hollow mesoporous graphene-analogous spheres as effective electrocatalyst for oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Yan, Jing; Meng, Hui; Xie, Fangyan; Yuan, Xiaoli; Yu, Wendan; Lin, Worong; Ouyang, Wenpeng; Yuan, Dingsheng

    2014-01-01

    Nitrogen-doped hollow mesoporous carbon spheres has been synthesized from mesoporous silica spheres using glycine as carbon and nitrogen precursor. The wall of the spheres is composed by broken graphene. The metal free nitrogen-doped hollow mesoporous carbon spheres are proven to be active electrocatalyst for the oxygen reduction reaction in alkaline solution. A unique advantage of the nitrogen-doped hollow mesoporous carbon sphere is its methanol-tolerant property because of the absence of active metal. The catalytic activity is ascribed to the pyridinic-nitrogen formed during pyrolysis and the graphene-like structure. To the best of our knowledge this is the first report on the nitrogen-doped hollow mesoporous carbon sphere as a metal-free electrocatalyst for the oxygen reduction reaction which is an important reaction in fuel cell. The prepared mesoporous carbon material can also be used as catalyst support and find application both in the anode and cathode of fuel cell.

  13. Concepts of Operations for a Reusable Launch Space Vehicle

    DTIC Science & Technology

    1996-06-01

    a Reusable Launch Space Vehicle Contract or Grant Number Program Element Number Authors Rampino, Michael A. Project Number Task Number Work Unit...of Operations for a Reusable Launch Space Vehicle by Michael A. Rampino A THESIS PRESENTED TO THE FACULTY OF THE SCHOOL OF ADVANCED AIR POWER STUDIES

  14. Methodology for Evaluating Quality and Reusability of Learning Objects

    ERIC Educational Resources Information Center

    Kurilovas, Eugenijus; Bireniene, Virginija; Serikoviene, Silvija

    2011-01-01

    The aim of the paper is to present the scientific model and several methods for the expert evaluation of quality of learning objects (LOs) paying especial attention to LOs reusability level. The activities of eQNet Quality Network for a European Learning Resource Exchange (LRE) aimed to improve reusability of LOs of European Schoolnet's LRE…

  15. Structural Integrity and Durability of Reusable Space Propulsion Systems

    NASA Technical Reports Server (NTRS)

    1985-01-01

    The space shuttle main engine (SSME), a reusable space propulsion system, is discussed. The advances in high pressure oxygen hydrogen rocket technology are reported to establish the basic technology and to develop new analytical tools for the evaluation in reusable rocket systems.

  16. 76 FR 24495 - Reprocessing of Reusable Medical Devices; Public Workshop

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-05-02

    ... HUMAN SERVICES Food and Drug Administration Reprocessing of Reusable Medical Devices; Public Workshop... Medical Devices Workshop.'' The purpose of the workshop is to discuss factors affecting the reprocessing of reusable medical devices and FDA's plans to address the identified issues. This workshop is part...

  17. Metal-free organic dye sensitized solar cell based on perpendicular zinc oxide nanosheet thick films with high conversion efficiency.

    PubMed

    Hosono, Eiji; Mitsui, Yosuke; Zhou, Haoshen

    2008-10-28

    Dye-sensitized solar cells (DSCs) with a high efficiency of 4.27%, which is superior to that of ZnO-based DSCs containing metal complex dyes such as N-719, under 100 mW cm(-2) illumination, are achieved by using metal-free organic dyes and a perpendicular ZnO nanosheet thick film synthesized by a self-templating method.

  18. Production of Metal-Free Composites Composed of Graphite Oxide and Oxidized Carbon Nitride Nanodots and Their Enhanced Photocatalytic Performances.

    PubMed

    Kim, Seung Yeon; Oh, Junghoon; Park, Sunghee; Shim, Yeonjun; Park, Sungjin

    2016-04-04

    A novel metal-free composite (GN) composed of two types of carbon-based nanomaterials, graphite oxide (GO) and 2D oxidized carbon nitride (OCN) nanodots was produced. Chemical and morphological characterizations reveal that GN contains a main component of GO with well-dispersed 2D OCN nanodots. GN shows enhanced photocatalytic performance for degrading an organic pollutant, Rhodamine B, under visible light. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Continuous-flow synthesis of primary amines: Metal-free reduction of aliphatic and aromatic nitro derivatives with trichlorosilane

    PubMed Central

    Porta, Riccardo; Colombo, Giacomo; Rossi, Sergio

    2016-01-01

    The metal-free reduction of nitro compounds to amines mediated by trichlorosilane was successfully performed for the first time under continuous-flow conditions. Aromatic as well as aliphatic nitro derivatives were converted to the corresponding primary amines in high yields and very short reaction times with no need for purification. The methodology was also extended to the synthesis of two synthetically relevant intermediates (precursors of baclofen and boscalid). PMID:28144331

  20. Precious-Metal-Free Heteroarylation of Azlactones: Direct Synthesis of α-Pyridyl, α-Substituted Amino Acid Derivatives.

    PubMed

    Johnson, Tarn C; Marsden, Stephen P

    2016-10-21

    A one-pot, three-component synthesis of α-pyridyl, α-substituted amino acid derivatives is described. The key transformation is a direct, precious-metal-free heteroarylation of readily available, amino acid derived azlactones with electrophilically activated pyridine N-oxides. The resulting intermediates can be used directly as efficient acylating agents for a range of nucleophiles, leading to the heteroarylated amino acid derivatives in a single vessel.

  1. Metal-free synthesis of N-fused heterocyclic iodides via C-H functionalization mediated by tert-butylhydroperoxide.

    PubMed

    Sharma, Krishna K; Patel, Dhananjay I; Jain, Rahul

    2015-10-21

    Direct, regioselective and metal-free synthesis of fused N-heterocyclic iodides is reported. This regioselective C-H functionalization is mediated by tert-butylhydroperoxide (TBHP), via dual activation of molecular iodine and a heterocyclic substrate, resulting in the in situ generation of electrophilic iodine species (I(+)), and free radical(s) (t)BuO˙ or (t)BuOO˙, driving the iodination reaction.

  2. Heteroatoms ternary-doped porous carbons derived from MOFs as metal-free electrocatalysts for oxygen reduction reaction

    PubMed Central

    Li, Ji-Sen; Li, Shun-Li; Tang, Yu-Jia; Li, Kui; Zhou, Lei; Kong, Ning; Lan, Ya-Qian; Bao, Jian-Chun; Dai, Zhi-Hui

    2014-01-01

    The nitrogen (N), phosphorus (P) and sulphur (S) ternary-doped metal-free porous carbon materials have been successfully synthesized using MOFs as templates (denoted as NPS-C-MOF-5) for oxygen reduction reaction (ORR) for the first time. The influences of porous carbons from carbonizing different MOFs and carbonization temperature on ORR have been systematically investigated. Due to the synergistic effect of N, P and S ternary-doping, the NPS-C-MOF-5 catalyst shows a higher onset potential as a metal-free electrocatalyst for ORR among the currently reported metal-free electrocatalysts, very close to the commercial Pt-C catalyst. In particular, the kinetic limiting current density of NPS-C-MOF-5 catalyst at −0.6 V is up to approximate −11.6 mA cm−2, which is 1.2 times higher than that of the commercial Pt-C catalyst. Furthermore, the outstanding methanol tolerance and excellent long-term stability of NPS-C-MOF-5 are superior to those of the commercial Pt-C catalyst for ORR in alkaline media. PMID:24875253

  3. Metal-free hydrogenation catalyzed by an air-stable borane: use of solvent as a frustrated Lewis base.

    PubMed

    Scott, Daniel J; Fuchter, Matthew J; Ashley, Andrew E

    2014-09-15

    In recent years 'frustrated Lewis pairs' (FLPs) have been shown to be effective metal-free catalysts for the hydrogenation of many unsaturated substrates. Even so, limited functional-group tolerance restricts the range of solvents in which FLP-mediated reactions can be performed, with all FLP-mediated hydrogenations reported to date carried out in non-donor hydrocarbon or chlorinated solvents. Herein we report that the bulky Lewis acids B(C6Cl5)x(C6F5)(3-x) (x=0-3) are capable of heterolytic H2 activation in the strong-donor solvent THF, in the absence of any additional Lewis base. This allows metal-free catalytic hydrogenations to be performed in donor solvent media under mild conditions; these systems are particularly effective for the hydrogenation of weakly basic substrates, including the first examples of metal-free catalytic hydrogenation of furan heterocycles. The air-stability of the most effective borane, B(C6Cl5)(C6F5)2, makes this a practically simple reaction method.

  4. Structural and biophysical properties of metal-free pathogenic SOD1 mutants A4V and G93A

    SciTech Connect

    Galaleldeen, Ahmad; Strange, Richard W.; Whitson, Lisa J.; Antonyuk, Svetlana V.; Narayana, Narendra; Taylor, Alexander B.; Schuermann, Jonathan P.; Holloway, Stephen P.; Hasnain, S.Samar; Hart, P. John

    2010-07-19

    Amyotrophic lateral sclerosis (ALS) is a fatal, progressive neurodegenerative disease characterized by the destruction of motor neurons in the spinal cord and brain. A subset of ALS cases are linked to dominant mutations in copper-zinc superoxide dismutase (SOD1). The pathogenic SOD1 variants A4V and G93A have been the foci of multiple studies aimed at understanding the molecular basis for SOD1-linked ALS. The A4V variant is responsible for the majority of familial ALS cases in North America, causing rapidly progressing paralysis once symptoms begin and the G93A SOD1 variant is overexpressed in often studied murine models of the disease. Here we report the three-dimensional structures of metal-free A4V and of metal-bound and metal-free G93A SOD1. In the metal-free structures, the metal-binding loop elements are observed to be severely disordered, suggesting that these variants may share mechanisms of aggregation proposed previously for other pathogenic SOD1 proteins.

  5. Nuclear spin hyperpolarization with ansa-aminoboranes: a metal-free perspective for parahydrogen-induced polarization.

    PubMed

    Zhivonitko, Vladimir V; Sorochkina, Kristina; Chernichenko, Konstantin; Kótai, Bianka; Földes, Tamás; Pápai, Imre; Telkki, Ville-Veikko; Repo, Timo; Koptyug, Igor

    2016-10-12

    The parahydrogen-induced polarization (PHIP) phenomenon, observed when parahydrogen is used in H2 addition processes, provides a means for substantial NMR signal enhancements and mechanistic studies of chemical reactions. Commonly, noble metal complexes are used for parahydrogen activation, whereas metal-free activation is rare. Herein, we report a series of unimolecular metal-free frustrated Lewis pairs based on an ansa-aminoborane (AAB) moiety in the context of PHIP. These molecules, which have a "molecular tweezers" structure, differ in their substituents at the boryl site (-H, -Ph, -o-iPr-Ph, and -Mes). PHIP effects were observed for all the AABs after exposing their solutions to parahydrogen in a wide temperature range, and experimental measurements of their kinetic and thermodynamic parameters were performed. A theoretical analysis of their nuclear spin polarization effects is presented, and the roles of chemical exchange, chemical equilibrium and spin dynamics are discussed in terms of the key dimensionless parameters. The analysis allowed us to formulate the prerequisites for achieving strong polarization effects with AAB molecules, which can be applied for further design of efficient metal-free tweezers-like molecules for PHIP. Mechanistic (chemical and physical) aspects of the observed effects are discussed in detail. In addition, we performed quantum chemical calculations, which confirmed that the J-coupling between the parahydrogen-originated protons in AAB-H2 molecules is mediated through dihydrogen bonding.

  6. A new method to synthesize sulfur-doped graphene as effective metal-free electrocatalyst for oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Zhai, Chunyang; Sun, Mingjuan; Zhu, Mingshan; Song, Shaoqing; Jiang, Shujuan

    2017-06-01

    The exploration of a metal-free catalyst with highly efficient yet low-cost for the oxygen-reduction reaction (ORR) is under wide spread investigation. In this paper, by using dimethyl sulfoxide (DMSO) as S source as well as solvent, we report a new, low-cost, and facile solvothermal route to synthesize S-doped reduced graphene oxide (S-RGO). The existence of S element in the framework of RGO was solidly confirmed by energy-dispersive X-ray (EDX) and X-ray photoelectron spectroscopy (XPS). The as-synthesized S-RGO can be worked as an efficient metal-free electrocatalyst for ORR. Moreover, compared to commercial Pt/C electrocatalyst, the S-RGO displays superior resistance to crossover effect and stability by evaluating the addition of methanol and CO poisoning experiment. This result not only shows S-RGO as a promising candidate instead of Pt-based catalyst for ORR, but also provides a new approach for the preparation of metal-free electrocatalyst in future.

  7. Heteroatoms ternary-doped porous carbons derived from MOFs as metal-free electrocatalysts for oxygen reduction reaction.

    PubMed

    Li, Ji-Sen; Li, Shun-Li; Tang, Yu-Jia; Li, Kui; Zhou, Lei; Kong, Ning; Lan, Ya-Qian; Bao, Jian-Chun; Dai, Zhi-Hui

    2014-05-30

    The nitrogen (N), phosphorus (P) and sulphur (S) ternary-doped metal-free porous carbon materials have been successfully synthesized using MOFs as templates (denoted as NPS-C-MOF-5) for oxygen reduction reaction (ORR) for the first time. The influences of porous carbons from carbonizing different MOFs and carbonization temperature on ORR have been systematically investigated. Due to the synergistic effect of N, P and S ternary-doping, the NPS-C-MOF-5 catalyst shows a higher onset potential as a metal-free electrocatalyst for ORR among the currently reported metal-free electrocatalysts, very close to the commercial Pt-C catalyst. In particular, the kinetic limiting current density of NPS-C-MOF-5 catalyst at -0.6 V is up to approximate -11.6 mA cm(-2), which is 1.2 times higher than that of the commercial Pt-C catalyst. Furthermore, the outstanding methanol tolerance and excellent long-term stability of NPS-C-MOF-5 are superior to those of the commercial Pt-C catalyst for ORR in alkaline media.

  8. Heteroatoms ternary-doped porous carbons derived from MOFs as metal-free electrocatalysts for oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Li, Ji-Sen; Li, Shun-Li; Tang, Yu-Jia; Li, Kui; Zhou, Lei; Kong, Ning; Lan, Ya-Qian; Bao, Jian-Chun; Dai, Zhi-Hui

    2014-05-01

    The nitrogen (N), phosphorus (P) and sulphur (S) ternary-doped metal-free porous carbon materials have been successfully synthesized using MOFs as templates (denoted as NPS-C-MOF-5) for oxygen reduction reaction (ORR) for the first time. The influences of porous carbons from carbonizing different MOFs and carbonization temperature on ORR have been systematically investigated. Due to the synergistic effect of N, P and S ternary-doping, the NPS-C-MOF-5 catalyst shows a higher onset potential as a metal-free electrocatalyst for ORR among the currently reported metal-free electrocatalysts, very close to the commercial Pt-C catalyst. In particular, the kinetic limiting current density of NPS-C-MOF-5 catalyst at -0.6 V is up to approximate -11.6 mA cm-2, which is 1.2 times higher than that of the commercial Pt-C catalyst. Furthermore, the outstanding methanol tolerance and excellent long-term stability of NPS-C-MOF-5 are superior to those of the commercial Pt-C catalyst for ORR in alkaline media.

  9. Rapid synthesis of fused N-heterocycles by transition-metal-free electrophilic amination of arene C-H bonds.

    PubMed

    Gao, Hongyin; Xu, Qing-Long; Yousufuddin, Muhammed; Ess, Daniel H; Kürti, László

    2014-03-03

    We disclose an efficient and operationally simple protocol for the preparation of fused N-heterocycles starting from readily available 2-nitrobiaryls and PhMgBr under mild conditions. More than two dozen N-heterocycles, including two bioactive natural products, have been synthesized using this method. A stepwise electrophilic aromatic cyclization mechanism was proposed by DFT calculations.

  10. Activation of organozinc reagents with t-Bu-P4 base for transition metal-free catalytic SN2' reaction.

    PubMed

    Kobayashi, Koji; Ueno, Masahiro; Naka, Hiroshi; Kondo, Yoshinori

    2008-08-28

    The t-Bu-P4 base was found to be an excellent catalyst for activating organozinc reagents and was used to promote the S(N)2' reaction of alpha,beta-unsaturated esters bearing a gamma-chloride using various organozinc reagents: these reactions proceeded in high yields with excellent chemo-and regioselectivity.

  11. A new approach for transition metal free magnetic SiC: Defect induced magnetism after self-ion implantation

    NASA Astrophysics Data System (ADS)

    Kummari, Venkata Chandra Sekhar

    SiC has become an attractive wide bandgap semiconductor due to its unique physical and electronic properties and is widely used in high temperature, high frequency, high power and radiation resistant applications. SiC has been used as an alternative to Si in harsh environments such as in the oil industry, nuclear power systems, aeronautical, and space applications. SiC is also known for its polytypism and among them 3C-SiC, 4H-SiC and 6H-SiC are the most common polytypes used for research purposes. Among these polytypes 4H-SiC is gaining importance due to its easy commercial availability with a large bandgap of 3.26 eV at room temperature. Controlled creation of defects in materials is an approach to modify the electronic properties in a way that new functionality may result. SiC is a promising candidate for defect-induced magnetism on which spintronic devices could be developed. The defects considered are of room temperature stable vacancy types, eliminating the need for magnetic impurities, which easily diffuse at room temperature. Impurity free vacancy type defects can be created by implanting the host atoms of silicon or carbon. The implantation fluence determines the defect density, which is a critical parameter for defect induced magnetism. Therefore, we have studied the influence of low fluence low energy silicon and carbon implantation on the creation of defects in n-type 4H-SiC. The characterization of the defects in these implanted samples was performed using the techniques, RBS-channeling and Raman spectroscopy. We have also utilized these characterization techniques to analyze defects created in much deeper layers of the SiC due to implantation of high energy nitrogen ions. The experimentally determined depths of the Si damage peaks due to low energy (60 keV) Si and C ions with low fluences (< 1015 cm-2) are consistent with the SRIM-2011 simulations. From RBS-C Si sub-lattice measurements for different fluences (1.1x1014 cm-2 to 3.2x1014 cm-2 ) of Si implantation in 4H-SiC, the Si vacancy density is estimated to range from 1.29x1022 cm-3 to 4.57x1022 cm-2, corresponding to average vacancy distances of 4.26 A to 2.79 A at the damage peak (50+/-5 nm). Similarly, for C implanted fluences (1.85x1014 cm -2 to 1x1015 cm-2), the Si vacancy density varies from 1.37x1022 cm-3 to 4.22x1022 cm-3 with the average vacancy distances from 4.17 A to 2.87 A at the damage peak (110+/-10 nm). From the Raman spectroscopy, the implantation-induced lattice disorders calculated along the c-axis (LO mode) and perpendicular to c-axis (TO mode) in 4H-SiC are found to be similar. Furthermore, the results obtained from SQUID measurements in C implanted n-type 4HSiC sample with fluences ranging from 1x10 12 to 1.7x1016 ions/cm2 have been discussed. The implanted samples showed diamagnetism similar to the unimplanted sample. To date, to our best of knowledge, no experimental work has been reported on investigating defect induced magnetism for self-ion implantation in n-type 4H-SiC. These first reports of experimental results can provide useful information in future studies for a better understanding of self-ion implantation in SiC-based DMS.

  12. Transition-Metal-Free Regioselective Alkylation of Pyridine N-Oxides Using 1,1-Diborylalkanes as Alkylating Reagents.

    PubMed

    Jo, Woohyun; Kim, Junghoon; Choi, Seoyoung; Cho, Seung Hwan

    2016-08-08

    Reported herein is an unprecedented base-promoted deborylative alkylation of pyridine N-oxides using 1,1-diborylalkanes as alkyl sources. The reaction proceeds efficiently for a wide range of pyridine N-oxides and 1,1-diborylalkanes with excellent regioselectivity. The utility of the developed method is demonstrated by the sequential C-H arylation and methylation of pyridine N-oxides. The reaction also can be applied for the direct introduction of a methyl group to 9-O-methylquinine N-oxide, thus it can serve as a powerful method for late-stage functionalization.

  13. Diazo- and transition-metal-free C-H insertion: a direct synthesis of β-lactams.

    PubMed

    Gomes, Luis F R; Veiros, Luís F; Maulide, Nuno; Afonso, Carlos A M

    2015-01-19

    Carbene intermediates are very useful species for a range of reactions including C-H insertions and cycloadditions. They are most commonly generated by metal-catalyzed release of nitrogen gas from diazo precursors. Herein, we present a novel C-H insertion of simple β-ketoamide substrates, through reaction with (diacetoxyiodo)benzene (DIB) in the presence of a base. This unprecedented transformation bypasses the use of either diazo precursors or metal catalysts and directly delivers β-lactam products by an iodonium ylide, in a single step under mild conditions. Mechanistic studies support the intermediacy of a free singlet carbene of unique reactivity and selectivity. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Aqueous synthesis of 1-H-2-substituted benzimidazoles via transition-metal-free intramolecular amination of aryl iodides.

    PubMed

    Chen, Chunxia; Chen, Chen; Li, Bin; Tao, Jingwei; Peng, Jinsong

    2012-10-24

    A straightforward method has been developed for the synthesis of the benzimidazole ring system through a carbon-nitrogen cross-coupling reaction. In the presence of 2.0 equiv. of K(2)CO(3) in water at 100 °C for 30 h, the intramolecular cyclization of N-(2-iodoaryl)benzamidine provides benzimidazole derivatives in moderate to high yields. Remarkably, the procedure occurs exclusively in water and doesn’t require the use of any additional reagent/catalyst, rendering the methodology highly valuable from both environmental and economical points of view.

  15. Reusable Rocket Engine Operability Modeling and Analysis

    NASA Technical Reports Server (NTRS)

    Christenson, R. L.; Komar, D. R.

    1998-01-01

    This paper describes the methodology, model, input data, and analysis results of a reusable launch vehicle engine operability study conducted with the goal of supporting design from an operations perspective. Paralleling performance analyses in schedule and method, this requires the use of metrics in a validated operations model useful for design, sensitivity, and trade studies. Operations analysis in this view is one of several design functions. An operations concept was developed given an engine concept and the predicted operations and maintenance processes incorporated into simulation models. Historical operations data at a level of detail suitable to model objectives were collected, analyzed, and formatted for use with the models, the simulations were run, and results collected and presented. The input data used included scheduled and unscheduled timeline and resource information collected into a Space Transportation System (STS) Space Shuttle Main Engine (SSME) historical launch operations database. Results reflect upon the importance not only of reliable hardware but upon operations and corrective maintenance process improvements.

  16. Multilayer insulation materials for reusable space vehicles.

    NASA Technical Reports Server (NTRS)

    Leonhard, K. E.; Hyde, E. H.

    1971-01-01

    Results of an extensive study conducted to evaluate multilayer insulation (MLI) materials suitable for repeated space vehicle operation are presented. Materials studied were radiation shields, shield spacers, blanket face sheets, fasteners, and adhesives. The Superfloc MLI concept - Kapton shields goldized on both sides as the radiation barrier with Dacron flock tufts as the spacers - appeared to be an excellent MLI for reusable cryogenic tankage. Superfloc configurations consisting of various combinations of film, spacer, and adhesive materials were manufactured and tested. Tensile, flexing, expansion, and cycling tests were performed on goldized Kapton and Mylar Superfloc and Beta glass reinforced Pyre ML face sheet material. A face sheet material that retains its shape was developed. Polyphenylene oxide material was selected for fabricating lightweight twin and tri-pin fasteners, together with grommets, face sheets, and reinforcement slabs. Measured material thermal conductivity values are tabulated.

  17. Reusable Metallic Thermal Protection Systems Development

    NASA Technical Reports Server (NTRS)

    Blosser, Max L.; Martin, Carl J.; Daryabeigi, Kamran; Poteet, Carl C.

    1998-01-01

    Metallic thermal protection systems (TPS) are being developed to help meet the ambitious goals of future reusable launch vehicles. Recent metallic TPS development efforts at NASA Langley Research Center are described. Foil-gage metallic honeycomb coupons, representative of the outer surface of metallic TPS were subjected to low speed impact, hypervelocity impact, rain erosion, and subsequent arcjet exposure. TPS panels were subjected to thermal vacuum, acoustic, and hot gas flow testing. Results of the coupon and panel tests are presented. Experimental and analytical tools are being developed to characterize and improve internal insulations. Masses of metallic TPS and advanced ceramic tile and blanket TPS concepts are compared for a wide range of parameters.

  18. Vertical Landing Aerodynamics of Reusable Rocket Vehicle

    NASA Astrophysics Data System (ADS)

    Nonaka, Satoshi; Nishida, Hiroyuki; Kato, Hiroyuki; Ogawa, Hiroyuki; Inatani, Yoshifumi

    The aerodynamic characteristics of a vertical landing rocket are affected by its engine plume in the landing phase. The influences of interaction of the engine plume with the freestream around the vehicle on the aerodynamic characteristics are studied experimentally aiming to realize safe landing of the vertical landing rocket. The aerodynamic forces and surface pressure distributions are measured using a scaled model of a reusable rocket vehicle in low-speed wind tunnels. The flow field around the vehicle model is visualized using the particle image velocimetry (PIV) method. Results show that the aerodynamic characteristics, such as the drag force and pitching moment, are strongly affected by the change in the base pressure distributions and reattachment of a separation flow around the vehicle.

  19. Reusable Rocket Engine Turbopump Health Management System

    NASA Technical Reports Server (NTRS)

    Surko, Pamela

    1994-01-01

    A health monitoring expert system software architecture has been developed to support condition-based health monitoring of rocket engines. Its first application is in the diagnosis decisions relating to the health of the high pressure oxidizer turbopump (HPOTP) of Space Shuttle Main Engine (SSME). The post test diagnostic system runs off-line, using as input the data recorded from hundreds of sensors, each running typically at rates of 25, 50, or .1 Hz. The system is invoked after a test has been completed, and produces an analysis and an organized graphical presentation of the data with important effects highlighted. The overall expert system architecture has been developed and documented so that expert modules analyzing other line replaceable units may easily be added. The architecture emphasizes modularity, reusability, and open system interfaces so that it may be used to analyze other engines as well.

  20. Suborbital Reusable Launch Vehicles and Applicable Markets

    NASA Astrophysics Data System (ADS)

    Martin, J. C.; Law, G. W.

    2002-10-01

    The purpose of this report is to survey and characterize suborbital reusable launch vehicles (RLVs) in development, as well as to identify current and emerging suborbital market opportunities that these systems may enable. Over the past 30 years, NASA has accepted the burden of developing technologies that will enable cheaper access to orbital space, as evidenced by its past X-programs and the current Space Launch Initiative. Various private companies have also attempted, and are still attempting, to develop new RLV systems for orbital space applications. However, the large development costs of such systems, coupled with the downturn of the low Earth orbit market (e.g., Iridium, GlobalStar), have made private sector development of orbital RLV systems increasingly difficult at this time. Given these hurdles, many commercial space transportation companies have begun shifting focus toward suborbital market opportunities, for which the technical challenge is much lower and the cost of market entry less expensive.

  1. X-33 Reusable Launch Vehicle (RLV) Liftoff

    NASA Technical Reports Server (NTRS)

    2004-01-01

    The wedge-shaped X-33 was a sub-scale technology demonstration prototype of a Reusable Launch Vehicle (RLV). Through demonstration flights and ground research, NASA's X-33 program was to provide the information needed for industry representatives such as Lockheed Martin (builder of the X-33 Venture Star) to decide by the year 2000 whether to proceed with the development of a full-scale, commercial RLV program. This program would dramatically increase reliability and lower the costs of putting a payload into space. This would in turn create new opportunities for space access and significantly improve U.S. economic competitiveness in the worldwide launch marketplace. NASA would be a customer, not the operator in the commercial RLV. The X-33 program was cancelled in 2001.

  2. Reproducibility and reusability of scientific software

    NASA Astrophysics Data System (ADS)

    Shamir, Lior

    2017-01-01

    Information science and technology has been becoming an integral part of astronomy research, and due to the consistent growth in the size and impact of astronomical databases, that trend is bound to continue. While software is a vital part information systems and data analysis processes, in many cases the importance of the software and the standards of reporting on the use of source code has not yet elevated in the scientific communication process to the same level as other parts of the research. The purpose of the discussion is to examine the role of software in the scientific communication process in the light of transparency, reproducibility, and reusability of the research, as well as discussing software in astronomy in comparison to other disciplines.

  3. A Hydrazone-Based Covalent Organic Framework as an Efficient and Reusable Photocatalyst for the Cross-Dehydrogenative Coupling Reaction of N-Aryltetrahydroisoquinolines.

    PubMed

    Liu, Wanting; Su, Qing; Ju, Pengyao; Guo, Bixuan; Zhou, Hui; Li, Guanghua; Wu, Qiaolin

    2017-02-22

    A hydrazone-based covalent organic framework (COF) was synthesized by condensation of 2,5-dimethoxyterephthalohydrazide with 1,3,5-triformylbenzene under solvothermal conditions. The COF material exhibits excellent porosity with a BET surface area of up to 1501 m(2)  g(-1) , high crystallinity, and good thermal and chemical stability. Moreover, it showed efficient photocatalytic activity towards cross-dehydrogenative coupling (CDC) reactions between tetrahydroisoquinolines and nucleophiles such as nitromethane, acetone, and phenylethyl ketone. The metal-free catalytic system also offers attractive advantages including simplicity of operation, wide substrate adaptability, ambient reaction conditions, and robust recycling capability of the catalyst, thus providing a promising platform for highly efficient and reusable photocatalysts.

  4. Aeroheating Design Issues for Reusable Launch Vehicles: A Perspective

    NASA Technical Reports Server (NTRS)

    Zoby, E. Vincent; Thompson, Richard A.; Wurster, Kathryn E.

    2004-01-01

    An overview of basic aeroheating design issues for Reusable Launch Vehicles (RLV), which addresses the application of hypersonic ground-based testing, and computational fluid dynamic (CFD) and engineering codes, is presented. Challenges inherent to the prediction of aeroheating environments required for the successful design of the RLV Thermal Protection System (TPS) are discussed in conjunction with the importance of employing appropriate experimental/computational tools. The impact of the information garnered by using these tools in the resulting analyses, ultimately enhancing the RLV TPS design is illustrated. A wide range of topics is presented in this overview; e.g. the impact of flow physics issues such as boundary-layer transition, including effects of distributed and discrete roughness, shock-shock interactions, and flow separation/reattachment. Also, the benefit of integrating experimental and computational studies to gain an improved understanding of flow phenomena is illustrated. From computational studies, the effect of low-density conditions and of uncertainties in material surface properties on the computed heating rates a r e highlighted as well as the significant role of CFD in improving the Outer Mold Line (OML) definition to reduce aeroheating while maintaining aerodynamic performance. Appropriate selection of the TPS design trajectories and trajectory shaping to mitigate aeroheating levels and loads are discussed. Lastly, an illustration of an aeroheating design process is presented whereby data from hypersonic wind-tunnel tests are integrated with predictions from CFD codes and engineering methods to provide heating environments along an entry trajectory as required for TPS design.

  5. Aeroheating Design Issues for Reusable Launch Vehicles: A Perspective

    NASA Technical Reports Server (NTRS)

    Zoby, E. Vincent; Thompson, Richard A.; Wurster, Kathryn E.

    2004-01-01

    An overview of basic aeroheating design issues for Reusable Launch Vehicles (RLV), which addresses the application of hypersonic ground-based testing, and computational fluid dynamic (CFD) and engineering codes, is presented. Challenges inherent to the prediction of aeroheating environments required for the successful design of the RLV Thermal Protection System (TPS) are discussed in conjunction with the importance of employing appropriate experimental/computational tools. The impact of the information garnered by using these tools in the resulting analyses, ultimately enhancing the RLV TPS design is illustrated. A wide range of topics is presented in this overview; e.g. the impact of flow physics issues such as boundary-layer transition, including effects of distributed and discrete roughness, shockshock interactions, and flow separation/reattachment. Also, the benefit of integrating experimental and computational studies to gain an improved understanding of flow phenomena is illustrated. From computational studies, the effect of low-density conditions and of uncertainties in material surface properties on the computed heating rates are highlighted as well as the significant role of CFD in improving the Outer Mold Line (OML) definition to reduce aeroheating while maintaining aerodynamic performance. Appropriate selection of the TPS design trajectories and trajectory shaping to mitigate aeroheating levels and loads are discussed. Lastly, an illustration of an aeroheating design process is presented whereby data from hypersonic wind-tunnel tests are integrated with predictions from CFD codes and engineering methods to provide heating environments along an entry trajectory as required for TPS design.

  6. Sustaining Human Presence on Mars Using ISRU and a Reusable Lander

    NASA Technical Reports Server (NTRS)

    Arney, Dale C.; Jones, Christopher A.; Klovstad, Jordan J.; Komar, D.R.; Earle, Kevin; Moses, Robert; Shyface, Hilary R.

    2015-01-01

    This paper presents an analysis of the impact of ISRU (In-Site Resource Utilization), reusability, and automation on sustaining a human presence on Mars, requiring a transition from Earth dependence to Earth independence. The study analyzes the surface and transportation architectures and compared campaigns that revealed the importance of ISRU and reusability. A reusable Mars lander, Hercules, eliminates the need to deliver a new descent and ascent stage with each cargo and crew delivery to Mars, reducing the mass delivered from Earth. As part of an evolvable transportation architecture, this investment is key to enabling continuous human presence on Mars. The extensive use of ISRU reduces the logistics supply chain from Earth in order to support population growth at Mars. Reliable and autonomous systems, in conjunction with robotics, are required to enable ISRU architectures as systems must operate and maintain themselves while the crew is not present. A comparison of Mars campaigns is presented to show the impact of adding these investments and their ability to contribute to sustaining a human presence on Mars.

  7. Synthetic and mechanistic studies of metal-free transfer hydrogenations applying polarized olefins as hydrogen acceptors and amine borane adducts as hydrogen donors.

    PubMed

    Yang, Xianghua; Fox, Thomas; Berke, Heinz

    2012-01-28

    Metal-free transfer hydrogenation of polarized olefins (RR'C=CEE': R, R' = H or organyl, E, E' = CN or CO(2)Me) using amine borane adducts RR'NH-BH(3) (R = R' = H, AB; R = Me, R' = H, MAB; R = (t)Bu, R' = H, tBAB; R = R' = Me, DMAB) as hydrogen donors, were studied by means of in situ NMR spectroscopy. Deuterium kinetic isotope effects and the traced hydroboration intermediate revealed that the double H transfer process occurred regio-specifically in two steps with hydride before proton transfer characteristics. Studies on substituent effects and Hammett correlation indicated that the rate determining step of the H(N) transfer is in agreement with a concerted transition state. The very reactive intermediate [NH(2)=BH(2)] generated from AB was trapped by addition of cyclohexene into the reaction mixture forming Cy(2)BNH(2). The final product borazine (BHNH)(3) is assumed to be formed by dehydrocoupling of [NH(2)=BH(2)] or its solvent stabilized derivative [NH(2)=BH(2)]-(solvent), rather than by dehydrogenation of cyclotriborazane (BH(2)NH(2))(3) which is the trimerization product of [NH(2)=BH(2)].

  8. Reusable high-temperature heat pipes and heat pipe panels

    NASA Technical Reports Server (NTRS)

    Camarda, Charles J. (Inventor); Ransone, Philip O. (Inventor)

    1989-01-01

    A reusable, durable heat pipe which is capable of operating at temperatures up to about 3000 F in an oxidizing environment and at temperatures above 3000 F in an inert or vacuum environment is produced by embedding a refractory metal pipe within a carbon-carbon composite structure. A reusable, durable heat pipe panel is made from an array of refractory-metal pipes spaced from each other. The reusable, durable, heat-pipe is employed to fabricate a hypersonic vehicle leading edge and nose cap.

  9. Condition monitoring helps make the Space Shuttle Main Engine reusable

    NASA Technical Reports Server (NTRS)

    Lacroix, W. P.

    1973-01-01

    The Space Shuttle Main Engine (SSME) is a reusable, high-performance liquid-propellant rocket engine being developed for the Space Shuttle Orbiter Vehicle. The SSME has been designed for long life, rapid postflight maintenance, and a fast vehicle turnaround cycle of 160 hours. To meet the unique reusability requirements, the SSME considers maintainability and condition monitoring much as airlines do today. The condition monitoring capabilities designed into this engine are discussed with major emphasis on internal inspection and techniques which ensure the reusability of the SSME.

  10. Conceptual Design of an APT Reusable Spaceplane

    NASA Astrophysics Data System (ADS)

    Corpino, S.; Viola, N.

    This paper concerns the conceptual design of an Aerial Propellant Transfer reusable spaceplane carried out during our PhD course under the supervision of prof. Chiesa. The new conceptual design methodology employed in order to develop the APT concept and the main characteristics of the spaceplane itself will be presented and discussed. The methodology for conceptual design has been worked out during the last three years. It was originally thought for atmospheric vehicle design but, thanks to its modular structure which makes it very flexible, it has been possible to convert it to space transportation systems design by adding and/or modifying a few modules. One of the major improvements has been for example the conception and development of the mission simulation and trajectory optimisation module. The methodology includes as main characteristics and innovations the latest techniques of geometric modelling and logistic, operational and cost aspects since the first stages of the project. Computer aided design techniques are used to obtain a better definition of the product at the end of the conceptual design phase and virtual reality concepts are employed to visualise three-dimensional installation and operational aspects, at least in part replacing full-scale mock- ups. The introduction of parametric three-dimensional CAD software integrated into the conceptual design methodology represents a great improvement because it allows to carry out different layouts and to assess them immediately. It is also possible to link the CAD system to a digital prototyping software which combines 3D visualisation and assembly analysis, useful to define the so-called Digital Mock-Up at Conceptual Level (DMUCL) which studies the integration between the on board systems, sized with simulation algorithms, and the airframe. DMUCL represents a very good means to integrate the conceptual design with a methodology turned towards dealing with Reliability, Availability, Maintainability and

  11. 14 CFR 431.79 - Reusable launch vehicle mission reporting requirements.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... 14 Aeronautics and Space 4 2011-01-01 2011-01-01 false Reusable launch vehicle mission reporting... ADMINISTRATION, DEPARTMENT OF TRANSPORTATION LICENSING LAUNCH AND REENTRY OF A REUSABLE LAUNCH VEHICLE (RLV) Post-Licensing Requirements-Reusable Launch Vehicle Mission License Terms and Conditions § 431.79 Reusable...

  12. Inhibitory Activity Of Curcumin Derivatives Towards Metal-free And Metal-induced Amyloid-β Aggregation.

    PubMed

    Kochi, Akiko; Lee, Hyuck Jin; Vithanarachchi, Sashiprabha M; Padmini, Vediappen; Allen, Matthew J; Lim, Mi Hee

    2015-01-01

    When Alzheimer's disease (AD) progresses, several pathological features arise including accumulation of misfolded protein aggregates [e.g., amyloid-β (Aβ) plaques], metal ion dyshomeostasis, and oxidative stress. These characteristics are recently suggested to be interconnected through a potential factor, metal-associated Aβ (metal-Aβ) species. The role of metal-Aβ species in AD pathogenesis remains unclear, however. To elucidate the contribution of metal-Aβ species to AD pathology, as well as to develop small molecules as chemical tools and/or theranostic (therapeutic and diagnostic) agents for this disease, curcumin (Cur), a natural product from turmeric, and its derivatives have been studied towards both metal-free and metal-induced Aβ aggregation. Although Cur has indicated anti-amyloidogenic activities and antioxidant properties, its biological use has been hindered due to low solubility and stability in physiologically relevant conditions. Herein, we report the reactivity of Cur and its derivatives (Gd-Cur, a potential multimodal Aβ imaging agent; Cur-S, a water soluble derivative of Cur that has substitution at the phenolic hydroxyls) with metal-free Aβ and metal-Aβ species. Our results and observations indicate that Gd-Cur could modulate Cu(II)-triggered Aβ aggregation more noticeably over metal-free or Zn(II)-induced analogues; however, Cur-S was not observed to noticeably modulate Aβ aggregation with and without metal ions. Overall, our studies present information that could aid in optimizing the molecular scaffold of Cur for the development of chemical tools or theranostics for metal-Aβ species.

  13. Inner hydrogen atom transfer in benzo-fused low symmetrical metal-free tetraazaporphyrin and phthalocyanine analogues: density functional theory studies.

    PubMed

    Qi, Dongdong; Zhang, Yuexing; Cai, Xue; Jiang, Jianzhuang; Bai, Ming

    2009-02-01

    Density functional theory (DFT) calculations were carried out to study the inner hydrogen atom transfer in low symmetrical metal-free tetrapyrrole analogues ranging from tetraazaporphyrin H(2)TAP (A(0)B(0)C(0)D(0)) to naphthalocyanine H(2)Nc (A(2)B(2)C(2)D(2)) via phthalocyanine H(2)Pc (A(1)B(1)C(1)D(1)). All the transition paths of sixteen different compounds (A(0)B(0)C(0)D(0)-A(2)B(2)C(2)D(2) and A(0)B(0)C(m)D(n), m transitivity of inner hydrogen atom and thus lower the transfer barrier of this inner hydrogen atom while fusing benzene rings onto the hydrogen-accepting pyrrole rings will increase the hydrogen transfer barrier to this pyrrole ring. The transient cis-isomer intermediate with hydrogen atoms joined to the two adjacent pyrrole rings with less fused benzene rings is much stable than the others. It is also found that the benzene rings fused directly onto pyrrole rings have more effect on the inner hydrogen atom transfer than the outer benzene rings fused onto the periphery of isoindole rings. The present work, representing the first effort towards systematically understanding the effect of ring enlargement through asymmetrical peripheral fusion of benzene ring(s) onto the TAP skeleton on the inner hydrogen transfer of tetrapyrrole derivatives, will be helpful in clarifying the N-H tautomerization phenomenon and detecting the cis-porphyrin isomer in bio-systems.

  14. Azaborabutadienes: Synthesis by Metal-Free Carboboration of Nitriles and Utility as Building Blocks for B,N-Heterocycles.

    PubMed

    Kong, Lingbing; Lu, Wei; Li, Yongxin; Ganguly, Rakesh; Kinjo, Rei

    2016-11-14

    Metal-free regioselective carboboration of arylnitriles with L2 PhB: (1: L=oxazol-2-ylidene) catalyzed by Et3 B afforded the unprecedented acyclic 2-aza-4-borabutadienes 2, thus demonstrating a new strategy to construct a B,C,N-mixed π-system involving B=C and C=N bonds. Thermal isomerization of 2 gave C-borylimines (3), and diverse reactivity of 2 a towards several substrates, such as H(+) , F(+) , O2 , S, Se, and isonitriles, allowed construction of boron-containing heterocycles with various ring sizes, thus illustrating the utility of 2 as a synthetic building block.

  15. Three-unit bridge construction in anterior single-pontic areas using a metal-free restorative.

    PubMed

    Narcisi, E M

    1999-02-01

    A new glass-ceramic material, IPS Empress 2, is revolutionizing esthetic restorative dentistry by allowing metal-free, three-unit bridge construction in anterior and premolar single-pontic areas. The case discussed in this article illustrates the material's application in the dual-arch restoration of a young woman with congenitally missing teeth. The material was used as an alternative to single-tooth implant restorations to place two maxillary three-unit bridges, one mandibular three-unit bridge, and two mandibular porcelain veneers. IPS Empress 2 provides an esthetic alternative to porcelain-fused-to-metal restorations by facilitating attractive, functional tooth restoration.

  16. Automated metal-free multiple-column nanoLC for improved phosphopeptide analysis sensitivity and throughput

    SciTech Connect

    Zhao, Rui; Ding, Shi-Jian; Shen, Yufeng; Camp, David G.; Livesay, Eric A.; Udseth, Harold R.; Smith, Richard D.

    2009-03-15

    We report on the development and characterization of an automated metal-free nanoscale multiple-capillary system for reversed-phase liquid chromatography-mass spectrometry analysis of phosphopeptides. The system incorporates a capillary column (50 um i.d. × 30 cm, packed with 5 um C18 particles) coupled on-line to a solid phase extraction column (150 um i.d. × 4 cm, packed with 5 um C18 particles). Electrospray ionization tips are constructed on the packed capillary column to couple the reversed-phase liquid chromatographic separation to a linear ion trap tandem mass spectrometer.

  17. Metal-free oxysulfenylation of alkenes with 1-(arylthio)pyrrolidine-2,5-diones and alcohols.

    PubMed

    Yu, Jipan; Gao, Chang; Song, Zhixuan; Yang, Haijun; Fu, Hua

    2015-05-07

    β-Alkoxy sulfides are widely used as versatile building blocks in organic synthesis. Therefore, it is highly desirable to develop a convenient and efficient method for oxysulfenylation of alkenes. In this communication, an easy and efficient metal-free approach to β-alkoxy sulfides has been developed. The protocol uses readily available 1-(arylthio)pyrrolidine-2,5-diones and alcohols as the oxysulfenylating agents, chloroform as the solvent, and no ligand, additive and exclusion of air were required. Therefore, the present method provides a useful strategy for synthesis of β-alkoxy sulfides.

  18. Metal-Free Synthesis of N-Aryl Amides using Organocatalytic Ring-Opening Aminolysis of Lactones.

    PubMed

    Guo, Wusheng; Gómez, José Enrique; Martínez-Rodríguez, Luis; Bandeira, Nuno A G; Bo, Carles; Kleij, Arjan W

    2017-04-05

    Catalytic ring-opening of bio-sourced non-strained lactones with aromatic amines can offer a straightforward, 100 % atom-economical, and sustainable pathway towards relevant N-aryl amide scaffolds. Herein, the first general, metal-free, and highly efficient N-aryl amide formation is reported from poorly reactive aromatic amines and non-strained lactones under mild operating conditions using an organic bicyclic guanidine catalyst. This protocol has high application potential as exemplified by the formal syntheses of drug-relevant molecules.

  19. Metal-free metathesis reaction of C-chiral allylic sulfilimines with aryl isocyanates: construction of chiral nonracemic allylic isocyanates.

    PubMed

    Grange, Rebecca L; Evans, P Andrew

    2014-08-27

    We report the facile and efficient metal-free metathesis reaction of C-chiral allylic sulfilimines with aryl isocyanates. This process facilitates the room temperature construction of an array of chiral nonracemic allylic isocyanates, which are versatile intermediates for the construction of unsymmetrical ureas, carbamates, thiocarbamates and amides. Furthermore, the sulfilimine/isocyanate metathesis reaction with 4,4'-methylene diphenyl diisocyanate (4,4'-MDI) circumvents harsh reaction conditions and/or hazardous reagents employed with more classical methods for the preparation of this important functional group.

  20. Metal-free α-Amination of Secondary Amines: Computational and Experimental Evidence for Azaquinone Methide and Azomethine Ylide Intermediates

    PubMed Central

    Dieckmann, Arne; Richers, Matthew T.; Platonova, Alena Yu.; Zhang, Chen; Seidel, Daniel; Houk, K. N.

    2013-01-01

    We have performed a combined computational and experimental study to elucidate the mechanism of a metal-free α-amination of secondary amines. Calculations predicted azaquinone methides and azomethine ylides as the reactive intermediates and showed that iminium ions are unlikely to participate in these transformations. These results were confirmed by experimental deuterium labeling studies and the successful trapping of the postulated azomethine ylide and azaquinone methide intermediates. In addition, computed barrier heights for the rate-limiting step correlate qualitatively with experimental findings. PMID:23517448

  1. Reusable Component Model Development Approach for Parallel and Distributed Simulation

    PubMed Central

    Zhu, Feng; Yao, Yiping; Chen, Huilong; Yao, Feng

    2014-01-01

    Model reuse is a key issue to be resolved in parallel and distributed simulation at present. However, component models built by different domain experts usually have diversiform interfaces, couple tightly, and bind with simulation platforms closely. As a result, they are difficult to be reused across different simulation platforms and applications. To address the problem, this paper first proposed a reusable component model framework. Based on this framework, then our reusable model development approach is elaborated, which contains two phases: (1) domain experts create simulation computational modules observing three principles to achieve their independence; (2) model developer encapsulates these simulation computational modules with six standard service interfaces to improve their reusability. The case study of a radar model indicates that the model developed using our approach has good reusability and it is easy to be used in different simulation platforms and applications. PMID:24729751

  2. Coatings and Surface Treatments for Reusable Entry Systems

    NASA Technical Reports Server (NTRS)

    Johnson, Sylvia M.

    2016-01-01

    This talk outlines work in coatings for TPS done at NASA Ames. coatings and surface treatments on reusable TPS are critical for controlling the behavior of the materials. coatings discussed include RCG, TUFI and HETC. TUFROc is also discussed.

  3. What's best--reusable or disposable incontinence products?

    PubMed

    Haeker, S

    1986-05-01

    To use paper or cloth? The director of nursing for a 72-bed intermediate care facility opted to continue using reusable incontinence products based on the results of a three-week study conducted by her staff.

  4. Considerations for the design of Ada reusable packages

    NASA Technical Reports Server (NTRS)

    Nise, Norman S.; Giffin, Chuck

    1986-01-01

    Two important considerations that precede the design of Ada reusable packages (commonality and programming standards) are discuessed. First, the importance of designing packages to yield widespread commonality is expressed. A means of measuring the degree of applicability of packages both within and across applications areas is presented. Design consideration that will improve commonality are also discussed. Second, considerations for the development of programming standards are set forth. These considerations will lead to standards that will improve the reusability of Ada packages.

  5. A Reusable Lunar Shuttlecraft (RLS): A systems study

    NASA Technical Reports Server (NTRS)

    1973-01-01

    A study effort to conceive and design a reusable lunar space vehicle system was conducted at a university. The purpose of the program was to expose students to the problems faced by other disciplines in the design of a complete vehicle system. The subjects investigated are: (1) objectives, feasibility, and cost of reusable lunar shuttlecraft, (2) trajectory analysis, (3) guidance and navigation, (4) communication system, (5) propulsion system, (6) electrical power system, and (7) landing gear design.

  6. Improvement of Reusable Surface Insulation (RSI) materials

    NASA Technical Reports Server (NTRS)

    Blome, J. C.

    1972-01-01

    The mullite fiber based hardened compacted fibers (HCF) type of reusable surface insulation was further developed for use in the Space Shuttle Program. Two hundred fifty formulations of fiber mixtures, fillers, binders, and organic processing aids were made using mullite fibers as the basic ingredient. Most of the work was accomplished on 15-lb/cu ft material. It was established that higher density materials are stronger with strength values as high as 250 lb/sq in. in tension. New measurement techniques and equipment were developed for accurate determination of strength and strain to failure. Room temperature to 2300 F stress-strain relationships were made. The room temperature tensile modulus of elasticity is 61,700 lb/sq in. and the strain at failure is 0.165 percent, typically, when measured longitudinally parallel to the long axes of the fibers. Thermal insulating effectiveness was increased 20 percent by reducing the diameter of some of the fibers in the material. Improvements were made in density uniformity and strength uniformity in a block of HCF by mixing improvements and by the use of organic additives. Specifications were established on the materials and processes used in making the insulation.

  7. Reusable Reentry Satellite (RRS): Configuration trade study

    NASA Technical Reports Server (NTRS)

    1990-01-01

    The overall Reusable Reentry Satellite (RRS) Phase B Study objective is to design a relatively inexpensive satellite to access space for extended periods of time, with eventual recovery of experiments on Earth. The expected principal use for such a system is research on the effects of variable gravity (0-1.5 g) and radiation on small animals, plants, lower life forms, tissue samples, and materials processes. The RRS will be capable of: (1) being launched by a variety of expendable launch vehicles; (2) operating in low earth orbit as a free flying unmanned laboratory; and (3) executing independent atmospheric reentry and soft landing. The RRS will be designed to be refurbished and reused up to three times a year for a period of 10 years. The information provided in this report describes the process involved in the evolution of the RRS overall configuration. This process considered reentry aerodynamics, aerothermodynamics, internal equipment layout, and vehicle mass properties. This report delineates the baseline design decisions that were used to initiate the RRS design effort. As a result, there will be deviations between this report and the RRS Final Report. In those instances, the RRS Final Report shall be considered to be the definitive reference.

  8. Reusable tube piercing tool for refrigerant recovery

    SciTech Connect

    Price, L.D.; Scheiben, F.M.

    1994-01-04

    A refrigerant tube piercing tool is described capable of being removably and sealingly mounted on a refrigerant tube of copper or the like in a sealed refrigerant system to enable the recovery of refrigerant from the sealed system without discharge into the atmosphere. The tool includes a pair of clamp members one of which includes a sealing member and passageway combined with a threaded, pointed piercing member that is manually threaded into engagement with the tube for forming a hole therein and a fitting having a Schrader valve incorporated therein to which a hose leading to a recovery tank can be connected to enable refrigerant to be transferred into the recovery tank for subsequent use. The tool is reusable and can be removed after the refrigerant has been transferred into the recovery tank in order that the leak or other problem with respect to the refrigerant system can be repaired at which time the hole formed in the tube is closed by soldering or the like with the refrigerant system then being recharged. 5 figs.

  9. Documenting Models for Interoperability and Reusability ...

    EPA Pesticide Factsheets

    Many modeling frameworks compartmentalize science via individual models that link sets of small components to create larger modeling workflows. Developing integrated watershed models increasingly requires coupling multidisciplinary, independent models, as well as collaboration between scientific communities, since component-based modeling can integrate models from different disciplines. Integrated Environmental Modeling (IEM) systems focus on transferring information between components by capturing a conceptual site model; establishing local metadata standards for input/output of models and databases; managing data flow between models and throughout the system; facilitating quality control of data exchanges (e.g., checking units, unit conversions, transfers between software languages); warning and error handling; and coordinating sensitivity/uncertainty analyses. Although many computational software systems facilitate communication between, and execution of, components, there are no common approaches, protocols, or standards for turn-key linkages between software systems and models, especially if modifying components is not the intent. Using a standard ontology, this paper reviews how models can be described for discovery, understanding, evaluation, access, and implementation to facilitate interoperability and reusability. In the proceedings of the International Environmental Modelling and Software Society (iEMSs), 8th International Congress on Environmental Mod

  10. A reusable knowledge acquisition shell: KASH

    NASA Technical Reports Server (NTRS)

    Westphal, Christopher; Williams, Stephen; Keech, Virginia

    1991-01-01

    KASH (Knowledge Acquisition SHell) is proposed to assist a knowledge engineer by providing a set of utilities for constructing knowledge acquisition sessions based on interviewing techniques. The information elicited from domain experts during the sessions is guided by a question dependency graph (QDG). The QDG defined by the knowledge engineer, consists of a series of control questions about the domain that are used to organize the knowledge of an expert. The content information supplies by the expert, in response to the questions, is represented in the form of a concept map. These maps can be constructed in a top-down or bottom-up manner by the QDG and used by KASH to generate the rules for a large class of expert system domains. Additionally, the concept maps can support the representation of temporal knowledge. The high degree of reusability encountered in the QDG and concept maps can vastly reduce the development times and costs associated with producing intelligent decision aids, training programs, and process control functions.

  11. Viability of a Reusable In-Space Transportation System

    NASA Technical Reports Server (NTRS)

    Jefferies, Sharon A.; McCleskey, Carey M.; Nufer, Brian M.; Lepsch, Roger A.; Merrill, Raymond G.; North, David D.; Martin, John G.; Komar, David R.

    2015-01-01

    The National Aeronautics and Space Administration (NASA) is currently developing options for an Evolvable Mars Campaign (EMC) that expands human presence from Low Earth Orbit (LEO) into the solar system and to the surface of Mars. The Hybrid in-space transportation architecture is one option being investigated within the EMC. The architecture enables return of the entire in-space propulsion stage and habitat to cis-lunar space after a round trip to Mars. This concept of operations opens the door for a fully reusable Mars transportation system from cis-lunar space to a Mars parking orbit and back. This paper explores the reuse of in-space transportation systems, with a focus on the propulsion systems. It begins by examining why reusability should be pursued and defines reusability in space-flight context. A range of functions and enablers associated with preparing a system for reuse are identified and a vision for reusability is proposed that can be advanced and implemented as new capabilities are developed. Following this, past reusable spacecraft and servicing capabilities, as well as those currently in development are discussed. Using the Hybrid transportation architecture as an example, an assessment of the degree of reusability that can be incorporated into the architecture with current capabilities is provided and areas for development are identified that will enable greater levels of reuse in the future. Implications and implementation challenges specific to the architecture are also presented.

  12. Surface-nitrogen-rich ordered mesoporous carbon as an efficient metal-free electrocatalyst for oxygen reduction reaction.

    PubMed

    Xiao, Chunhui; Chen, Xu; Fan, Zhaoyang; Liang, Jin; Zhang, Bo; Ding, Shujiang

    2016-11-04

    Exploring efficient metal-free electrocatalysts for oxygen reduction reactions (ORR) will have a great impact on the field of fuel cells and metal-air batteries. In this paper, we report a simple and efficient routine to coat ordered mesoporous carbon (CMK-3) with nitrogen-doped carbon via pyrolysis of the surface-self-polymerized polydopamine. The optimized CMK-3 catalyst with a coating of nitrogen-doped carbon demonstrates excellent electrocatalytic activity towards ORR in alkaline media. The coating procedure under optimized conditions lowers the ORR half-wave-potential by 80 mV, giving a genuine metal-free catalyst with an onset ORR potential of 0.96 V (vs reversible hydrogen electrode (RHE)) and half-wave potential of 0.83 V (vs RHE) in 0.1 M KOH, which is much better than other carbon material-based catalysts (such as carbon nanotubes and their composites). The performance of this surface-nitrogen-rich CMK-3 catalyst is also superior to that of N-doped ordered mesoporous carbon synthesized by means of the 'nanocasting' technique. Furthermore, the as-prepared catalyst performs comparably in terms of activity, superior durability, and higher tolerance to methanol compared with commercially available Pt/C.

  13. Metal-free molecular junctions on ITO via amino-silane binding-towards optoelectronic molecular junctions.

    PubMed

    Sergani, S; Furmansky, Y; Visoly-Fisher, I

    2013-11-15

    Light control over currents in molecular junctions is desirable as a non-contact input with high spectral and spatial resolution provided by the photonic input and the molecular electronics element, respectively. Expanding the study of molecular junctions to non-metallic transparent substrates, such as indium tin oxide (ITO), is vital for the observation of molecular optoelectronic effects. Non-metallic electrodes are expected to decrease the probability of quenching of molecular photo-excited states, light-induced plasmonic effects, or significant electrode expansion under visible light. We have developed micron-sized, metal free, optically addressable ITO molecular junctions with a conductive polymer serving as the counter-electrode. The electrical transport was shown to be dominated by the nature of the self-assembled monolayer (SAM). The use of amino-silane (APTMS) as the chemical binding scheme to ITO was found to be significant in determining the transport properties of the junctions. APTMS allows high junction yields and the formation of dense molecular layers preventing electrical short. However, polar amino-silane binding to the ITO significantly decreased the conductance compared to thiol-bound SAMs, and caused tilted geometry and disorder in the molecular layer. As the effect of the molecular structure on transport properties is clearly observed in our junctions, such metal-free junctions are suitable for characterizing the optoelectronic properties of molecular junctions.

  14. Metal-free molecular junctions on ITO via amino-silane binding—towards optoelectronic molecular junctions

    NASA Astrophysics Data System (ADS)

    Sergani, S.; Furmansky, Y.; Visoly-Fisher, I.

    2013-11-01

    Light control over currents in molecular junctions is desirable as a non-contact input with high spectral and spatial resolution provided by the photonic input and the molecular electronics element, respectively. Expanding the study of molecular junctions to non-metallic transparent substrates, such as indium tin oxide (ITO), is vital for the observation of molecular optoelectronic effects. Non-metallic electrodes are expected to decrease the probability of quenching of molecular photo-excited states, light-induced plasmonic effects, or significant electrode expansion under visible light. We have developed micron-sized, metal free, optically addressable ITO molecular junctions with a conductive polymer serving as the counter-electrode. The electrical transport was shown to be dominated by the nature of the self-assembled monolayer (SAM). The use of amino-silane (APTMS) as the chemical binding scheme to ITO was found to be significant in determining the transport properties of the junctions. APTMS allows high junction yields and the formation of dense molecular layers preventing electrical short. However, polar amino-silane binding to the ITO significantly decreased the conductance compared to thiol-bound SAMs, and caused tilted geometry and disorder in the molecular layer. As the effect of the molecular structure on transport properties is clearly observed in our junctions, such metal-free junctions are suitable for characterizing the optoelectronic properties of molecular junctions.

  15. Silicon and phosphorus dual doped graphene as the promising metal-free catalysts for oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Lu, Zhansheng; Li, Shuo; Yang, Zongxian; Wu, Ruqian

    The pathways of oxygen reduction reaction (ORR) on the metal-free silicon and phosphorus dual doped graphene (Si-P-G) catalyst are systematically investigated based on the dispersion-corrected density functional theory (DFT-D) method. It is found that the Si-P-G can be stable at high temperature from the first-principles molecular dynamics simulation and the local region of dopants displays an important role in the adsorption and reduction of oxygen. Both of the four-electron O2 direct dissociation and the two-electron OOH dissociation pathways are probable for ORR on the Si-P-G, while the latter pathway is mainly followed by the pathway of the OH hydrogenation into H2O. For the OOH dissociation pathway, the hydrogenation of O2 to OOH is the rate-limiting step with a rather small barrier energy of 0.66 eV. The current results indicate that the Si-P-G is a novel metal-free catalyst for ORR, and which is comparable to that of the Pt catalyst. Work was supported by the National Science Foundation Center for Chemical Innovation on Chemistry at the Space-Time Limit (CaSTL) under Grant No. CHE-1414466, and the National Natural Science Foundation of China (Grant Nos. 51401078, and 11474086).

  16. Bonding state of metal-free CAD/CAM onlay restoration after cyclic loading with and without immediate dentin sealing.

    PubMed

    Ishii, Noriko; Maseki, Toshio; Nara, Yoichiro

    2017-05-31

    To examine the bonding state of metal-free CAD/CAM onlay restorations made from two popular resin composite blocks and a typical glass-ceramic block after cyclic loading, with and without immediate dentin sealing (IDS). Standardized mesial-distal-occlusalbuccal (MODB) cavities in 24 extracted human molars were prepared. The intra-cavity dentin surfaces of half of the cavities were immediately sealed with all-in-one adhesive and flowable composite, while those of the other half were not. All cavities were scanned, from which CAD/CAM onlays were fabricated from three types of block and cemented with an adhesive resin cement system. The restored specimens were subjected to cyclic loading and the intra-cavity microtensile bond strength was measured. IDS improves not only the internal bond strength, but also the bond reliability of metal-free CAD/CAM onlay restorations. The resin composite block seems to be more effective than a typical glass-ceramic block for achieving both high bond strength and excellent bond reliability.

  17. Surface-nitrogen-rich ordered mesoporous carbon as an efficient metal-free electrocatalyst for oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Xiao, Chunhui; Chen, Xu; Fan, Zhaoyang; Liang, Jin; Zhang, Bo; Ding, Shujiang

    2016-11-01

    Exploring efficient metal-free electrocatalysts for oxygen reduction reactions (ORR) will have a great impact on the field of fuel cells and metal-air batteries. In this paper, we report a simple and efficient routine to coat ordered mesoporous carbon (CMK-3) with nitrogen-doped carbon via pyrolysis of the surface-self-polymerized polydopamine. The optimized CMK-3 catalyst with a coating of nitrogen-doped carbon demonstrates excellent electrocatalytic activity towards ORR in alkaline media. The coating procedure under optimized conditions lowers the ORR half-wave-potential by 80 mV, giving a genuine metal-free catalyst with an onset ORR potential of 0.96 V (vs reversible hydrogen electrode (RHE)) and half-wave potential of 0.83 V (vs RHE) in 0.1 M KOH, which is much better than other carbon material-based catalysts (such as carbon nanotubes and their composites). The performance of this surface-nitrogen-rich CMK-3 catalyst is also superior to that of N-doped ordered mesoporous carbon synthesized by means of the ‘nanocasting’ technique. Furthermore, the as-prepared catalyst performs comparably in terms of activity, superior durability, and higher tolerance to methanol compared with commercially available Pt/C.

  18. Electrochemical dopamine sensor based on P-doped graphene: Highly active metal-free catalyst and metal catalyst support.

    PubMed

    Chu, Ke; Wang, Fan; Zhao, Xiao-Lin; Wang, Xin-Wei; Tian, Ye

    2017-12-01

    Heteroatom doping is an effective strategy to enhance the catalytic activity of graphene and its hybrid materials. Despite a growing interest of P-doped graphene (P-G) in energy storage/generation applications, P-G has rarely been investigated for electrochemical sensing. Herein, we reported the employment of P-G as both metal-free catalyst and metal catalyst support for electrochemical detection of dopamine (DA). As a metal-free catalyst, P-G exhibited prominent DA sensing performances due to the important role of P doping in improving the electrocatalytic activity of graphene toward DA oxidation. Furthermore, P-G could be an efficient supporting material for loading Au nanoparticles, and resulting Au/P-G hybrid showed a dramatically enhanced electrocatalytic activity and extraordinary sensing performances with a wide linear range of 0.1-180μM and a low detection limit of 0.002μM. All these results demonstrated that P-G might be a very promising electrode material for electrochemical sensor applications. Copyright © 2017 Elsevier B.V. All rights reserved.

  19. Is It Worth It? - the Economics of Reusable Space Transportation

    NASA Technical Reports Server (NTRS)

    Webb, Richard

    2016-01-01

    Over the past several decades billions of dollars have been invested by governments and private companies in the pursuit of lower cost access to space through earth-to-orbit (ETO) space transportation systems. Much of that investment has been focused on the development and operation of various forms of reusable transportation systems. From the Space Shuttle to current efforts by private commercial companies, the overarching belief of those making such investments has been that reusing system elements will be cheaper than utilizing expendable systems that involve throwing away costly engines, avionics, and other hardware with each flight. However, the view that reusable systems are ultimately a "better" approach to providing ETO transportation is not held universally by major stakeholders within the space transportation industry. While the technical feasibility of at least some degree of reusability has been demonstrated, there continues to be a sometimes lively debate over the merits and drawbacks of reusable versus expendable systems from an economic perspective. In summary, is it worth it? Based on our many years of direct involvement with the business aspects of several expendable and reusable transportation systems, it appears to us that much of the discussion surrounding reusability is hindered by a failure to clearly define and understand the financial and other metrics by which the financial "goodness" of a reusable or expandable approach is measured. As stakeholders, the different users and suppliers of space transportation have a varied set of criteria for determining the relative economic viability of alternative strategies, including reusability. Many different metrics have been used to measure the affordability of space transportation, such as dollars per payload pound (kilogram) to orbit, cost per flight, life cycle cost, net present value/internal rate of return, and many others. This paper will examine the key considerations that influence

  20. Performance of a New Reusable Insulin Pen

    PubMed Central

    2011-01-01

    Abstract Background The aim of this multinational (Canada, France, Germany, United Kingdom, and United States), task and interview-based study was to compare the ease of use and performance of the ClikSTAR® (sanofi-aventis, Paris, France) insulin pen with other commonly used reusable pens based on participant and interviewer assessments. Methods People with diabetes (n = 654) were asked to demonstrate four pens consecutively—ClikSTAR, Lilly Luxura® (Eli Lilly, Indianapolis, IN), and NovoPen® 3 and 4 (Novo Nordisk, Bagsvaerd, Denmark)—according to the respective instruction manuals. The endpoint was assessed by a rating from the participants and the interviewer. While the participants focused on the pen's ease of use, the interviewer considered the participants' difficulty in preparing and delivering a 40-unit dose and their requirement for help. Results Twenty percent of U.S. participants and 24% of participants from the other countries had type 1 diabetes. Approximately 50% of participants in each group had prior insulin pen experience. A higher proportion of participants, including those with dexterity or visual impairments, reported ClikSTAR as easier to use than other pens (P < 0.05). Participants using ClikSTAR did not experience any difficulty in completing the tasks. The proportion of participants not requiring help in completing the tasks with ClikSTAR was rated as numerically higher than, or similar to, that observed with Lilly Luxura or NovoPen 3 or 4 (75%, 74%, 62%, and 65%, respectively). According to participants, ClikSTAR and NovoPen 4 emerged as the most highly rated pens. Conclusions In comparison with other pens, ClikSTAR was significantly easier to use, which, when taken together with overall performance, meets the need of people with diabetes. PMID:21291331

  1. Dynamic reusable workflows for ocean science

    USGS Publications Warehouse

    Signell, Richard; Fernandez, Filipe; Wilcox, Kyle

    2016-01-01

    Digital catalogs of ocean data have been available for decades, but advances in standardized services and software for catalog search and data access make it now possible to create catalog-driven workflows that automate — end-to-end — data search, analysis and visualization of data from multiple distributed sources. Further, these workflows may be shared, reused and adapted with ease. Here we describe a workflow developed within the US Integrated Ocean Observing System (IOOS) which automates the skill-assessment of water temperature forecasts from multiple ocean forecast models, allowing improved forecast products to be delivered for an open water swim event. A series of Jupyter Notebooks are used to capture and document the end-to-end workflow using a collection of Python tools that facilitate working with standardized catalog and data services. The workflow first searches a catalog of metadata using the Open Geospatial Consortium (OGC) Catalog Service for the Web (CSW), then accesses data service endpoints found in the metadata records using the OGC Sensor Observation Service (SOS) for in situ sensor data and OPeNDAP services for remotely-sensed and model data. Skill metrics are computed and time series comparisons of forecast model and observed data are displayed interactively, leveraging the capabilities of modern web browsers. The resulting workflow not only solves a challenging specific problem, but highlights the benefits of dynamic, reusable workflows in general. These workflows adapt as new data enters the data system, facilitate reproducible science, provide templates from which new scientific workflows can be developed, and encourage data providers to use standardized services. As applied to the ocean swim event, the workflow exposed problems with two of the ocean forecast products which led to improved regional forecasts once errors were corrected. While the example is specific, the approach is general, and we hope to see increased use of dynamic

  2. Reusable Reentry Satellite (RRS) system design study

    NASA Technical Reports Server (NTRS)

    1991-01-01

    The Reusable Reentry Satellite (RRS) is intended to provide investigators in several biological disciplines with a relatively inexpensive method to access space for up to 60 days with eventual recovery on Earth. The RRS will permit totally intact, relatively soft, recovery of the vehicle, system refurbishment, and reflight with new and varied payloads. The RRS is to be capable of three reflights per year over a 10-year program lifetime. The RRS vehicle will have a large and readily accessible volume near the vehicle center of gravity for the Payload Module (PM) containing the experiment hardware. The vehicle is configured to permit the experimenter late access to the PM prior to launch and rapid access following recovery. The RRS will operate in one of two modes: (1) as a free-flying spacecraft in orbit, and will be allowed to drift in attitude to provide an acceleration environment of less than 10(exp -5) g. the acceleration environment during orbital trim maneuvers will be less than 10(exp -3) g; and (2) as an artificial gravity system which spins at controlled rates to provide an artificial gravity of up to 1.5 Earth g. The RRS system will be designed to be rugged, easily maintained, and economically refurbishable for the next flight. Some systems may be designed to be replaced rather than refurbished, if cost effective and capable of meeting the specified turnaround time. The minimum time between recovery and reflight will be approximately 60 days. The PMs will be designed to be relatively autonomous, with experiments that require few commands and limited telemetry. Mass data storage will be accommodated in the PM. The hardware development and implementation phase is currently expected to start in 1991 with a first launch in late 1993.

  3. Entry Guidance for the Reusable Launch Vehicle

    NASA Technical Reports Server (NTRS)

    Lu, Ping

    1999-01-01

    The X-33 Advanced Technology Demonstrator is a half-scale prototype developed to test the key technologies needed for a full-scale single-stage reusable launch vehicle (RLV). The X-33 is a suborbital vehicle that will be launched vertically, and land horizontally. The goals of this research were to develop an alternate entry guidance scheme for the X-33 in parallel to the actual X-33 entry guidance algorithms, provide comparative and complementary study, and identify potential new ways to improve entry guidance performance. Toward these goals, the nominal entry trajectory is defined by a piecewise linear drag-acceleration-versus-energy profile, which is in turn obtained by the solution of a semi-analytical parameter optimization problem. The closed-loop guidance is accomplished by tracking the nominal drag profile with primarily bank-angle modulation on-board. The bank-angle is commanded by a single full-envelope nonlinear trajectory control law. Near the end of the entry flight, the guidance logic is switched to heading control in order to meet strict conditions at the terminal area energy management interface. Two methods, one on ground-track control and the other on heading control, were proposed and examined for this phase of entry guidance where lateral control is emphasized. Trajectory dispersion studies were performed to evaluate the effectiveness of the entry guidance algorithms against a number of uncertainties including those in propulsion system, atmospheric properties, winds, aerodynamics, and propellant loading. Finally, a new trajectory-regulation method is introduced at the end as a promising precision entry guidance method. The guidance principle is very different and preliminary application in X-33 entry guidance simulation showed high precision that is difficult to achieve by existing methods.

  4. Mars Conjunction Crewed Missions With a Reusable Hybrid Architecture

    NASA Technical Reports Server (NTRS)

    Merrill, Raymond G.; Strange, Nathan J.; Qu, Min; Hatten, Noble

    2015-01-01

    A new crew Mars architecture has been developed that provides many potential benefits for NASA-led human Mars moons and surface missions beginning in the 2030s or 2040s. By using both chemical and electric propulsion systems where they are most beneficial and maintaining as much orbital energy as possible, the Hybrid spaceship that carries crew round trip to Mars is pre-integrated before launch and can be delivered to orbit by a single launch. After check-out on the way to cis-lunar space, it is refueled and can travel round trip to Mars in less than 1100 days, with a minimum of 300 days in Mars vicinity (opportunity dependent). The entire spaceship is recaptured into cis-lunar space and can be reused. The spaceship consists of a habitat for 4 crew attached to the Hybrid propulsion stage which uses long duration electric and chemical in-space propulsion technologies that are in use today. The hybrid architecture's con-ops has no in-space assembly of the crew transfer vehicle and requires only rendezvous of crew in a highly elliptical Earth orbit for arrival at and departure from the spaceship. The crew transfer vehicle does not travel to Mars so it only needs be able to last in space for weeks and re-enter at lunar velocities. The spaceship can be refueled and resupplied for multiple trips to Mars (every other opportunity). The hybrid propulsion stage for crewed transits can also be utilized for cargo delivery to Mars every other opportunity in a reusable manner to pre-deploy infrastructure required for Mars vicinity operations. Finally, the Hybrid architecture provides evolution options for mitigating key long-duration space exploration risks, including crew microgravity and radiation exposure.

  5. The Road from the NASA Access to Space Study to a Reusable Launch Vehicle

    NASA Technical Reports Server (NTRS)

    Powell, Richard W.; Cook, Stephen A.; Lockwood, Mary Kae

    1998-01-01

    NASA is cooperating with the aerospace industry to develop a space transportation system that provides reliable access-to-space at a much lower cost than is possible with today's launch vehicles. While this quest has been on-going for many years it received a major impetus when the U.S. Congress mandated as part of the 1993 NASA appropriations bill that: "In view of budget difficulties, present and future..., the National Aeronautics and Space Administration shall ... recommend improvements in space transportation." NASA, working with other organizations, including the Department of Transportation, and the Department of Defense identified three major transportation architecture options that were to be evaluated in the areas of reliability, operability and cost. These architectural options were: (1) retain and upgrade the Space Shuttle and the current expendable launch vehicles; (2) develop new expendable launch vehicles using conventional technologies and transition to these new vehicles beginning in 2005; and (3) develop new reusable vehicles using advanced technology, and transition to these vehicles beginning in 2008. The launch needs mission model was based on 1993 projections of civil, defense, and commercial payload requirements. This "Access to Space" study concluded that the option that provided the greatest potential for meeting the cost, operability, and reliability goals was a rocket-powered single-stage-to-orbit fully reusable launch vehicle (RLV) fleet designed with advanced technologies.

  6. Chloro-benquinone Modified on Graphene Oxide as Metal-free Catalyst: Strong Promotion of Hydroxyl Radical and Generation of Ultra-Small Graphene Oxide

    PubMed Central

    Zhao, He; Wang, Juehua; Zhang, Di; Dai, Qin; Han, Qingzhen; Du, Penghui; Liu, Chenming; Xie, Yongbing; Zhang, Yi; Cao, Hongbin; Fan, Zhuangjun

    2017-01-01

    Carbon-based metal-free catalyst has attracted more and more attention. It is a big challenge to improve catalytic activity of metal-free catalyst for decomposition of H2O2 to produce hydroxyl radical (HO•). Here, we report chloro-benquinone (TCBQ) modified on graphene oxide (GO) as metal-free catalyst for strong promotion of HO•. By the incorporation of GO, the HO• production by H2O2 and TCBQ is significantly promoted. Based on density functional theory, TCBQ modified GO (GO-TCBQ) is more prone to be nucleophilic attacked by H2O2 to yield HO• via electron transfer acceleration. Furthermore, the generated HO• can cut GO nanosheets into uniform ultra-small graphene oxide (USGO) through the cleavage of epoxy and C-C bonds. Interestingly, the damaged GO and in situ formed GO fragments can further enhance decomposition of H2O2 to produce HO•. Different from other catalytic processes, the GO-TCBQ metal-free catalysis process can be enhanced by GO itself, producing more HO•, and uniform USGO also can be generated. Thus, the metal free catalysis will be considered a fabrication method for uniform USGO, and may be extended to other fields including detoxifying organic pollutants and the application as disinfectants. PMID:28350005

  7. Metal-free carbon materials-catalyzed sulfate radical-based advanced oxidation processes: A review on heterogeneous catalysts and applications.

    PubMed

    Zhao, Qingxia; Mao, Qiming; Zhou, Yaoyu; Wei, Jianhong; Liu, Xiaocheng; Yang, Junying; Luo, Lin; Zhang, Jiachao; Chen, Hong; Chen, Hongbo; Tang, Lin

    2017-09-13

    In recent years, advanced oxidation processes (AOPs), especially sulfate radical based AOPs have been widely used in various fields of wastewater treatment due to their capability and adaptability in decontamination. Recently, metal-free carbon materials catalysts in sulfate radical production has been more and more concerned because these materials have been demonstrated to be promising alternatives to conventional metal-based catalysts, but the review of metal-free catalysts is rare. The present review outlines the current state of knowledge on the generation of sulfate radical using metal-free catalysts including carbon nanotubes, graphene, mesoporous carbon, activated carbon, activated carbon fiber, nanodiamond. The mechanism such as the radical pathway and non-radical pathway, and factors influencing of the activation of sulfate radical was also be revealed. Knowledge gaps and research needs have been identified, which include the perspectives on challenges related to metal-free catalyst, heterogeneous metal-free catalyst/persulfate systems and their potential in practical environmental remediation. Copyright © 2017 Elsevier Ltd. All rights reserved.

  8. Chloro-benquinone Modified on Graphene Oxide as Metal-free Catalyst: Strong Promotion of Hydroxyl Radical and Generation of Ultra-Small Graphene Oxide.

    PubMed

    Zhao, He; Wang, Juehua; Zhang, Di; Dai, Qin; Han, Qingzhen; Du, Penghui; Liu, Chenming; Xie, Yongbing; Zhang, Yi; Cao, Hongbin; Fan, Zhuangjun

    2017-03-28

    Carbon-based metal-free catalyst has attracted more and more attention. It is a big challenge to improve catalytic activity of metal-free catalyst for decomposition of H2O2 to produce hydroxyl radical (HO•). Here, we report chloro-benquinone (TCBQ) modified on graphene oxide (GO) as metal-free catalyst for strong promotion of HO•. By the incorporation of GO, the HO• production by H2O2 and TCBQ is significantly promoted. Based on density functional theory, TCBQ modified GO (GO-TCBQ) is more prone to be nucleophilic attacked by H2O2 to yield HO• via electron transfer acceleration. Furthermore, the generated HO• can cut GO nanosheets into uniform ultra-small graphene oxide (USGO) through the cleavage of epoxy and C-C bonds. Interestingly, the damaged GO and in situ formed GO fragments can further enhance decomposition of H2O2 to produce HO•. Different from other catalytic processes, the GO-TCBQ metal-free catalysis process can be enhanced by GO itself, producing more HO•, and uniform USGO also can be generated. Thus, the metal free catalysis will be considered a fabrication method for uniform USGO, and may be extended to other fields including detoxifying organic pollutants and the application as disinfectants.

  9. Chloro-benquinone Modified on Graphene Oxide as Metal-free Catalyst: Strong Promotion of Hydroxyl Radical and Generation of Ultra-Small Graphene Oxide

    NASA Astrophysics Data System (ADS)

    Zhao, He; Wang, Juehua; Zhang, Di; Dai, Qin; Han, Qingzhen; Du, Penghui; Liu, Chenming; Xie, Yongbing; Zhang, Yi; Cao, Hongbin; Fan, Zhuangjun

    2017-03-01

    Carbon-based metal-free catalyst has attracted more and more attention. It is a big challenge to improve catalytic activity of metal-free catalyst for decomposition of H2O2 to produce hydroxyl radical (HO•). Here, we report chloro-benquinone (TCBQ) modified on graphene oxide (GO) as metal-free catalyst for strong promotion of HO•. By the incorporation of GO, the HO• production by H2O2 and TCBQ is significantly promoted. Based on density functional theory, TCBQ modified GO (GO-TCBQ) is more prone to be nucleophilic attacked by H2O2 to yield HO• via electron transfer acceleration. Furthermore, the generated HO• can cut GO nanosheets into uniform ultra-small graphene oxide (USGO) through the cleavage of epoxy and C-C bonds. Interestingly, the damaged GO and in situ formed GO fragments can further enhance decomposition of H2O2 to produce HO•. Different from other catalytic processes, the GO-TCBQ metal-free catalysis process can be enhanced by GO itself, producing more HO•, and uniform USGO also can be generated. Thus, the metal free catalysis will be considered a fabrication method for uniform USGO, and may be extended to other fields including detoxifying organic pollutants and the application as disinfectants.

  10. Contribution of electric-field-induced metal-free porphyrin dication to photocurrent in mixed solid of metal-free porphyrin and o-chloranil/Al Schottky-barrier cell

    SciTech Connect

    Takahashi, Kohshin; Terada, Tetsuya; Yamaguchi, Takahiro; Komura, Teruhisa; Murata, Kazuhiko

    1999-05-01

    Although a Al/H{sub 2}tpp (5, 10, 15, 20-tetraphenylporphyrin) Schottky-barrier cell did not show a clear rectification property because of the large electric resistance of the H{sub 2}tpp solid, the rectification property was remarkably improved when o-chloranil was added into the H{sub 2}tpp solid. The short-circuit dark-current was observed for the Al/dye cells with the mixed solid in contrast to that with the pure H{sub 2}tpp solid, and it increased with increasing molar ratio (R) of o-chloranil to H{sub 2}tpp. Furthermore, a much larger photocurrent was observed for the mixed-solid cells than for the pure H{sub 2}tpp cell, but in the former cells in contrast to the latter cell, the open-circuit photovoltage was approximately the same as the open-circuit dark-voltage. These results indicate that the photocurrent of the mixed-solid cells was from the photocorrosion of the Al electrode. The short-circuit photocurrent action spectra obtained by irradiating from the Al side followed the absorption spectra of the dye solid films on the Al substrate below the R value of about 1, but above R = 1.5, a clear difference was observed in the spectra. This difference arises because a small amount of metal-free porphyrin dications, which is hardly detected by UV-visible spectra, was produced in the immediate neighborhood of the Al electrode when spin-coated with a larger R value because of dark-corrosion of aluminum by both assistance of the hydrogen bonds (between H{sub 2}tpp and o-chloranil) and the electric fields (in a Schottky barrier built during the spin coating). Thus the metal-free porphyrin dications efficiently underwent a photoinduced charge-separation by the potential gradient in the Schottky barrier.

  11. A highly efficient noble metal free photocatalytic hydrogen evolution system containing MoP and CdS quantum dots

    NASA Astrophysics Data System (ADS)

    Yin, Shengming; Han, Jianyu; Zou, Yinjun; Zhou, Tianhua; Xu, Rong

    2016-07-01

    We report the construction of a highly efficient noble metal free photocatalytic hydrogen (H2) evolution system using CdS quantum dots as the light absorber and metallic MoP as the cocatalyst. MoP can be prepared by a facile temperature programmed reduction method and small clusters of MoP nanoparticles sized 10-30 nm were obtained by probe ultrasonication. The effect of synthesis conditions on the electrocatalytic and photocatalytic H2 evolution activity of MoP was investigated. The highest H2 evolution rate of 1100 μmol h-1 can be achieved by the optimized system under visible light (λ >= 420 nm), which is comparable to that when Pt was used as the cocatalyst. A high quantum efficiency of 45% is obtained at 460 nm irradiation.We report the construction of a highly efficient noble metal free photocatalytic hydrogen (H2) evolution system using CdS quantum dots as the light absorber and metallic MoP as the cocatalyst. MoP can be prepared by a facile temperature programmed reduction method and small clusters of MoP nanoparticles sized 10-30 nm were obtained by probe ultrasonication. The effect of synthesis conditions on the electrocatalytic and photocatalytic H2 evolution activity of MoP was investigated. The highest H2 evolution rate of 1100 μmol h-1 can be achieved by the optimized system under visible light (λ >= 420 nm), which is comparable to that when Pt was used as the cocatalyst. A high quantum efficiency of 45% is obtained at 460 nm irradiation. Electronic supplementary information (ESI) available: SEM image with EDS, XPS survey spectrum, XRD and TEM images of MoP samples prepared under different conditions; XRD, TEM, UV-vis and photoluminescence spectra of CdS QDs; H2 evolution activity comparison for different MoP/CdS samples; the effect of pH value on H2 evolution activity of a MoP/CdS system; the XPS spectrum of MoP/CdS after photoreaction; table of literature studies on H2 evolution activity by different noble metal free photocatalytic systems

  12. Future Launch Vehicle Structures - Expendable and Reusable Elements

    NASA Astrophysics Data System (ADS)

    Obersteiner, M. H.; Borriello, G.

    2002-01-01

    Further evolution of existing expendable launch vehicles will be an obvious element influencing the future of space transportation. Besides this reusability might be the change with highest potential for essential improvement. The expected cost reduction and finally contributing to this, the improvement of reliability including safe mission abort capability are driving this idea. Although there are ideas of semi-reusable launch vehicles, typically two stages vehicles - reusable first stage or booster(s) and expendable second or upper stage - it should be kept in mind that the benefit of reusability will only overwhelm if there is a big enough share influencing the cost calculation. Today there is the understanding that additional technology preparation and verification will be necessary to master reusability and get enough benefits compared with existing launch vehicles. This understanding is based on several technology and system concepts preparation and verification programmes mainly done in the US but partially also in Europe and Japan. The major areas of necessary further activities are: - System concepts including business plan considerations - Sub-system or component technologies refinement - System design and operation know-how and capabilities - Verification and demonstration oriented towards future mission mastering: One of the most important aspects for the creation of those coming programmes and activities will be the iterative process of requirements definition derived from concepts analyses including economical considerations and the results achieved and verified within technology and verification programmes. It is the intention of this paper to provide major trends for those requirements focused on future launch vehicles structures. This will include the aspects of requirements only valid for reusable launch vehicles and those common for expendable, semi-reusable and reusable launch vehicles. Structures and materials is and will be one of the

  13. Long-term/strategic scenario for reusable booster stages

    NASA Astrophysics Data System (ADS)

    Sippel, Martin; Manfletti, Chiara; Burkhardt, Holger

    2006-02-01

    This paper describes the final design status of a partially reusable space transportation system which has been under study for five years within the German future launcher technology research program ASTRA. It consists of dual booster stages, which are attached to an advanced expendable core. The design of the reference liquid fly-back boosters (LFBB) is focused on LOX/LH2 propellant and a future advanced gas-generator cycle rocket motor. The preliminary design study was performed in close cooperation between DLR and the German space industry. The paper's first part describes recent progress in the design of this reusable booster stage. The second part of the paper assesses a long-term, strategic scenario of the reusable stage's operation. The general idea is the gradual evolution of the above mentioned basic fly-back booster vehicle into three space transportation systems performing different tasks: Reusable First Stage for a small launcher application, successive development to a fully reusable TSTO, and booster for a super-heavy-lift rocket to support an ambitious space flight program like manned Mars missions. The assessment addresses questions of technical sanity, preliminary sizing and performance issues and, where applicable, examines alternative options.

  14. Metal-Free Photocatalyst for H2 Evolution in Visible to Near-Infrared Region: Black Phosphorus/Graphitic Carbon Nitride.

    PubMed

    Zhu, Mingshan; Kim, Sooyeon; Mao, Liang; Fujitsuka, Mamoru; Zhang, Junying; Wang, Xinchen; Majima, Tetsuro

    2017-09-20

    In the drive toward green and sustainable chemistry, exploring efficient and stable metal-free photocatalysts with broadband solar absorption from the UV to near-infrared region for the photoreduction of water to H2 remains a big challenge. To this end, a binary nanohybrid (BP/CN) of two-dimensional (2D) black phosphorus (BP) and graphitic carbon nitride (CN) was designed and used as a metal-free photocatalyst for the first time. During irradiation of BP/CN in water with >420 and >780 nm light, solid H2 gas was generated, respectively. Owing to the interfacial interaction between BP and CN, efficient charge transfer occurred, thereby enhancing the photocatalytic performance. The efficient charge-trapping and transfer processes were thoroughly investigated with time-resolved diffuse reflectance spectroscopic measurement. The present results show that BP/CN is a metal-free photocatalyst for artificial photosynthesis and renewable energy conversion.

  15. Undeniable Confirmation of the syn-Addition Mechanism for Metal-Free Diboration by Using the Crystalline Sponge Method.

    PubMed

    Cuenca, Ana B; Zigon, Nicolas; Duplan, Vincent; Hoshino, Manabu; Fujita, Makoto; Fernández, Elena

    2016-03-24

    The stereochemical outcome of the recently developed metal-free 1,2-diboration of aliphatic alkenes has, until now, only been elucidated by indirect means (e.g. derivatization). This is because classical conformational analysis of the resulting 1,2-diboranes is not viable; in the (1)H NMR spectrum the relevant (1)H resonances are broadened by (11)B, and the occurrence of the products as oily compounds precludes X-ray crystallographic analysis. Herein, the crystalline sponge method is used to display the crystal structures of the diboronic esters formed from internal E and Z olefins, evidencing the stereospecific syn addition mechanism of the reaction, which is fully consistent with the prediction from DFT calculations. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Nitrogen-doped Carbon Derived from ZIF-8 as a High-performance Metal-free Catalyst for Acetylene Hydrochlorination

    NASA Astrophysics Data System (ADS)

    Chao, Songlin; Zou, Fang; Wan, Fanfan; Dong, Xiaobin; Wang, Yanlin; Wang, Yuxuan; Guan, Qingxin; Wang, Guichang; Li, Wei

    2017-01-01

    Acetylene hydrochlorination is a major industrial technology for manufacturing vinyl chloride monomer in regions with abundant coal resources; however, it is plagued by the use of mercury(II) chloride catalyst. The development of a nonmercury catalyst has been extensively explored. Herein, we report a N-doped carbon catalyst derived from ZIF-8 with both high activity and quite good stability. The acetylene conversion reached 92% and decreased slightly during a 200 h test at 220 °C and atmospheric pressure. Experimental studies and theoretical calculations indicate that C atoms adjacent to the pyridinic N are the active sites, and coke deposition covering pyridinic N is the main reason for catalyst deactivation. The performance of those N-doped carbons makes it possible for practical applications with further effort. Furthermore, the result also provides guidance for designing metal-free catalysts for similar reactions.

  17. Electrochemical study on the TiO2 porous electrodes for metal-free dye-sensitized solar cells

    NASA Astrophysics Data System (ADS)

    Zhang, D. W.; Chen, S.; Li, X. D.; Wang, Z. A.; Shi, J. H.; Sun, Z.; Yin, X. J.; Huang, S. M.

    2009-08-01

    Nanocrystalline TiO2 porous electrodes were prepared by screen-printing method in order to efficiently control the fabrication process. TiO2 viscous pastes were prepared from commercial TiO2 nano powder using ethyl cellulose as a porosity controlling agent. A metal-free organic dye (indoline dye D102) was used as a sensitizer. TiO2 porous electrodes with different thicknesses were investigated. The optical and physical properties of the TiO2 films, dye adsorption behavior and performance of dye-sensitized solar cells (DSCs) were investigated systemically. The electronic and ionic processes in DSCs were analysized and discussed by electrochemical impedance spectroscopy (EIS). High conversion efficiencies over 8.00 % under illumination of simulated AM1.5 sunlight (60mW/cm2) were achieved.

  18. An Admix Approach To Determine Counter Anion Effects on Metal-Free Arylation Reactions with Diaryliodonium Salts.

    PubMed

    Seidl, Thomas L; Stuart, David R

    2017-08-24

    A method to determine the effect of counter anions in metal-free arylation reactions of diaryliodonium salts is described. This approach avoids the independent synthesis of individual diaryliodonium salts and potentially enables assessment of a large number of different counter anions, including those that are synthetically challenging to install. Diaryliodonium tosylate salts serve as a general precursor for this approach, and an azide arylation reaction was used to develop this strategy. Further optimization and representative scope of azide arylation is demonstrated in yields that range from 74-95% (89% average). The use of this method as a screening tool has also been validated with arylation reactions of three different nucleophiles employing diphenyliodonium tosylate.

  19. Manganese Oxide Nanorod-Decorated Mesoporous ZSM-5 Composite as a Precious-Metal-Free Electrode Catalyst for Oxygen Reduction.

    PubMed

    Cui, Xiangzhi; Hua, Zile; Chen, Lisong; Zhang, Xiaohua; Chen, Hangrong; Shi, Jianlin

    2016-05-10

    A precious-metal-free cathode catalyst, MnO2 nanorod-decorated mesoporous ZSM-5 zeolite nanocomposite (MnO2 / m-ZSM-5), has been successfully synthesized by a hydrothermal and electrostatic interaction approach for efficient electrochemical catalysis of the oxygen reduction reaction (ORR). The active MnOOH species, that is, Mn(4+) /Mn(3+) redox couple and Brønsted acid sites on the mesoporous ZSM-5 matrix facilitate an approximately 4 e(-) process for the catalysis of the ORR comparable to commercial 20 wt % Pt/C. Stable electrocatalytic activity with 90 % current retention after 5000 cycles, and more importantly, excellent methanol tolerance is observed. Synergetic catalytic effects between the MnO2 nanorods and the mesoporous ZSM-5 matrix are proposed to account for the high electrochemical catalytic performance.

  20. Can metal-free silicon-doped hexagonal boron nitride nanosheets and nanotubes exhibit activity toward CO oxidation?

    PubMed

    Lin, Sen; Ye, Xinxin; Huang, Jing

    2015-01-14

    Si-doped hexagonal boron nitride nanosheets (Si-BNNS) and nanotubes (Si-BNNT) have been investigated by first-principle methods. The strong interaction between the silicon atom and the hexagonal boron nitride nanosheet or nanotube with a boron vacancy indicates that such nanocomposites should be very stable. The significant charge transfer from the Si-BNNS substrate to the O2 molecule, which could occupy the antibonding 2π* orbitals of O2, results in the activation of the adsorbed O2. The catalytic activity of the Si-BNNS for CO oxidation is explored and the calculated barrier (0.29 eV) of the reaction CO + O2→ CO2 + O is much lower than those on the traditional noble metals. This opens a new avenue to fabricate low cost and high activity boron nitride-based metal-free catalysts.

  1. Carbon nitride frameworks padded with graphene as efficient metal-free catalyst for HER in acidic and alkali electrolytes

    NASA Astrophysics Data System (ADS)

    Meng, Shiming; Li, Bin; Li, Songmei; Yang, Shubin

    2017-05-01

    Although hydrogen evolution reaction (HER) is one of the most promising pathways to generate hydrogen in large-scale for future fuels, it is still lacking efficient and low-cost electrocatalysts. Here, carbon nitride frameworks padded with graphene (CNF-G) are explored as efficient metal-free catalysts with low-cost and good durability via a directly annealing commercial melamine sponge with graphene oxide. Owing to the high electrical conductivity of graphene, CNF-G exhibits outstanding catalytic activity during HER process in wide pH ranges. The overpotentials and Tafel slopes of CNF-G were 149 mV and 116 mV dec-1 in 0.5 M H2SO4, as well as 319 mV and 160 mV dec-1 in 1 M KOH, respectively. More importantly, CNF-G shows a high and stable catalytic activity demonstrated by a multiple cyclic voltammetry and long potentiostatic polarization.

  2. Metal-free organic dyes for dye-sensitized solar cells: from structure: property relationships to design rules.

    PubMed

    Mishra, Amaresh; Fischer, Markus K R; Bäuerle, Peter

    2009-01-01

    Dye-sensitized solar cells (DSSC) have attracted considerable attention in recent years as they offer the possibility of low-cost conversion of photovoltaic energy. This Review focuses on recent advances in molecular design and technological aspects of metal-free organic dyes for applications in dye-sensitized solar cells. Special attention has been paid to the design principles of these dyes and on the effect of various electrolyte systems. Cosensitization, an emerging technique to extend the absorption range, is also discussed as a way to improve the performance of the device. In addition, we report on inverted dyes for photocathodes, which constitutes a relatively new approach for the production of tandem cells. Special consideration has been paid to the correlation between the molecular structure and physical properties to their performance in DSSCs.

  3. Phenyl Benzo[b]phenothiazine as a Visible Light Photoredox Catalyst for Metal-Free Atom Transfer Radical Polymerization.

    PubMed

    Dadashi-Silab, Sajjad; Pan, Xiangcheng; Matyjaszewski, Krzysztof

    2016-12-23

    This paper reports use of phenyl benzo[b]phenothiazine (Ph-benzoPTZ) as a visible light-induced metal-free atom transfer radical polymerization (ATRP) photoredox catalyst. Well-controlled polymerizations of various methacrylate monomers were conducted under a 392 nm visible light LED using Ph-benzoPTZ to activate different alkyl halides. The use of the photocatalyst enabled temporal control over the growth of polymer chains during intermittent on/off periods. The polymerization was initiated and progressed only under stimulation by light and completely stopped in the absence of light. Block copolymers were synthesized to demonstrate high retention of chain end fidelity in the polymers and livingness of the process.

  4. Nitrogen-doped Carbon Derived from ZIF-8 as a High-performance Metal-free Catalyst for Acetylene Hydrochlorination

    PubMed Central

    Chao, Songlin; Zou, Fang; Wan, Fanfan; Dong, Xiaobin; Wang, Yanlin; Wang, Yuxuan; Guan, Qingxin; Wang, Guichang; Li, Wei

    2017-01-01

    Acetylene hydrochlorination is a major industrial technology for manufacturing vinyl chloride monomer in regions with abundant coal resources; however, it is plagued by the use of mercury(II) chloride catalyst. The development of a nonmercury catalyst has been extensively explored. Herein, we report a N-doped carbon catalyst derived from ZIF-8 with both high activity and quite good stability. The acetylene conversion reached 92% and decreased slightly during a 200 h test at 220 °C and atmospheric pressure. Experimental studies and theoretical calculations indicate that C atoms adjacent to the pyridinic N are the active sites, and coke deposition covering pyridinic N is the main reason for catalyst deactivation. The performance of those N-doped carbons makes it possible for practical applications with further effort. Furthermore, the result also provides guidance for designing metal-free catalysts for similar reactions. PMID:28051131

  5. Ambiphilic Frustrated Lewis Pair Exhibiting High Robustness and Reversible Water Activation: Towards the Metal-Free Hydrogenation of Carbon Dioxide.

    PubMed

    Rochette, Étienne; Courtemanche, Marc-André; Pulis, Alexander P; Bi, Wenhua; Fontaine, Frédéric-Georges

    2015-06-29

    The synthesis and structural characterization of a phenylene-bridged Frustrated Lewis Pair (FLP) having a 2,2,6,6‑tetramethylpiperidine (TMP) as the Lewis base and a 9-borabicyclo[3.3.1]nonane (BBN) as the Lewis acid is reported. This FLP exhibits unique robustness towards the products of carbon dioxide hydrogenation. The compound shows reversible splitting of water, formic acid and methanol while no reaction is observed in the presence of excess formaldehyde. The molecule is incredibly robust, showing little sign of degradation after heating at 80 °C in benzene with 10 equiv. of formic acid for 24 h. The robustness of the system could be exploited in the design of metal-free catalysts for the hydrogenation of carbon dioxide.

  6. Nitrogen-doped Carbon Derived from ZIF-8 as a High-performance Metal-free Catalyst for Acetylene Hydrochlorination.

    PubMed

    Chao, Songlin; Zou, Fang; Wan, Fanfan; Dong, Xiaobin; Wang, Yanlin; Wang, Yuxuan; Guan, Qingxin; Wang, Guichang; Li, Wei

    2017-01-04

    Acetylene hydrochlorination is a major industrial technology for manufacturing vinyl chloride monomer in regions with abundant coal resources; however, it is plagued by the use of mercury(II) chloride catalyst. The development of a nonmercury catalyst has been extensively explored. Herein, we report a N-doped carbon catalyst derived from ZIF-8 with both high activity and quite good stability. The acetylene conversion reached 92% and decreased slightly during a 200 h test at 220 °C and atmospheric pressure. Experimental studies and theoretical calculations indicate that C atoms adjacent to the pyridinic N are the active sites, and coke deposition covering pyridinic N is the main reason for catalyst deactivation. The performance of those N-doped carbons makes it possible for practical applications with further effort. Furthermore, the result also provides guidance for designing metal-free catalysts for similar reactions.

  7. Micelle-Template Synthesis of Nitrogen-Doped Mesoporous Graphene as an Efficient Metal-Free Electrocatalyst for Hydrogen Production

    PubMed Central

    Huang, Xiaodan; Zhao, Yufei; Ao, Zhimin; Wang, Guoxiu

    2014-01-01

    Synthesis of mesoporous graphene materials by soft-template methods remains a great challenge, owing to the poor self-assembly capability of precursors and the severe agglomeration of graphene nanosheets. Herein, a micelle-template strategy to prepare porous graphene materials with controllable mesopores, high specific surface areas and large pore volumes is reported. By fine-tuning the synthesis parameters, the pore sizes of mesoporous graphene can be rationally controlled. Nitrogen heteroatom doping is found to remarkably render electrocatalytic properties towards hydrogen evolution reactions as a highly efficient metal-free catalyst. The synthesis strategy and the demonstration of highly efficient catalytic effect provide benchmarks for preparing well-defined mesoporous graphene materials for energy production applications. PMID:25523276

  8. Micelle-Template Synthesis of Nitrogen-Doped Mesoporous Graphene as an Efficient Metal-Free Electrocatalyst for Hydrogen Production

    NASA Astrophysics Data System (ADS)

    Huang, Xiaodan; Zhao, Yufei; Ao, Zhimin; Wang, Guoxiu

    2014-12-01

    Synthesis of mesoporous graphene materials by soft-template methods remains a great challenge, owing to the poor self-assembly capability of precursors and the severe agglomeration of graphene nanosheets. Herein, a micelle-template strategy to prepare porous graphene materials with controllable mesopores, high specific surface areas and large pore volumes is reported. By fine-tuning the synthesis parameters, the pore sizes of mesoporous graphene can be rationally controlled. Nitrogen heteroatom doping is found to remarkably render electrocatalytic properties towards hydrogen evolution reactions as a highly efficient metal-free catalyst. The synthesis strategy and the demonstration of highly efficient catalytic effect provide benchmarks for preparing well-defined mesoporous graphene materials for energy production applications.

  9. Metal-free aqueous redox capacitor via proton rocking-chair system in an organic-based couple.

    PubMed

    Tomai, Takaaki; Mitani, Satoshi; Komatsu, Daiki; Kawaguchi, Yuji; Honma, Itaru

    2014-01-07

    Safe and inexpensive energy storage devices with long cycle lifetimes and high power and energy densities are mandatory for the development of electrical power grids that connect with renewable energy sources. In this study, we demonstrated metal-free aqueous redox capacitors using couples comprising low-molecular-weight organic compounds. In addition to the electric double layer formation, proton insertion/extraction reactions between a couple consisting of inexpensive quinones/hydroquinones contributed to the energy storage. This energy storage mechanism, in which protons are shuttled back and forth between two electrodes upon charge and discharge, can be regarded as a proton rocking-chair system. The fabricated capacitor showed a large capacity (>20 Wh/kg), even in the applied potential range between 0-1 V, and high power capability (>5 A/g). The support of the organic compounds in nanoporous carbon facilitated the efficient use of the organic compounds with a lifetime of thousands of cycles.

  10. N,P-Codoped Carbon Networks as Efficient Metal-free Bifunctional Catalysts for Oxygen Reduction and Hydrogen Evolution Reactions.

    PubMed

    Zhang, Jintao; Qu, Liangti; Shi, Gaoquan; Liu, Jiangyong; Chen, Jianfeng; Dai, Liming

    2016-02-05

    The high cost and scarcity of noble metal catalysts, such as Pt, have hindered the hydrogen production from electrochemical water splitting, the oxygen reduction in fuel cells and batteries. Herein, we developed a simple template-free approach to three-dimensional porous carbon networks codoped with nitrogen and phosphorus by pyrolysis of a supermolecular aggregate of self-assembled melamine, phytic acid, and graphene oxide (MPSA/GO). The pyrolyzed MPSA/GO acted as the first metal-free bifunctional catalyst with high activities for both oxygen reduction and hydrogen evolution. Zn-air batteries with the pyrolyzed MPSA/GO air electrode showed a high peak power density (310 W g(-1) ) and an excellent durability. Thus, the pyrolyzed MPSA/GO is a promising bifunctional catalyst for renewable energy technologies, particularly regenerative fuel cells.

  11. 3D graphene preparation via covalent amide functionalization for efficient metal-free electrocatalysis in oxygen reduction

    PubMed Central

    Ahmed, Mohammad Shamsuddin; Kim, Young-Bae

    2017-01-01

    3D and porous reduced graphene oxide (rGO) catalysts have been prepared with sp3-hybridized 1,4-diaminobutane (sp3-DABu, rGO-sp3-rGO) and sp2-hybridized 1,4-diaminobenzene (sp2-DABe, rGO-sp2-rGO) through a covalent amidation and have employed as a metal-free electrocatalyst for oxygen reduction reaction (ORR) in alkaline media. Both compounds have used as a junction between functionalized rGO layers to improve electrical conductivity and impart electrocatalytic activity to the ORR resulting from the interlayer charge transfer. The successful amidation and the subsequent reduction in the process of catalyst preparation have confirmed by X-ray photoelectron spectroscopy. A hierarchical porous structure is also confirmed by surface morphological analysis. Specific surface area and thermal stability have increased after successful the amidation by sp3-DABu. The investigated ORR mechanism reveals that both functionalized rGO is better ORR active than nonfunctionalized rGO due to pyridinic-like N content and rGO-sp3-rGO is better ORR active than rGO-sp2-rGO due to higher pyridinic-like N content and π-electron interaction-free interlayer charge transfer. Thus, the rGO-sp3-rGO has proven as an efficient metal-free electrocatalyst with better electrocatalytic activity, stability, and tolerance to the crossover effect than the commercially available Pt/C for ORR. PMID:28240302

  12. Orbital Debris Impact Damage to Reusable Launch Vehicles

    NASA Technical Reports Server (NTRS)

    Robinson, Jennifer H.

    1998-01-01

    In an effort by the National Aeronautics and Space Administration (NASA), hypervelocity impact tests were performed on thermal protection systems (TPS) applied on the external surfaces of reusable launch vehicles (RLV) to determine the potential damage from orbital debris impacts. Three TPS types were tested, bonded to composite structures representing RLV fuel tank walls. The three heat shield materials tested were Alumina-Enhanced Thermal Barrier-12 (AETB-12), Flexible Reusable Surface Insulation (FRSI), and Advanced Flexible Reusable Surface Insulation (AFRSI). Using this test data, predictor equations were developed for the entry hole diameters in the three TPS materials, with correlation coefficients ranging from 0.69 to 0.86. Possible methods are proposed for approximating damage occurring at expected orbital impact velocities higher than tested, with references to other published work.

  13. 2nd Generation Reusable Launch Vehicle Potential Commercial Development Scenarios

    NASA Technical Reports Server (NTRS)

    Creech, Stephen D.; Rogacki, John R. (Technical Monitor)

    2001-01-01

    The presentation will discuss potential commercial development scenarios for a Second Generation Reusable Launch Vehicle. The analysis of potential scenarios will include commercial rates of return, government return on investment, and market considerations. The presentation will include policy considerations in addition to analysis of Second Generation Reusable Launch Vehicle economics. The data discussed is being developed as a part of NASA's Second Generation Reusable Launch Vehicle Program, for consideration as potential scenarios for enabling a next generation system. Material will include potential scenarios not previously considered by NASA or presented at other conferences. Candidate paper has not been presented at a previous meeting, and conference attendance of the author has been approved by NASA.

  14. Benefits of Government Incentives for Reusable Launch Vehicle Development

    NASA Technical Reports Server (NTRS)

    Shaw, Eric J.; Hamaker, Joseph W.; Prince, Frank A.

    1998-01-01

    Many exciting new opportunities in space, both government missions and business ventures, could be realized by a reduction in launch prices. Reusable launch vehicle (RLV) designs have the potential to lower launch costs dramatically from those of today's expendable and partially-expendable vehicles. Unfortunately, governments must budget to support existing launch capability, and so lack the resources necessary to completely fund development of new reusable systems. In addition, the new commercial space markets are too immature and uncertain to motivate the launch industry to undertake a project of this magnitude and risk. Low-cost launch vehicles will not be developed without a mature market to service; however, launch prices must be reduced in order for a commercial launch market to mature. This paper estimates and discusses the various benefits that may be reaped from government incentives for a commercial reusable launch vehicle program.

  15. Reusable Cryogenic Tank VHM Using Fiber Optic Distributed Sensing Technology

    NASA Technical Reports Server (NTRS)

    Bodan-Sanders, Patricia; Bouvier, Carl

    1998-01-01

    The reusable oxygen and hydrogen tanks are key systems for both the X-33 (sub-scale, sub-orbital technology demonstrator) and the commercial Reusable Launch Vehicle (RLV). The backbone of the X-33 Reusable Cryogenic Tank Vehicle Health Management (VHM) system lies in the optical network of distributed strain temperature and hydrogen sensors. This network of fiber sensors will create a global strain and temperature map for monitoring the health of the tank structure, cryogenic insulation, and Thermal Protection System. Lockheed Martin (Sanders and LMMSS) and NASA Langley have developed this sensor technology for the X-33 and have addressed several technical issues such as fiber bonding and laser performance in this harsh environment.

  16. 2nd Generation Reusable Launch Vehicle Potential Commercial Development Scenarios

    NASA Technical Reports Server (NTRS)

    Creech, Stephen D.; Rogacki, John R. (Technical Monitor)

    2001-01-01

    The presentation will discuss potential commercial development scenarios for a Second Generation Reusable Launch Vehicle. The analysis of potential scenarios will include commercial rates of return, government return on investment, and market considerations. The presentation will include policy considerations in addition to analysis of Second Generation Reusable Launch Vehicle economics. The data discussed is being developed as a part of NASA's Second Generation Reusable Launch Vehicle Program, for consideration as potential scenarios for enabling a next generation system. Material will include potential scenarios not previously considered by NASA or presented at other conferences. Candidate paper has not been presented at a previous meeting, and conference attendance of the author has been approved by NASA.

  17. Benefits of Government Incentives for Reusable Launch Vehicle Development

    NASA Technical Reports Server (NTRS)

    Shaw, Eric J.; Hamaker, Joseph W.; Prince, Frank A.

    1998-01-01

    Many exciting new opportunities in space, both government missions and business ventures, could be realized by a reduction in launch prices. Reusable launch vehicle (RLV) designs have the potential to lower launch costs dramatically from those of today's expendable and partially-expendable vehicles. Unfortunately, governments must budget to support existing launch capability, and so lack the resources necessary to completely fund development of new reusable systems. In addition, the new commercial space markets are too immature and uncertain to motivate the launch industry to undertake a project of this magnitude and risk. Low-cost launch vehicles will not be developed without a mature market to service; however, launch prices must be reduced in order for a commercial launch market to mature. This paper estimates and discusses the various benefits that may be reaped from government incentives for a commercial reusable launch vehicle program.

  18. Reusable and disposable cups: An energy-based evaluation

    NASA Astrophysics Data System (ADS)

    Hocking, Martin B.

    1994-11-01

    A group of five different types of reusable and disposable hot drink cups have been analyzed in detail with respect to their overall energy costs during fabrication and use. Electricity generating methods and efficiencies have been found to be key factors in the primary energy consumption for the washing of reusable cups and a less important factor in cup fabrication. In Canada or the United States, over 500 or more use cycles, reusable cups are found to have about the same or slightly more energy consumption, use for use, as moulded polystyrene foam cups used once and then discarded. For the same area paper cups used once and discarded are found to consume less fossil fuel energy per use than any of the other cup types examined. Details of this analysis, which could facilitate the comparative assessment of other scenarios, are presented.

  19. Reusable rocket engine intelligent control system framework design, phase 2

    NASA Technical Reports Server (NTRS)

    Nemeth, ED; Anderson, Ron; Ols, Joe; Olsasky, Mark

    1991-01-01

    Elements of an advanced functional framework for reusable rocket engine propulsion system control are presented for the Space Shuttle Main Engine (SSME) demonstration case. Functional elements of the baseline functional framework are defined in detail. The SSME failure modes are evaluated and specific failure modes identified for inclusion in the advanced functional framework diagnostic system. Active control of the SSME start transient is investigated, leading to the identification of a promising approach to mitigating start transient excursions. Key elements of the functional framework are simulated and demonstration cases are provided. Finally, the advanced function framework for control of reusable rocket engines is presented.

  20. Cryopumping in Cryogenic Insulations for a Reusable Launch Vehicle

    NASA Technical Reports Server (NTRS)

    Johnson, Theodore F.; Weiser, Erik S.; Grimsley, Brian W.; Jensen, Brian J.

    2003-01-01

    Testing at cryogenic temperatures was performed to verify the material characteristics and manufacturing processes of reusable propellant tank cryogenic insulations for a Reusable Launch Vehicle (RLV). The unique test apparatus and test methods developed for the investigation of cryopumping in cryogenic insulations are described. Panel level test specimens with various types of cryogenic insulations were subjected to a specific thermal profile where the temperature varied from -262 C to 21 C. Cryopumping occurred if the interior temperature of the specimen exhibited abnormal temperature fluctuations, such as a sudden decrease in temperature during the heating phase.

  1. How X-37 Technology Demonstration Supports Reusable Launch Vehicles

    NASA Technical Reports Server (NTRS)

    Manley, David J.; Cervisi, Richard T.; Staszak, Paul R.

    2000-01-01

    This presentation discusses, in viewgraph form, how X-37 Technology Demonstration Supports Reusable Launch Vehicles. The topics include: 1) X-37 Program Objectives; 2) X-37 Description; 3) X-37 Vehicle Characteristics; 4) X-37 Expands the Testbed Envelope to Orbital Capability; 5) Overview of X-37 Flight Test Program; 6) Thirty-Nine Technologies and Experiments are Being Demonstrated on the X-37; 7) X-37 Airframe/Structures Technologies; 8) X-37 Mechanical, Propulsion, and Thermal System Technologies and Experiments; 9) X-37 GN&C Technologies; 10) X-37 Avionics, Power, and Software Technologies and Experiments; and 11) X-37 Technologies and Experiments Support Reusable Launch Vehicle Needs.

  2. Reusables get high marks in adult incontinence care market.

    PubMed

    Tison-Rossman, J

    1992-11-01

    The adult incontinence care market is coming of age. As environmental concerns gradually erode the popularity of disposables, nursing homes and hospitals are looking at reusables in a new light. In addition, the aging of the U.S. population is expected to increase the demand for incontinence care products. A recent study found that the sales of reusable cloth diapers and pads accounted for $385 million annually. All of these factors add up to a lucrative market for textile rental companies that can supply these products.

  3. Vehicle/payload interface specification for the reusable reentry satellite

    NASA Technical Reports Server (NTRS)

    1991-01-01

    This document describes the common interface requirements between the Vehicle Segment and the Payload Segment of the Reusable Reentry Satellite (RRS) system. The system consists of a single transport vehicle design that provides a uniform, unidirectional payload gravitational environment which is selectable during on-orbit operations over the range of 10(exp -5) (microgravity) to 1.5 g's. The initial Reusable Reentry Vehicle/Payload Module (RRV/PM) integration and checkout will occur at the launch base unless otherwise agreed to in a mission-unique addendum to this specification. Pre-integration interface qualification shall be done using emulators as described.

  4. Reusable Hot-Wire Cable Cutter

    NASA Technical Reports Server (NTRS)

    Pauken, Michael T.; Steinkraus, Joel M.

    2010-01-01

    During the early development stage of balloon deployment systems for missions, nichrome wire cable cutters were often used in place of pyro-actuated cutters. Typically, a nichrome wire is wrapped around a bundle of polymer cables with a low melting point and connected to a relay-actuated electric circuit. The heat from the nichrome reduces the strength of the cable bundle, which quickly breaks under a mechanical load and can thus be used as a release mechanism for a deployment system. However, the use of hand-made heated nichrome wire for cutters is not very reliable. Often, the wrapped nichrome wire does not cut through the cable because it either pulls away from its power source or does not stay in contact with the cable being cut. Because nichrome is not readily soldered to copper wire, unreliable mechanical crimps are often made to connect the nichrome to an electric circuit. A self-contained device that is reusable and reliable was developed to sever cables for device release or deployment. The nichrome wire in this new device is housed within an enclosure to prevent it from being damaged by handling. The electric power leads are internally connected within the unit to the nichrome wire using a screw terminal connection. A bayonet plug, a quick and secure method of connecting the cutter to the power source, is used to connect the cutter to the power leads similar to those used in pyro-cutter devices. A small ceramic tube [0.25-in. wide 0.5-in. long (.6.4-mm wide 13-mm long)] houses a spiraled nichrome wire that is heated when a cable release action is required. The wire is formed into a spiral coil by wrapping it around a mandrel. It is then laid inside the ceramic tube so that it fits closely to the inner surface of the tube. The ceramic tube provides some thermal and electrical insulation so that most of the heat generated by the wire is directed toward the cable bundle in the center of the spiral. The ceramic tube is cemented into an aluminum block, which

  5. Surface and Interface Engineering of Noble-Metal-Free Electrocatalysts for Efficient Energy Conversion Processes.

    PubMed

    Zhu, Yun Pei; Guo, Chunxian; Zheng, Yao; Qiao, Shi-Zhang

    2017-04-18

    Developing cost-effective and high-performance electrocatalysts for renewable energy conversion and storage is motivated by increasing concerns regarding global energy security and creating sustainable technologies dependent on inexpensive and abundant resources. Recent achievements in the design and synthesis of efficient non-precious-metal and even non-metal electrocatalysts make the replacement of noble metal counterparts for the hydrogen evolution reaction (HER), oxygen evolution reaction (OER), and oxygen reduction reaction (ORR) with earth-abundant elements, for example, C, N, Fe, Mn, and Co, a realistic possibility. It has been found that surface atomic engineering (e.g., heteroatom-doping) and interface atomic or molecular engineering (e.g., interfacial bonding) can induce novel physicochemical properties and strong synergistic effects for electrocatalysts, providing new and efficient strategies to greatly enhance the catalytic activities. In this Account, we discuss recent progress in the design and fabrication of efficient electrocatalysts based on carbon materials, graphitic carbon nitride, and transition metal oxides or hydroxides for efficient ORR, OER, and HER through surface and interfacial atomic and molecular engineering. Atomic and molecular engineering of carbon materials through heteroatom doping with one or more elements of noticeably different electronegativities can maximally tailor their electronic structures and induce a synergistic effect to increase electrochemical activity. Nonetheless, the electrocatalytic performance of chemically modified carbonaceous materials remains inferior to that of their metallic counterparts, which is mainly due to the relatively limited amount of electrocatalytic active sites induced by heteroatom doping. Accordingly, coupling carbon substrates with other active electrocatalysts to produce composite structures can impart novel physicochemical properties, thereby boosting the electroactivity even further

  6. Metal-free oxidation of aromatic carbon-hydrogen bonds through a reverse-rebound mechanism.

    PubMed

    Yuan, Changxia; Liang, Yong; Hernandez, Taylor; Berriochoa, Adrian; Houk, Kendall N; Siegel, Dionicio

    2013-07-11

    Methods for carbon-hydrogen (C-H) bond oxidation have a fundamental role in synthetic organic chemistry, providing functionality that is required in the final target molecule or facilitating subsequent chemical transformations. Several approaches to oxidizing aliphatic C-H bonds have been described, drastically simplifying the synthesis of complex molecules. However, the selective oxidation of aromatic C-H bonds under mild conditions, especially in the context of substituted arenes with diverse functional groups, remains a challenge. The direct hydroxylation of arenes was initially achieved through the use of strong Brønsted or Lewis acids to mediate electrophilic aromatic substitution reactions with super-stoichiometric equivalents of oxidants, significantly limiting the scope of the reaction. Because the products of these reactions are more reactive than the starting materials, over-oxidation is frequently a competitive process. Transition-metal-catalysed C-H oxidation of arenes with or without directing groups has been developed, improving on the acid-mediated process; however, precious metals are required. Here we demonstrate that phthaloyl peroxide functions as a selective oxidant for the transformation of arenes to phenols under mild conditions. Although the reaction proceeds through a radical mechanism, aromatic C-H bonds are selectively oxidized in preference to activated Csp3-H bonds. Notably, a wide array of functional groups are compatible with this reaction, and this method is therefore well suited for late-stage transformations of advanced synthetic intermediates. Quantum mechanical calculations indicate that this transformation proceeds through a novel addition-abstraction mechanism, a kind of 'reverse-rebound' mechanism as distinct from the common oxygen-rebound mechanism observed for metal-oxo oxidants. These calculations also identify the origins of the experimentally observed aryl selectivity.

  7. Silylations of Arenes with Hydrosilanes: From Transition-Metal-Catalyzed C¢X Bond Cleavage to Environmentally Benign Transition-Metal-Free C¢H Bond Activation.

    PubMed

    Xu, Zheng; Xu, Li-Wen

    2015-07-08

    The construction of carbon-silicon bonds is highlighted as an exciting achievement in the field of organosilicon chemistry and green chemistry. Recent developments in this area will enable the sustainable chemical conversion of silicon resources into synthetically useful compounds. Especially, the catalytic silylation through C¢H bond activation without directing groups and hydrogen acceptors is one of the most challenging topics in organic chemistry and green chemistry. These remarkable findings on catalytic silylation can pave the way to a more environmentally benign utilization of earth-abundant silicon-based resources in synthetic chemistry.

  8. Soda-lime glass as a binder in reusable experimental investment for dental castings.

    PubMed

    Yagi, Satoshi; Zhang, Zutai; Aida, Yoshiteru; Hotta, Yasuhiro; Tamaki, Yukimichi; Miyazaki, Takashi

    2011-01-01

    In this study, different glasses were investigated to improve reusable investments. Borosilicate glass (BSG) powder and soda-lime glass (SLG) powder were prepared by milling broken beakers and microscope slides, respectively, and used in experimental investments (I-BSG, I-SLG) by blending glass powder (10 wt%) with cristobalite (90 wt%). Some properties and casting fits were evaluated with commercial gypsum-bonded investment as the control. Both BSG and SLG were mainly composed of Si, but SLG had a large Ca content. The glass transition temperatures were approximately 800°C (BSG) and 700°C (SLG). Experimental investments with heating showed the significantly (p<0.05) higher expansion than that of the control. The compressive strength of I-SLG was higher than that of I-BSG, and increased with temperature. The MOD inlay obtained from I-SLG had a significantly smaller gap than that from I-BSG, and was comparable to the control. These results suggest SLG could be applied clinically as a reusable dental investment.

  9. Reusability Studies for Ares I and Ares V Propulsion

    NASA Technical Reports Server (NTRS)

    Williams, Thomas J.; Priskos, Alex S.; Schorr, Andrew A.; Barrett, Greg

    2008-01-01

    looks at one of the most important trade studies to date, the "Ares I First Stage Expendability Trade Study." The purpose of this study was to determine the utility of flying the first stage as an expendable booster rather than making it reusable. To lower the study complexity, four operational scenarios (or cases) were defined. This assessment then included an evaluation of the development, reliability, performance, and transition impacts associated with an expendable solution. This paper looks at these scenarios from the perspectives of cost, reliability, and performance.

  10. Reusability Studies for Ares I and Ares V Propulsion

    NASA Technical Reports Server (NTRS)

    Williams, Thomas J.; Priskos, Alex S.; Schorr, Andrew A.; Barrett, Gregory

    2008-01-01

    looks at one of the most important trade studies to date, the "Ares I First Stage Expendability Trade Study." The purpose of this study was to determine the utility of flying the first stage as an expendable booster rather than making it reusable. To lower the study complexity, four operational scenarios (or cases) were defined. This assessment then included an evaluation of the development, reliability, performance, and transition impacts associated with an expendable solution. The paper looks at these scenarios from the perspectives of cost, reliability, and performance. The presentation provides an overview of the paper.

  11. Mobile Authoring of Open Educational Resources as Reusable Learning Objects

    ERIC Educational Resources Information Center

    Kinshuk; Jesse, Ryan

    2013-01-01

    E-learning technologies have allowed authoring and playback of standardized reusable learning objects (RLO) for several years. Effective mobile learning requires similar functionality at both design time and runtime. Mobile devices can play RLO using applications like SMILE, mobile access to a learning management system (LMS), or other systems…

  12. Reusable Reentry Satellite (RRS): Thermal control trade study

    NASA Technical Reports Server (NTRS)

    Wallace, Clark

    1990-01-01

    The design and assessment work performed in defining the on-orbit Thermal Control Subsystem (TCS) requirements for the Reusable Reentry Satellite (RRS) is discussed. Specifically, it describes the hardware and design measures necessary for maintaining the Payload Module (PM) Environmental Control Life Support System (ECLSS) heat exchanger, the hydrazine propellant, and PM water supply within their required temperature limits.

  13. Reusable chelating resins concentrate metal ions from highly dilute solutions

    NASA Technical Reports Server (NTRS)

    Bauman, A. J.; Weetal, H. H.; Weliky, N.

    1966-01-01

    Column chromatographic method uses new metal chelating resins for recovering heavy-metal ions from highly dilute solutions. The absorbed heavy-metal cations may be removed from the chelating resins by acid or base washes. The resins are reusable after the washes are completed.

  14. Reusable neoprene jacket protects parts for chemical milling

    NASA Technical Reports Server (NTRS)

    1965-01-01

    Reusable neoprene jacket is used to prepare metal part or panel for chemical milling. Jacket covers back and upper rim of part and is sealed before the masking solution is applied to surface to be milled. This reduces amount of masking material required for milling identical parts and increases production.

  15. Reusable Launch Vehicle (RLV) Mission/Market Model

    NASA Technical Reports Server (NTRS)

    Prince, Frank A.

    1999-01-01

    The goal of this model was to assess the Reusable Launch Vehicle's (RLV) capability to support the International Space Station (ISS) servicing, determine the potential to leverage the commercial marketplace to reduce NASA's cost, and to evaluate the RLV's ability to expand the space economy. The presentation is in view-graph format.

  16. Smart, reusable labels for assessing self-cleaning films.

    PubMed

    Mills, A; Wells, N

    2015-03-11

    Novel, reversible (reusable) photocatalyst activity indicator labels, which undergo a rapid colour change when in contact with a photocatalytic film via the photoreduction of methylene blue contained within the label's adhesive, are explored as a method for assessing the activity of self-cleaning glass in situ and the laboratory, using digital photography.

  17. Reusable Reentry Satellite (RRS): Thermal control trade study

    NASA Astrophysics Data System (ADS)

    Wallace, Clark

    1990-04-01

    The design and assessment work performed in defining the on-orbit Thermal Control Subsystem (TCS) requirements for the Reusable Reentry Satellite (RRS) is discussed. Specifically, it describes the hardware and design measures necessary for maintaining the Payload Module (PM) Environmental Control Life Support System (ECLSS) heat exchanger, the hydrazine propellant, and PM water supply within their required temperature limits.

  18. Design optimization for a space based, reusable orbit transfer vehicle

    NASA Technical Reports Server (NTRS)

    Redd, L.

    1985-01-01

    Future NASA and DOD missions will benefit from high performance, reusable orbit transfer vehicles. With the advent of a space station, advanced engine technology, and various new vehicle concepts, reusable orbit transfer vehicles that provide significant economic benefits and mission capability improvements will be realized. Engine and vehicle design criteria previously have lacked definition with regard to issues such as space basing and servicing, man-rating and reliability, performance, mission flexibility, and life cycle cost for a reusable vehicle. The design study described here has resulted in the definition of a reusable orbit transfer vehicle concept and subsequent recommendations for the design criteria of an advanced LO2/LH2 engine. These design criteria include number of engines per vehicle, nozzle design, etc. The major characteristics of the vehicle preliminary design include low lift to drag aerocapture capability, a main propulsion system failure criteria of fail operational/fail safe, and either two main engines with a high performance attitude control system for back-up or three main engines with which to meet this failure criteria. In addition, a maintenance approach has been established for the advanced vehicle concept.

  19. A Re-Usable Algorithm for Teaching Procedural Skills.

    ERIC Educational Resources Information Center

    Jones, Mark K.; And Others

    The design of a re-usable instructional algorithm for computer based instruction (CBI) is described. The prototype is implemented on IBM PC compatibles running the Windows(TM) graphical environment, using the prototyping tool ToolBook(TM). The algorithm is designed to reduce development and life cycle costs for CBI by providing an authoring…

  20. Structural Integrity and Durability of Reusable Space Propulsion Systems

    NASA Technical Reports Server (NTRS)

    1987-01-01

    A two-day conference on the structural integrity and durability of reusable space propulsion systems was held on May 12 and 13, 1987, at the NASA Lewis research Center. Aerothermodynamic loads; instrumentation; fatigue, fracture, and constitutive modeling; and structural dynamics were discussed.

  1. 2nd Generation Reusable Launch Vehicle NASA Led Propulsion Tasks

    NASA Technical Reports Server (NTRS)

    Richards, Steve

    2000-01-01

    Design, development and test of a 2nd generation Reusable Launch Vehicle (RLV) is presented. This current paper discusses the following: 2nd Generation RLV Propulsion Project, Overview of NASA Led Tasks in Propulsion, Gen2 Turbo Machinery Technology Demonstrator, and Combustion Devices Test Bed, GRCop-84 Sheet For Combustion Chambers, Nozzles and Large Actively Cooled Structures

  2. 14 CFR 431.79 - Reusable launch vehicle mission reporting requirements.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 14 Aeronautics and Space 4 2010-01-01 2010-01-01 false Reusable launch vehicle mission reporting requirements. 431.79 Section 431.79 Aeronautics and Space COMMERCIAL SPACE TRANSPORTATION, FEDERAL AVIATION...-Licensing Requirements-Reusable Launch Vehicle Mission License Terms and Conditions § 431.79 Reusable launch...

  3. 14 CFR 431.13 - Transfer of a reusable launch vehicle mission license.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 14 Aeronautics and Space 4 2010-01-01 2010-01-01 false Transfer of a reusable launch vehicle... AVIATION ADMINISTRATION, DEPARTMENT OF TRANSPORTATION LICENSING LAUNCH AND REENTRY OF A REUSABLE LAUNCH VEHICLE (RLV) General § 431.13 Transfer of a reusable launch vehicle mission license. (a) Only the FAA...

  4. 14 CFR 431.9 - Issuance of a reusable launch vehicle mission license.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 14 Aeronautics and Space 4 2010-01-01 2010-01-01 false Issuance of a reusable launch vehicle... AVIATION ADMINISTRATION, DEPARTMENT OF TRANSPORTATION LICENSING LAUNCH AND REENTRY OF A REUSABLE LAUNCH VEHICLE (RLV) General § 431.9 Issuance of a reusable launch vehicle mission license. (a) The FAA...

  5. 14 CFR 431.3 - Types of reusable launch vehicle mission licenses.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... 14 Aeronautics and Space 4 2011-01-01 2011-01-01 false Types of reusable launch vehicle mission... ADMINISTRATION, DEPARTMENT OF TRANSPORTATION LICENSING LAUNCH AND REENTRY OF A REUSABLE LAUNCH VEHICLE (RLV) General § 431.3 Types of reusable launch vehicle mission licenses. (a) Mission-specific license. A...

  6. 14 CFR 431.15 - Rights not conferred by a reusable launch vehicle mission license.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... 14 Aeronautics and Space 4 2011-01-01 2011-01-01 false Rights not conferred by a reusable launch..., FEDERAL AVIATION ADMINISTRATION, DEPARTMENT OF TRANSPORTATION LICENSING LAUNCH AND REENTRY OF A REUSABLE LAUNCH VEHICLE (RLV) General § 431.15 Rights not conferred by a reusable launch vehicle mission...

  7. 14 CFR 431.3 - Types of reusable launch vehicle mission licenses.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 14 Aeronautics and Space 4 2010-01-01 2010-01-01 false Types of reusable launch vehicle mission... ADMINISTRATION, DEPARTMENT OF TRANSPORTATION LICENSING LAUNCH AND REENTRY OF A REUSABLE LAUNCH VEHICLE (RLV) General § 431.3 Types of reusable launch vehicle mission licenses. (a) Mission-specific license. A...

  8. 14 CFR 431.9 - Issuance of a reusable launch vehicle mission license.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... 14 Aeronautics and Space 4 2011-01-01 2011-01-01 false Issuance of a reusable launch vehicle... AVIATION ADMINISTRATION, DEPARTMENT OF TRANSPORTATION LICENSING LAUNCH AND REENTRY OF A REUSABLE LAUNCH VEHICLE (RLV) General § 431.9 Issuance of a reusable launch vehicle mission license. (a) The FAA...

  9. 14 CFR 431.13 - Transfer of a reusable launch vehicle mission license.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... 14 Aeronautics and Space 4 2011-01-01 2011-01-01 false Transfer of a reusable launch vehicle... AVIATION ADMINISTRATION, DEPARTMENT OF TRANSPORTATION LICENSING LAUNCH AND REENTRY OF A REUSABLE LAUNCH VEHICLE (RLV) General § 431.13 Transfer of a reusable launch vehicle mission license. (a) Only the FAA...

  10. 14 CFR 431.15 - Rights not conferred by a reusable launch vehicle mission license.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 14 Aeronautics and Space 4 2010-01-01 2010-01-01 false Rights not conferred by a reusable launch..., FEDERAL AVIATION ADMINISTRATION, DEPARTMENT OF TRANSPORTATION LICENSING LAUNCH AND REENTRY OF A REUSABLE LAUNCH VEHICLE (RLV) General § 431.15 Rights not conferred by a reusable launch vehicle mission...

  11. Base-promoted coupling of carbon dioxide, amines, and diaryliodonium salts: a phosgene- and metal-free route to O-aryl carbamates.

    PubMed

    Xiong, Wenfang; Qi, Chaorong; Peng, Youbin; Guo, Tianzuo; Zhang, Min; Jiang, Huanfeng

    2015-10-05

    A phosgene- and metal-free synthesis of O-aryl carbamates is realized through a three-component coupling of carbon dioxide, amines and diaryliodonium salts. The reaction only requires a base as the promoter, providing access to a diverse array of O-aryl carbamates in moderate to high yields with excellent chemoselectivity.

  12. Forming heterojunction: an effective strategy to enhance the photocatalytic efficiency of a new metal-free organic photocatalyst for water splitting.

    PubMed

    Li, Hengshuai; Hu, Haiquan; Bao, Chunjiang; Guo, Feng; Zhang, Xiaoming; Liu, Xiaobiao; Hua, Juan; Tan, Jie; Wang, Aizhu; Zhou, Hongcai; Yang, Bo; Qu, Yuanyuan; Liu, Xiangdong

    2016-07-29

    Photocatalytic water splitting is a new technology for the conversion and utilization of solar energy and has a potential prospect. One important aspect of enhancing the photocatalytic efficiency is how to improve the electron-hole separation. Up to now, there is still no ideal strategy to improve the electron-hole separation. In this article, for metal-free organic photocatalysts, we propose a good strategy- forming heterojunction, which can effectively improve the electron-hole separation. We provide a metal-free organic photocatalyst g-C12N7H3 for water splitting. The stability of g-C12N7H3 has been investigated, the X-ray diffraction spectra has been simulated. Using first-principles calculations, we have systematically studied the electronic structure, band edge alignment, and optical properties for the g-C12N7H3. The results demonstrated that g-C12N7H3 is a new organocatalyst material for water splitting. In order to enhance the photocatalytic efficiency, we provided four strategies, i.e., multilayer stacking, raising N atoms, forming g-C9N10/g-C12N7H3 heterojunction, and forming graphene/g-C12N7H3 heterojunction. Our research is expected to stimulate experimentalists to further study novel 2D metal-free organic materials as visible light photocatalysts. Our strategies, especially forming heterojunction, will substantially help to enhance the photocatalytic efficiency of metal-free organic photocatalyst.

  13. Metal-free arylation of ethyl acetoacetate with hypervalent diaryliodonium salts: an immediate access to diverse 3-aryl-4(1H)-quinolones.

    PubMed

    Monastyrskyi, Andrii; Namelikonda, Niranjan K; Manetsch, Roman

    2015-03-06

    A clean arylation protocol of ethyl acetoacetate was developed using hypervalent diaryliodonium salts under mild and metal-free conditions. The scope of the reaction, using symmetric and unsymmetric iodonium salts with varying sterics and electronics, was examined. Further, this method has been applied for the synthesis of antimalarial compound ELQ-300, which is currently in preclinical development.

  14. Metal-free oxidative olefination of primary amines with benzylic C-H bonds through direct deamination and C-H bond activation.

    PubMed

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

    2014-09-14

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

  15. Synthesis of carbodiimides by I2/CHP-mediated cross-coupling reaction of isocyanides with amines under metal-free conditions.

    PubMed

    Zhu, Tong-Hao; Wang, Shun-Yi; Tao, Yang-Qing; Ji, Shun-Jun

    2015-04-17

    An I2/CHP-mediated cross-coupling reaction of isocyanides with readily accessible amines via C-N formation is described for carbodiimide synthesis in moderate to excellent yields. This represents a metal-free strategy for a coupling reaction of isocyanides with amines, and it provides an efficient approach for symmetric and unsymmetric functionalized carbodiimide derivative synthesis under mild conditions.

  16. Direct fabrication of metal-free hollow graphene balls with a self-supporting structure as efficient cathode catalysts of fuel cell

    NASA Astrophysics Data System (ADS)

    Lu, Yanqi; Liu, Mingda; Nie, Huagui; Gu, Cancan; Liu, Ming; Yang, Zhi; Yang, Keqin; Chen, Xi'an; Huang, Shaoming

    2016-06-01

    Despite the good progress in developing carbon catalysts for oxygen reduction reaction (ORR), the current metal-free carbon catalysts are still far from satisfactory for large-scale applications of fuel cell. Developing hollow graphene balls with a self-supporting structure is considered to be an ideal method to inhibit graphene stacking and improve their catalytic performance. Herein, we fabricated metal-free hollow graphene balls with a self-supporting structure, through using a new strategy that involves direct metal-free catalytic growth from assembly of SiO2 spheres. To our knowledge, although much researches involving the synthesis of graphene balls have been reported, investigations into the direct metal-free catalytic growth of hollow graphene balls are rare. Furthermore, the electrocatalytic performance shows that the resulting hollow graphene balls have significantly high catalytic activity. More importantly, such catalysts also possess much improved stability and better methanol tolerance in alkaline media during the ORR compared with commercial Pt/C catalysts. The outstanding performances coupled with an easy and inexpensive preparing method indicated the great potential of the hollow graphene balls with a self-supporting structure in large-scale applications of fuel cell.

  17. The Ability of Dental Specialists to Distinguish Lateral Incisor Metal-Free From Porcelain-Fused-to-Metal Implant Supported Crowns.

    PubMed

    De Melo, Eduardo V; Kauling, Ana Elisa C; Freitas, Sérgio Fernando T; Cardoso, Antônio C; Ferreira, Cimara Fortes

    2014-12-01

    The objective of this study was to evaluate the ability of dental specialists to distinguish lateral incisor metal-free from porcelain-fused-to-metal implant supported crowns in the anterior region. Five single-tooth implants in the maxillary lateral incisor region were restored with two types of implant-supported crowns (porcelain-fused-to-metal and metal-free). Photographs were presented to 20 evaluators. The evaluators had to answer whether the crown was: metal-free, porcelain-fused-to-metal or they could not tell the difference. The results showed that groups 1 (all participants), 3 (Restorative & Prosthodontic specialists), 4 (graduated 10 years) and 5 (graduated > 10 years) failed to respond correctly (P > 0.05) to which type of crown was presented to them. Group 2 (Periodontology & Implantology specialists) showed an accuracy rate of 35.6% (P = 0.009), in relation to metal-free crowns, 5.6 which is below the random index. The authors concluded that the evaluators from the 5 groups studied were unable to significantly distinguish which type of crown was used in the 10 presented situations.

  18. Direct, metal-free amination of heterocyclic amides/ureas with NH-heterocycles and N-substituted anilines in POCl3.

    PubMed

    Deng, Xiaohu; Roessler, Armin; Brdar, Ivana; Faessler, Roger; Wu, Jiejun; Sales, Zachary S; Mani, Neelakandha S

    2011-10-21

    A POCl(3)-mediated, direct amination reaction of heterocyclic amides/ureas with NH-heterocycles or N-substituted anilines is described. Compared to the existing methods, this operationally simple protocol provides unique reactivity and functional group compatibility because of the metal-free, acidic reaction conditions. The yields are generally excellent.

  19. Asymmetric Construction of Functionalized 1,2-Dihydropyridine and Pyridine Derivatives with Adjacent Stereocenters via a Unified Metal-Free Catalytic Approach.

    PubMed

    Zou, Gong-Feng; Zhang, Shi-Qiang; Wang, Jia-Xin; Liao, Wei-Wei

    2016-07-01

    A novel asymmetric catalytic approach for the construction of enantioenriched functionalized 1,2-dihydropyridines and pyridine derivatives incorporating adjacent quaternary and tertiary stereocenters has been reported. This process involved a metal-free catalytic asymmetric allylic alkylation and a stereospecifically nonoxidative aromatization approach for the desired chiral molecules.

  20. Bantam: A Systematic Approach to Reusable Launch Vehicle Technology Development

    NASA Technical Reports Server (NTRS)

    Griner, Carolyn; Lyles, Garry

    1999-01-01

    The Bantam technology project is focused on providing a low cost launch capability for very small (100 kilogram) NASA and University science payloads. The cost goal has been set at one million dollars per launch. The Bantam project, however, represents much more than a small payload launch capability. Bantam represents a unique, systematic approach to reusable launch vehicle technology development. This technology maturation approach will enable future highly reusable launch concepts in any payload class. These launch vehicle concepts of the future could deliver payloads for hundreds of dollars per pound, enabling dramatic growth in civil and commercial space enterprise. The National Aeronautics and Space Administration (NASA) has demonstrated a better, faster, and cheaper approach to science discovery in recent years. This approach is exemplified by the successful Mars Exploration Program lead by the Jet Propulsion Laboratory (JPL) for the NASA Space Science Enterprise. The Bantam project represents an approach to space transportation technology maturation that is very similar to the Mars Exploration Program. The NASA Advanced Space Transportation Program (ASTP) and Future X Pathfinder Program will combine to systematically mature reusable space transportation technology from low technology readiness to system level flight demonstration. New reusable space transportation capability will be demonstrated at a small (Bantam) scale approximately every two years. Each flight demonstration will build on the knowledge derived from the previous flight tests. The Bantam scale flight demonstrations will begin with the flights of the X-34. The X-34 will demonstrate reusable launch vehicle technologies including; flight regimes up to Mach 8 and 250,000 feet, autonomous flight operations, all weather operations, twenty-five flights in one year with a surge capability of two flights in less than twenty-four hours and safe abort. The Bantam project will build on this initial

  1. Synthesis, structures, and properties of crystalline salts with radical anions of metal-containing and metal-free phthalocyanines.

    PubMed

    Konarev, Dmitri V; Kuzmin, Alexey V; Faraonov, Maxim A; Ishikawa, Manabu; Khasanov, Salavat S; Nakano, Yoshiaki; Otsuka, Akihiro; Yamochi, Hideki; Saito, Gunzi; Lyubovskaya, Rimma N

    2015-01-12

    Radical anion salts of metal-containing and metal-free phthalocyanines [MPc(3-)](·-), where M = Cu(II), Ni(II), H2, Sn(II), Pb(II), Ti(IV)O, and V(IV)O (1-10) with tetraalkylammonium cations have been obtained as single crystals by phthalocyanine reduction with sodium fluorenone ketyl. Their formation is accompanied by the Pc ligand reduction and affects the molecular structure of metal phthalocyanine radical anions as well as their optical and magnetic properties. Radical anions are characterized by the alternation of short and long C-Nimine bonds in the Pc ligand owing to the disruption of its aromaticity. Salts 1-10 show new bands at 833-1041 nm in the NIR range, whereas the Q- and Soret bands are blue-shifted by 0.13-0.25 eV (38-92 nm) and 0.04-0.07 eV (4-13 nm), respectively. Radical anions with Ni(II), Sn(II), Pb(II), and Ti(IV)O have S = 1/2 spin state, whereas [Cu(II)Pc(3-)](·-) and [V(IV)OPc(3-)](·-) containing paramagnetic Cu(II) and V(IV)O have two S = 1/2 spins per radical anion. Central metal atoms strongly affect EPR spectra of phthalocyanine radical anions. Instead of narrow EPR signals characteristic of metal-free phthalocyanine radical anions [H2Pc(3-)](·-) (linewidth of 0.08-0.24 mT), broad EPR signals are manifested (linewidth of 2-70 mT) with g-factors and linewidths that are strongly temperature-dependent. Salt 11 containing the [Na(I)Pc(2-)](-) anions as well as previously studied [Fe(I)Pc(2-)](-) and [Co(I)Pc(2-)](-) anions that are formed without reduction of the Pc ligand do not show changes in molecular structure or optical and magnetic properties characteristic of [MPc(3-)](·-) in 1-10.

  2. The Mass Spectrum of Metal-free Stars Resulting from Photodissociation Feedback: A Scenario for the Formation of Low-Mass Population III Stars

    NASA Astrophysics Data System (ADS)

    Omukai, Kazuyuki; Yoshii, Yuzuru

    2003-12-01

    The initial mass function (IMF) of metal-free stars that form in the initial starburst of massive (virial temperatures >~104 K) metal-free protogalaxies is studied. In particular, we focus on the effect of H2 photodissociation by preexisting stars on the fragmentation mass scale, presumedly determined by the Jeans mass at the end of the initial free-fall phase, i.e., at the so-called loitering phase, characterized by the temporary temperature minimum. Photodissociation diminishes the Jeans mass at the loitering phase, thereby reducing the fragmentation mass scale of primordial clouds. Thus, in a given cloud, far-ultraviolet (FUV) radiation from the first star, which is supposedly very massive (~103Msolar), reduces the mass scale for subsequent fragmentation. Through a series of similar processes the IMF for metal-free stars is established. If FUV radiation exceeds a threshold level, the star-forming clumps collapse solely through atomic cooling. Correspondingly, the fragmentation scale drops discontinuously from a few × 10Msolar to subsolar scales. In compact clouds (<~1.6 kpc for clouds of gas mass 108Msolar), this level of radiation field is attained and subsolar-mass stars are formed, even in a metal-free environment. Consequently, the IMF becomes bimodal, with peaks at a few tenths Msolar and a few × 10 Msolar. The high-mass portion of the IMF, ξhigh(m*), is found to be a very steep function of the stellar mass m*, ξhigh(m*)~m-5*. Therefore, the typical mass scale of metal-free stars is significantly smaller than that of the very first stars. In an appendix we study the thermal instability in collapsing primordial prestellar cores and discuss why the thermal instability occurring during the three-body H2 formation does not appear to manifest itself in causing further fragmentation of such cores.

  3. Metal-free organic dyes for TiO2 and ZnO dye-sensitized solar cells

    PubMed Central

    Selopal, Gurpreet Singh; Wu, Hui-Ping; Lu, Jianfeng; Chang, Yu-Cheng; Wang, Mingkui; Vomiero, Alberto; Concina, Isabella; Diau, Eric Wei-Guang

    2016-01-01

    We report the synthesis and characterization of new metal-free organic dyes (namely B18, BTD-R, and CPTD-R) which designed with D-π-A concept to extending the light absorption region by strong conjugation group of π-linker part and applied as light harvester in dye sensitized solar cells (DSSCs). We compared the photovoltaic performance of these dyes in two different photoanodes: a standard TiO2 mesoporous photoanode and a ZnO photoanode composed of hierarchically assembled nanostructures. The results demonstrated that B18 dye has better photovoltaic properties compared to other two dyes (BTD-R and CPTD-R) and each dye has higher current density (Jsc) when applied to hierarchical ZnO nanocrystallites than the standard TiO2 mesoporous film. Transient photocurrent and photovoltage decay measurements (TCD/TVD) were applied to systematically study the charge transport and recombination kinetics in these devices, showing the electron life time (τR) of B18 dye in ZnO and TiO2 based DSSCs is higher than CPTD-R and BTD-R based DSSCs, which is consistent with the photovoltaic performances. The conversion efficiency in ZnO based DSSCs can be further boosted by 35%, when a compact ZnO blocking layer (BL) is applied to inhibit electron back reaction. PMID:26738698

  4. Efficient noble-metal-free γ-Fe₂O₃@NiO core-shell nanostructured photocatalysts for water oxidation.

    PubMed

    Du, Xiaoqiang; Wei, Jie; Zhao, Jinli; Han, Ruixin; Ding, Yong

    2014-10-01

    Flowerlike noble-metal-free γ-Fe2O3@NiO core-shell hierarchical nanostructures have been fabricated and examined as a catalyst in the photocatalytic oxidation of water with [Ru(bpy)3](ClO4)2 as a photosensitizer and Na2S2O8 as a sacrificial electron acceptor. An apparent TOF of 0.29 μmols(-1) m(-2) and oxygen yield of 51% were obtained with γ-Fe2O3@NiO. The γ-Fe2O3@NiO core-shell hierarchical nanostructures could be easily separated from the reaction solution whilst maintaining excellent water-oxidation activity in the fourth and fifth runs. The surface conditions of γ-Fe2O3@NiO also remained unchanged after the photocatalytic reaction, as confirmed by X-ray photoelectron spectroscopy (XPS). © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Metal-Free Carbon-Based Materials: Promising Electrocatalysts for Oxygen Reduction Reaction in Microbial Fuel Cells

    PubMed Central

    Sawant, Sandesh Y.; Han, Thi Hiep; Cho, Moo Hwan

    2016-01-01

    Microbial fuel cells (MFCs) are a promising green approach for wastewater treatment with the simultaneous advantage of energy production. Among the various limiting factors, the cathodic limitation, with respect to performance and cost, is one of the main obstacles to the practical applications of MFCs. Despite the high performance of platinum and other metal-based cathodes, their practical use is limited by their high cost, low stability, and environmental toxicity. Oxygen is the most favorable electron acceptor in the case of MFCs, which reduces to water through a complicated oxygen reduction reaction (ORR). Carbon-based ORR catalysts possessing high surface area and good electrical conductivity improve the ORR kinetics by lowering the cathodic overpotential. Recently, a range of carbon-based materials have attracted attention for their exceptional ORR catalytic activity and high stability. Doping the carbon texture with a heteroatom improved their ORR activity remarkably through the favorable adsorption of oxygen and weaker molecular bonding. This review provides better insight into ORR catalysis for MFCs and the properties, performance, and applicability of various metal-free carbon-based electrocatalysts in MFCs to find the most appropriate cathodic catalyst for the practical applications. The approaches for improvement, key challenges, and future opportunities in this field are also explored. PMID:28029116

  6. Metal-Free Carbon-Based Materials: Promising Electrocatalysts for Oxygen Reduction Reaction in Microbial Fuel Cells.

    PubMed

    Sawant, Sandesh Y; Han, Thi Hiep; Cho, Moo Hwan

    2016-12-24

    Microbial fuel cells (MFCs) are a promising green approach for wastewater treatment with the simultaneous advantage of energy production. Among the various limiting factors, the cathodic limitation, with respect to performance and cost, is one of the main obstacles to the practical applications of MFCs. Despite the high performance of platinum and other metal-based cathodes, their practical use is limited by their high cost, low stability, and environmental toxicity. Oxygen is the most favorable electron acceptor in the case of MFCs, which reduces to water through a complicated oxygen reduction reaction (ORR). Carbon-based ORR catalysts possessing high surface area and good electrical conductivity improve the ORR kinetics by lowering the cathodic overpotential. Recently, a range of carbon-based materials have attracted attention for their exceptional ORR catalytic activity and high stability. Doping the carbon texture with a heteroatom improved their ORR activity remarkably through the favorable adsorption of oxygen and weaker molecular bonding. This review provides better insight into ORR catalysis for MFCs and the properties, performance, and applicability of various metal-free carbon-based electrocatalysts in MFCs to find the most appropriate cathodic catalyst for the practical applications. The approaches for improvement, key challenges, and future opportunities in this field are also explored.

  7. Metal-free organic dyes for TiO2 and ZnO dye-sensitized solar cells

    NASA Astrophysics Data System (ADS)

    Selopal, Gurpreet Singh; Wu, Hui-Ping; Lu, Jianfeng; Chang, Yu-Cheng; Wang, Mingkui; Vomiero, Alberto; Concina, Isabella; Diau, Eric Wei-Guang

    2016-01-01

    We report the synthesis and characterization of new metal-free organic dyes (namely B18, BTD-R, and CPTD-R) which designed with D-π-A concept to extending the light absorption region by strong conjugation group of π-linker part and applied as light harvester in dye sensitized solar cells (DSSCs). We compared the photovoltaic performance of these dyes in two different photoanodes: a standard TiO2 mesoporous photoanode and a ZnO photoanode composed of hierarchically assembled nanostructures. The results demonstrated that B18 dye has better photovoltaic properties compared to other two dyes (BTD-R and CPTD-R) and each dye has higher current density (Jsc) when applied to hierarchical ZnO nanocrystallites than the standard TiO2 mesoporous film. Transient photocurrent and photovoltage decay measurements (TCD/TVD) were applied to systematically study the charge transport and recombination kinetics in these devices, showing the electron life time (τR) of B18 dye in ZnO and TiO2 based DSSCs is higher than CPTD-R and BTD-R based DSSCs, which is consistent with the photovoltaic performances. The conversion efficiency in ZnO based DSSCs can be further boosted by 35%, when a compact ZnO blocking layer (BL) is applied to inhibit electron back reaction.

  8. Metal-free organic dyes for TiO2 and ZnO dye-sensitized solar cells.

    PubMed

    Selopal, Gurpreet Singh; Wu, Hui-Ping; Lu, Jianfeng; Chang, Yu-Cheng; Wang, Mingkui; Vomiero, Alberto; Concina, Isabella; Diau, Eric Wei-Guang

    2016-01-07

    We report the synthesis and characterization of new metal-free organic dyes (namely B18, BTD-R, and CPTD-R) which designed with D-π-A concept to extending the light absorption region by strong conjugation group of π-linker part and applied as light harvester in dye sensitized solar cells (DSSCs). We compared the photovoltaic performance of these dyes in two different photoanodes: a standard TiO2 mesoporous photoanode and a ZnO photoanode composed of hierarchically assembled nanostructures. The results demonstrated that B18 dye has better photovoltaic properties compared to other two dyes (BTD-R and CPTD-R) and each dye has higher current density (Jsc) when applied to hierarchical ZnO nanocrystallites than the standard TiO2 mesoporous film. Transient photocurrent and photovoltage decay measurements (TCD/TVD) were applied to systematically study the charge transport and recombination kinetics in these devices, showing the electron life time (τR) of B18 dye in ZnO and TiO2 based DSSCs is higher than CPTD-R and BTD-R based DSSCs, which is consistent with the photovoltaic performances. The conversion efficiency in ZnO based DSSCs can be further boosted by 35%, when a compact ZnO blocking layer (BL) is applied to inhibit electron back reaction.

  9. Co4N Nanowires: Noble-Metal-Free Peroxidase Mimetic with Excellent Salt- and Temperature-Resistant Abilities.

    PubMed

    Li, Yu-Zhen; Li, Tong-Tong; Chen, Wei; Song, Yan-Yan

    2017-09-06

    Compared to natural enzymes, nanomaterial-based artificial enzymes have attracted immense attention because of their high stability and cost-effectiveness. In this study, cobalt nitride (Co4N) as a noble-metal-free artificial enzyme exhibiting highly intrinsic peroxidase-like activity and good stability was reported. Kinetic studies revealed that the resultant Co4N nanowires (NWs) exhibited a stronger affinity for 3,3',5,5'-tetramethylbenzidine (TMB) and H2O2 than HRP. Compared to Co3O4 NWs, Co4N NWs exhibited highly improved catalytic activities, with H2O2 exhibiting an apparent Km approximately 2 orders of magnitude less than that of Co3O4. In particular, the peroxidase-like activity of Co4N was maintained well over a wide range of temperatures and ionic strength. A Co4N-based method was further developed for the detection of glucose with good sensitivity and reliability. Because of advantages such as easy storage, cost-effectiveness, high sensitivity, and outstanding stability, Co4N NWs demonstrate the potential for replacing noble-metal-based peroxidase mimetics in a wide range of promising applications.

  10. An Intramolecular Silylene Borane Capable of Facile Activation of Small Molecules, Including Metal-Free Dehydrogenation of Water.

    PubMed

    Mo, Zhenbo; Szilvási, Tibor; Zhou, Yu-Peng; Yao, Shenglai; Driess, Matthias

    2017-02-27

    The first single-component N-heterocyclic silylene borane 1 (LSi-R-BMes2 ; L=PhC(N(t) Bu)2 ; R=1,12-xanthendiyl spacer; Mes=2,4,6-Me3 C6 H2 ), acting as a frustrated Lewis pair (FLP) in small-molecule activation, can be synthesized in 65 % yields. Its HOMO is largely localized at the silicon(II) atom and the LUMO has mainly boron 2p character. In small-molecule activation 1 allows access to the intramolecular silanone-borane 3 featuring a Si=O→B interaction through reaction with O2 , N2 O, or CO2 , and formation of silanethione borane 4 from reaction with S8 . The Si(II) center in 1 undergoes immediate hydrogenation if exposed to H2 at 1 atm pressure in benzene, affording the silane borane 5-H2 , L(H2 )Si-R-BMes2 . Remarkably, no H2 activation occurs if the single silylene LSiPh and Mes3 B intermolecularly separated are exposed to dihydrogen. Unexpectedly, the pre-organized Si-B separation in 1 enables a metal-free dehydrogenation of H2 O to give the silanone-borane 3 as reactive intermediate.

  11. A Noble-Metal-Free Nickel(II) Polypyridyl Catalyst for Visible-Light-Driven Hydrogen Production from Water.

    PubMed

    Yuan, Yong-Jun; Lu, Hong-Wei; Tu, Ji-Ren; Fang, Yong; Yu, Zhen-Tao; Fan, Xiao-Xing; Zou, Zhi-Gang

    2015-10-05

    The complex [Ni(bpy)3](2+) (bpy=2,2'-bipyridine) is an active catalyst for visible-light-driven H2 production from water when employed with [Ir(dfppy)2 (Hdcbpy)] [dfppy=2-(3,4-difluorophenyl)pyridine, Hdcbpy=4-carboxy-2,2'-bipyridine-4'-carboxylate] as the photosensitizer and triethanolamine as the sacrificial electron donor. The highest turnover number of 520 with respect to the nickel(II) catalyst is obtained in a 8:2 acetonitrile/water solution at pH 9. The H2 -evolution system is more stable after the addition of an extra free bpy ligand, owing to faster catalyst regeneration. The photocatalytic results demonstrate that the nickel(II) polypyridyl catalyst can act as a more effective catalyst than the commonly utilized [Co(bpy)3 ](2+). This study may offer a new paradigm for constructing simple and noble-metal-free catalysts for photocatalytic hydrogen production. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Metal free columns for determination of deoxynucleotide monophosphate by liquid chromatography/mass spectrometry and application to oligonucleotide.

    PubMed

    Shibayama, Sachie; Sakamaki, Hiroshi; Yamazaki, Taichi; Takatsu, Akiko

    2015-08-07

    We have developed a highly sensitive method for the analysis of deoxynucleotide monophosphates (dNMPs), which involves the use of liquid chromatography/mass spectrometry (LC/MS) and a new metal-free column. The new column solves the problem that the phosphate group in dNMPs interacts with the metal portion of the device or column. After optimization of the analytical conditions, the limits of detection (LODs) of dNMPs were from 5.4ng/g to 6.3ng/g. Those values were 10 times lower than the LODs of previous methods. We applied the method to the determination of the base composition and the quantification of 20-mer oligonucleotide. Despite use of a very small sample amount of 14.5ng, we were able to determine the base composition, and the result was consistent with theoretical values. We were also able to quantify the mass fraction of oligonucleotide with 8.2% expanded uncertainty (k=2). By means of the developed method, we were able to analyze dNMPs with high sensitivity as well as determine the base composition and quantify the mass fraction of oligonucleotide despite use of a small amount of sample. Copyright © 2015 Elsevier B.V. All rights reserved.

  13. Modeling the interactions of phthalocyanines in water: from the Cu(II)-tetrasulphonate to the metal-free phthalocyanine.

    PubMed

    Martín, Elisa I; Martínez, Jose M; Sánchez Marcos, Enrique

    2011-01-14

    A quantum and statistical study on the effects of the ions Cu(2+) and SO(3)(-) in the solvent structure around the metal-free phthalocyanine (H(2)Pc) is presented. We developed an ab initio interaction potential for the system CuPc-H(2)O based on quantum chemical calculations and studied its transferability to the H(2)Pc-H(2)O and [CuPc(SO(3))(4)](4-)-H(2)O interactions. The use of the molecular dynamics technique allows the determination of energetic and structural properties of CuPc, H(2)Pc, and [CuPc(SO(3))(4)](4-) in water and the understanding of the keys for the different behaviors of the three phthalocyanine (Pc) derivatives in water. The inclusion of the Cu(2+) cation in the Pc structure reinforces the appearance of two axial water molecules and second-shell water molecules in the solvent structure, whereas the presence of SO(3)(-) anions implies a well defined hydration shell of about eight water molecules around them making the macrocycle soluble in water. Debye-Waller factors for axial water molecules have been obtained in order to examine the potential sensitivity of the extended x-ray absorption fine structure technique to detect the axial water molecules.

  14. Facile synthesis of nitrogen and sulfur codoped carbon from ionic liquid as metal-free catalyst for oxygen reduction reaction.

    PubMed

    She, Yiyi; Lu, Zhouguang; Ni, Meng; Li, Li; Leung, Michael K H

    2015-04-08

    Developing metal-free catalysts for oxygen reduction reaction (ORR) is a great challenge in the development of fuel cells. Nitrogen and sulfur codoped carbon with remarkably high nitrogen content up to 13.00 at % was successfully fabricated by pyrolysis of homogeneous mixture of exfoliated graphitic flakes and ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([Bimi][Tf2N]). The exfoliated graphite flakes served as a structure-directing substance as well as additional carbon source in the fabrication. It was demonstrated that the use of graphite flakes increased the nitrogen doping level, optimized the composition of active nitrogen configurations, and enlarged the specific surface area of the catalysts. Electrochemical characterizations revealed that the N and S codoped carbon fabricated by this method exhibited superior catalytic activities toward ORR under both acidic and alkaline conditions. Particularly in alkaline solution, the current catalyst compared favorably to the conventional 20 wt % Pt/C catalyst via four-electron transfer pathway with better ORR selectivity. The excellent catalytic activity was mainly ascribed to high nitrogen doping content, appropriate constitution of active nitrogen configurations, large specific surface area, and synergistic effect of N and S codoping.

  15. Time-Resolved Electron Paramagnetic Resonance and Theoretical Investigations of Metal-Free Room-Temperature Triplet Emitters.

    PubMed

    Matsuoka, Hideto; Retegan, Marius; Schmitt, Lisa; Höger, Sigurd; Neese, Frank; Schiemann, Olav

    2017-09-20

    Utilization of triplets is important for preparing organic light-emitting diodes with high efficiency. Very recently, both electrophosphorescence and electrofluorescence could be observed at room temperature for thienyl-substituted phenazines without any heavy metals ( Ratzke et al. J. Phys. Chem. Lett. , 2016 , 7 , 4802 ). It was found that the phosphorescence efficiency depends on the orientation of fused thiophenes. In this work, the thienyl-substituted phenazines are investigated in more detail by time-resolved electron paramagnetic resonance (EPR) and quantum chemical calculations. Spin dynamics, zero-field splitting constants, and electron-spin structures of the excited triplet states for the metal-free room-temperature triplet emitters are correlated with phosphorescence efficiency. Complete active space self-consistent field (CASSCF) calculations clearly show that the electron spin density distributions of the first excited triplet states are strongly affected by the molecular geometry. For the phosphorescent molecules, the electron spins are localized on the phenazine unit, in which the sulfur atom of the fused thiophene points upward. The electron spins are delocalized onto the thiophene unit just by changing the orientation of the fused thiophenes from upward to downward, resulting in the suppression of phosphorescence. Time-resolved EPR measurements and time-dependent density functional theory (TD-DFT) calculations demonstrate that the electron spins delocalized onto the thiophene unit lead to the acceleration of nonradiative decays, in conjunction with the narrowing of the singlet-triplet energy gap.

  16. Biomass-derived nitrogen self-doped porous carbon as effective metal-free catalysts for oxygen reduction reaction.

    PubMed

    Liu, Xiaojun; Zhou, Yucheng; Zhou, Weijia; Li, Ligui; Huang, Shaobin; Chen, Shaowei

    2015-04-14

    Biomass-derived nitrogen self-doped porous carbon was synthesized by a facile procedure based on simple pyrolysis of water hyacinth (eichhornia crassipes) at controlled temperatures (600-800 °C) with ZnCl2 as an activation reagent. The obtained porous carbon exhibited a BET surface area up to 950.6 m(2) g(-1), and various forms of nitrogen (pyridinic, pyrrolic and graphitic) were found to be incorporated into the carbon molecular skeleton. Electrochemical measurements showed that the nitrogen self-doped carbons possessed a high electrocatalytic activity for ORR in alkaline media that was highly comparable to that of commercial 20% Pt/C catalysts. Experimentally, the best performance was identified with the sample prepared at 700 °C, with the onset potential at ca. +0.98 V vs. RHE, that possessed the highest concentrations of pyridinic and graphitic nitrogens among the series. Moreover, the porous carbon catalysts showed excellent long-term stability and much enhanced methanol tolerance, as compared to commercial Pt/C. The performance was also markedly better than or at least comparable to the leading results in the literature based on biomass-derived carbon catalysts for ORR. The results suggested a promising route based on economical and sustainable biomass towards the development and engineering of value-added carbon materials as effective metal-free cathode catalysts for alkaline fuel cells.

  17. Magnesiothermic synthesis of sulfur-doped graphene as an efficient metal-free electrocatalyst for oxygen reduction

    PubMed Central

    Wang, Jiacheng; Ma, Ruguang; Zhou, Zhenzhen; Liu, Guanghui; Liu, Qian

    2015-01-01

    Efficient metal-free electrocatalysts for oxygen reduction reaction (ORR) are highly expected in future low-cost energy systems. We have successfully prepared crumpled, sheet-like, sulfur-doped graphene by magnesiothermic reduction of easily available, low-cost, nontoxic CO2 (in the form of Na2CO3) and Na2SO4 as the carbon and sulfur sources, respectively. At high temperature, Mg can reduce not only carbon in the oxidation state of +4 in CO32− to form graphene, but also sulfur in SO42− from its highest (+6) to lowest valence which was hybridized into the carbon sp2 framework. Various characterization results show that sulfur-doped graphene with only few layers has an appropriate sulfur content, hierarchically robust porous structure, large surface area/pore volume, and highly graphitized textures. The S-doped graphene samples exhibit not only a high activity for ORR with a four-electron pathway, but also superior durability and tolerance to MeOH crossover to 40% Pt/C. This is mainly ascribed to the combination of sulfur-related active sites and hierarchical porous textures, facilitating fast diffusion of oxygen molecules and electrolyte to catalytic sites and release of products from the sites. PMID:25790856

  18. Modeling the interactions of phthalocyanines in water: From the Cu(II)-tetrasulphonate to the metal-free phthalocyanine

    NASA Astrophysics Data System (ADS)

    Martín, Elisa I.; Martínez, Jose M.; Marcos, Enrique Sánchez

    2011-01-01

    A quantum and statistical study on the effects of the ions Cu^{2+} and SO3- in the solvent structure around the metal-free phthalocyanine (H2Pc) is presented. We developed an ab initio interaction potential for the system CuPc-H2O based on quantum chemical calculations and studied its transferability to the H2Pc-H2O and [CuPc(SO3)4]^{4-}-H2O interactions. The use of the molecular dynamics technique allows the determination of energetic and structural properties of CuPc, H2Pc, and [CuPc(SO3)4]^{4-} in water and the understanding of the keys for the different behaviors of the three phthalocyanine (Pc) derivatives in water. The inclusion of the Cu^{2+} cation in the Pc structure reinforces the appearance of two axial water molecules and second-shell water molecules in the solvent structure, whereas the presence of SO3{}^- anions implies a well defined hydration shell of about eight water molecules around them making the macrocycle soluble in water. Debye-Waller factors for axial water molecules have been obtained in order to examine the potential sensitivity of the extended x-ray absorption fine structure technique to detect the axial water molecules.

  19. Self-Supported Cu-Based Nanowire Arrays as Noble-Metal-Free Electrocatalysts for Oxygen Evolution.

    PubMed

    Hou, Chun-Chao; Fu, Wen-Fu; Chen, Yong

    2016-08-23

    Crystalline Cu-based nanowire arrays (NWAs) including Cu(OH)2 , CuO, Cu2 O, and CuOx are facilely grown on Cu foil and are found to act as highly efficient, low-cost, and robust electrocatalysts for the oxygen evolution reaction (OER). Impressively, this noble-metal-free 3 D Cu(OH)2 -NWAs/Cu foil electrode shows the highest catalytic activity with a Tafel slope of 86 mV dec(-1) , an overpotential (η) of about 530 mV at ∼10 mA cm(-2) (controlled-potential electrolysis method without iR correction) and almost 100 % Faradic efficiency, paralleling the performance of the state-of-the-art RuO2 OER catalyst in 0.1 m NaOH solution (pH 12.8). To the best of our knowledge, this work represents one of the best results ever reported on Cu-based OER systems.

  20. Visible-Near-Infrared-Light-Driven Oxygen Evolution Reaction with Noble-Metal-Free WO2-WO3 Hybrid Nanorods.

    PubMed

    Wang, Song Ling; Mak, Yan Lin; Wang, Shijie; Chai, Jianwei; Pan, Feng; Foo, Maw Lin; Chen, Wei; Wu, Kai; Xu, Guo Qin

    2016-12-13

    Understanding and manipulating the one half-reaction of photoinduced hole-oxidation to oxygen are of fundamental importance to design and develop an efficient water-splitting process. To date, extensive studies on oxygen evolution from water splitting have focused on visible-light harvesting. However, capturing low-energy photons for oxygen evolution, such as near-infrared (NIR) light, is challenging and not well-understood. This report presents new insights into photocatalytic water oxidation using visible and NIR light. WO2-WO3 hybrid nanorods were in situ fabricated using a wet-chemistry route. The presence of metallic WO2 strengthens light absorption and promotes the charge-carrier separation of WO3. The efficiency of the oxygen evolution reaction over noble-metal-free WO2-WO3 hybrids was found to be significantly promoted. More importantly, NIR light (≥700 nm) can be effectively trapped to cause the photocatalytic water oxidation reaction. The oxygen evolution rates are even up to around 220 (λ = 700 nm) and 200 (λ = 800 nm) mmol g(-1) h(-1). These results demonstrate that the WO2-WO3 material is highly active for water oxidation with low-energy photons and opens new opportunities for multichannel solar energy conversion.

  1. A Bio-Inspired, Heavy-Metal-Free, Dual-Electrolyte Liquid Battery towards Sustainable Energy Storage.

    PubMed

    Ding, Yu; Yu, Guihua

    2016-04-04

    Wide-scale exploitation of renewable energy requires low-cost efficient energy storage devices. The use of metal-free, inexpensive redox-active organic materials represents a promising direction for environmental-friendly, cost-effective sustainable energy storage. To this end, a liquid battery is designed using hydroquinone (H2BQ) aqueous solution as catholyte and graphite in aprotic electrolyte as anode. The working potential can reach 3.4 V, with specific capacity of 395 mA h g(-1) and stable capacity retention about 99.7% per cycle. Such high potential and capacity is achieved using only C, H and O atoms as building blocks for redox species, and the replacement of Li metal with graphite anode can circumvent potential safety issues. As H2BQ can be extracted from biomass directly and its redox reaction mimics the bio-electrochemical process of quinones in nature, using such a bio-inspired organic compound in batteries enables access to greener and more sustainable energy-storage technology.

  2. Electrochemical Stimuli-Driven Facile Metal-Free Hydrogen Evolution from Pyrene-Porphyrin-Based Crystalline Covalent Organic Framework.

    PubMed

    Bhunia, Subhajit; Das, Sabuj Kanti; Jana, Rajkumar; Peter, Sebastian C; Bhattacharya, Santanu; Addicoat, Matthew; Bhaumik, Asim; Pradhan, Anirban

    2017-07-19

    A [2 + 2] Schiff base type condensation between 5,10,15,20-tetrakis(4-aminophenyl)porphyrin (TAP) and 1,3,6,8-tetrakis (4-formylphenyl) pyrene (TFFPy) under solvothermal condition yields a crystalline, quasi-two-dimensional covalent organic framework (SB-PORPy-COF). The porphyrin and pyrene units are alternatively occupied in the vertex of 3D triclinic crystal having permanent microporosity with moderately high surface area (∼869 m(2) g(-1)) and promising chemical stability. The AA stacking of the monolayers give a pyrene bridged conducting channel. SB-PORPy-COF has been exploited for metal free hydrogen production to understand the electrochemical behavior using the imine based docking site in acidic media. SB-PORPy-COF has shown the onset potential of 50 mV and the Tafel slope of 116 mV dec(-1). We expect that the addendum of the imine based COF would not only enrich the structural variety but also help to understand the electrochemical behavior of these class of materials.

  3. Li-Metal-Free Prelithiation of Si-Based Negative Electrodes for Full Li-Ion Batteries.

    PubMed

    Zhou, Haitao; Wang, Xuehang; Chen, De

    2015-08-24

    Most of the high-capacity positive-electrode materials [for example, S, O2 (air), and MOx (M: V, Mn, Fe, etc.)] are Li-deficient and require the use of a Li-metal electrode or prelithiation. Herein, we report a novel electrolytic cell in which the Si electrode can be prelithiated in a well-controlled manner from Li-containing aqueous solution in a Li-metal-free way. MnOx/Si and S/Si Li-ion full cells were assembled by using the prelithiated Si negative electrodes, which resulted in high specific energies of 349 and 732 Wh kg(-1), respectively. The MnOx/Si full cell still retains 138 Wh kg(-1) even at a high specific power of 1710 W kg(-1). This is the first report of a whole process of making a full Li-ion battery with both Li-deficient electrodes without the use of Li metal as the Li source. This novel prelithiation process, with high controllability, no short circuiting, and an abundant Li source, is expected to contribute significantly to the development of safe, green, and powerful Li-ion batteries. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. SBA-15-functionalized 3-oxo-ABNO as recyclable catalyst for aerobic oxidation of alcohols under metal-free conditions.

    PubMed

    Karimi, Babak; Farhangi, Elham; Vali, Hojatollah; Vahdati, Saleh

    2014-09-01

    The nitroxyl radical 3-oxo-9-azabicyclo [3.3.1]nonane-N-oxyl (3-oxo-ABNO) has been prepared using a simple protocol. This organocatalyst is found to be an efficient catalyst for the aerobic oxidation of a wide variety of alcohols under metal-free conditions. In addition, the preparation and characterization of a supported version of 3-oxo-ABNO on ordered mesoporous silica SBA-15 (SABNO) is described for the first time. The catalyst has been characterized using several techniques including simultaneous thermal analysis (STA), transmission electron microscopy (TEM), and nitrogen sorption analysis. This catalyst exhibits catalytic performance comparable to its homogeneous analogue and much superior catalytic activity in comparison with (2,2,6,6-tetramethylpiperidin-1-yl)oxy (TEMPO) for the aerobic oxidation of almost the same range of alcohols under identical reaction conditions. It is also found that SABNO can be conveniently recovered and reused at least 12 times without significant effect on its catalytic efficiency.

  5. Facile access to potent antiviral quinazoline heterocycles with fluorescence properties via merging metal-free domino reactions

    NASA Astrophysics Data System (ADS)

    Held, Felix E.; Guryev, Anton A.; Fröhlich, Tony; Hampel, Frank; Kahnt, Axel; Hutterer, Corina; Steingruber, Mirjam; Bahsi, Hanife; von Bojničić-Kninski, Clemens; Mattes, Daniela S.; Foertsch, Tobias C.; Nesterov-Mueller, Alexander; Marschall, Manfred; Tsogoeva, Svetlana B.

    2017-05-01

    Most of the known approved drugs comprise functionalized heterocyclic compounds as subunits. Among them, non-fluorescent quinazolines with four different substitution patterns are found in a variety of clinically used pharmaceuticals, while 4,5,7,8-substituted quinazolines and those displaying their own specific fluorescence, favourable for cellular uptake visualization, have not been described so far. Here we report the development of a one-pot synthetic strategy to access these 4,5,7,8-substituted quinazolines, which are fluorescent and feature strong antiviral properties (EC50 down to 0.6+/-0.1 μM) against human cytomegalovirus (HCMV). Merging multistep domino processes in one-pot under fully metal-free conditions leads to sustainable, maximum efficient and high-yielding organic synthesis. Furthermore, generation of artesunic acid-quinazoline hybrids and their application against HCMV (EC50 down to 0.1+/-0.0 μM) is demonstrated. Fluorescence of new antiviral hybrids and quinazolines has potential applications in molecular imaging in drug development and mechanistic studies, avoiding requirement of linkage to external fluorescent markers.

  6. Modeling Electrochemical Performance of the Hierarchical Morphology of Precious Group Metal-free Cathode for Polymer Electrolyte Fuel Cell

    DOE PAGES

    Komini Babu, Siddharth; Chung, Hoon Taek; Zelenay, Piotr; ...

    2017-08-04

    Here, this paper presents a two-dimensional (2D) computational model of a polymer electrolyte fuel cell (PEFC) with a platinum group metal-free (PGM-free) catalyst cathode that can significantly reduce PEFC costs by eliminating the need for expensive platinum catalysts. Due to their comparatively low volumetric activity, PGM-free cathodes are an order of magnitude thicker than their Pt-based counterpart. The resulting need for greater electrode thickness to achieve sufficient power density requires careful attention to the transport losses across the thicker cathodes. The presented model is used to correlate the composition and morphology of the cathode to PEFC performance. The model ismore » a complete cell, continuum model that includes an advanced agglomerate model for a microstructurally consistent representation of the cathode. A unique feature of the approach is the integration of morphology and transport parameter statistics extracted from nano-scale resolution X-ray computed tomography (nano-CT) imaging of PGM-free cathodes. The model was validated with experimental results of PGM-free cathodes with varying Nafion loading. Lastly, our key findings are a need for increased cathode hydrophobicity and increased ionomer conductivity through either reduced tortuosity or increased bulk conductivity. We further use the model to evaluate targets for the volumetric activity and active site density for future catalysts.« less

  7. Regioselectivity and Mechanism of Synthesizing N-Substituted 2-Pyridones and 2-Substituted Pyridines via Metal-Free C-O and C-N Bond-Cleaving of Oxazoline[3,2-a]pyridiniums

    NASA Astrophysics Data System (ADS)

    Li, Bo; Xue, Susu; Yang, Yang; Feng, Jia; Liu, Peng; Zhang, Yong; Zhu, Jianming; Xu, Zhijian; Hall, Adrian; Zhao, Bo; Shi, Jiye; Zhu, Weiliang

    2017-01-01

    Novel intermediate oxazoline[3,2-a]pyridiniums were facilely prepared from 2-(2,2-dimethoxyethoxy)-pyridines via acid promoted intramolecular cyclization. Sequentially, the quaternary ammonium salts were treated with different nucleophiles for performing regioselective metal-free C-O and C-N bond-cleaving to afford prevalent heterocyclic structures of N-substituted pyridones and 2-substituted pyridines. The reaction mechanism and regioselectivity were then systematically explored by quantum chemistry calculations at B3LYP/6-31 g(d) level. The calculated free energy barrier of the reactions revealed that aniline and aliphatic amines (e.g., methylamine) prefer to attack C8 of intermediate 4a, affording N-substituted pyridones, while phenylmethanamine, 2-phenylethan-1-amine and 3-phenylpropan-1-amine favor to attack C2 of the intermediate to form 2-substituted pyridines. With the optimized geometries of the transition states, we found that the aromatic ring of the phenyl aliphatic amines may form cation-π interaction with the pyridinium of the intermediates, which could stabilize the transition states and facilitate the formation of 2-substituted pyridines.

  8. Regioselectivity and Mechanism of Synthesizing N-Substituted 2-Pyridones and 2-Substituted Pyridines via Metal-Free C-O and C-N Bond-Cleaving of Oxazoline[3,2-a]pyridiniums

    PubMed Central

    Li, Bo; Xue, Susu; Yang, Yang; Feng, Jia; Liu, Peng; Zhang, Yong; Zhu, Jianming; Xu, Zhijian; Hall, Adrian; Zhao, Bo; Shi, Jiye; Zhu, Weiliang

    2017-01-01

    Novel intermediate oxazoline[3,2-a]pyridiniums were facilely prepared from 2-(2,2-dimethoxyethoxy)-pyridines via acid promoted intramolecular cyclization. Sequentially, the quaternary ammonium salts were treated with different nucleophiles for performing regioselective metal-free C-O and C-N bond-cleaving to afford prevalent heterocyclic structures of N-substituted pyridones and 2-substituted pyridines. The reaction mechanism and regioselectivity were then systematically explored by quantum chemistry calculations at B3LYP/6-31 g(d) level. The calculated free energy barrier of the reactions revealed that aniline and aliphatic amines (e.g., methylamine) prefer to attack C8 of intermediate 4a, affording N-substituted pyridones, while phenylmethanamine, 2-phenylethan-1-amine and 3-phenylpropan-1-amine favor to attack C2 of the intermediate to form 2-substituted pyridines. With the optimized geometries of the transition states, we found that the aromatic ring of the phenyl aliphatic amines may form cation-π interaction with the pyridinium of the intermediates, which could stabilize the transition states and facilitate the formation of 2-substituted pyridines. PMID:28120894

  9. Nuclear-electric reusable orbital transfer vehicle

    NASA Astrophysics Data System (ADS)

    Jaffe, Leonard D.

    1988-10-01

    To help determine the systems requirements for a 300-kWe space nuclear reactor power system, a mission and spacecraft have been examined that utilize electric propulsion supported by the nuclear reactor's power for multiple transfers of cargo between low earth orbit (LEO) and geosynchronous earth orbit (GEO). A propulsion system employing ion thrusters and xenon propellant was selected. Propellant and thrusters are replaced after each sortie to GEO. The mass of the orbital transfer vehicle (OTV), empty and dry, is 11,000 kg; nominal propellant load is 5000 kg. The OTV operates between a circular orbit at 925-km altitude, 28.5-deg inclination, and GEO. Cargo is brought to the OTV by Shuttle and an orbital maneuvering vehicle (OMV); the OTV then takes it to GEO. The OTV can also bring cargo back from GEO for transfer by OMV to the Shuttle. OTV propellant is resupplied, and the ion thrusters are replaced, by the OMV before each sortie to GEO. At the end of mission life, the OTV's electric propulsion is used to place it in a heliocentric orbit so that the reactor will not return to earth. The nominal cargo capability to GEO is 6000 kg, with a transit time of 120 days; 1350 kg can be transferred in 90 days, and 14,300 kg in 240 days. These capabilities can be considerably increased by using separate Shuttle launches to bring up propellant and cargo or by changing to mercury propellant.

  10. Nuclear-electric reusable orbital transfer vehicle

    NASA Technical Reports Server (NTRS)

    Jaffe, Leonard D.

    1988-01-01

    To help determine the systems requirements for a 300-kWe space nuclear reactor power system, a mission and spacecraft have been examined that utilize electric propulsion supported by the nuclear reactor's power for multiple transfers of cargo between low earth orbit (LEO) and geosynchronous earth orbit (GEO). A propulsion system employing ion thrusters and xenon propellant was selected. Propellant and thrusters are replaced after each sortie to GEO. The mass of the orbital transfer vehicle (OTV), empty and dry, is 11,000 kg; nominal propellant load is 5000 kg. The OTV operates between a circular orbit at 925-km altitude, 28.5-deg inclination, and GEO. Cargo is brought to the OTV by Shuttle and an orbital maneuvering vehicle (OMV); the OTV then takes it to GEO. The OTV can also bring cargo back from GEO for transfer by OMV to the Shuttle. OTV propellant is resupplied, and the ion thrusters are replaced, by the OMV before each sortie to GEO. At the end of mission life, the OTV's electric propulsion is used to place it in a heliocentric orbit so that the reactor will not return to earth. The nominal cargo capability to GEO is 6000 kg, with a transit time of 120 days; 1350 kg can be transferred in 90 days, and 14,300 kg in 240 days. These capabilities can be considerably increased by using separate Shuttle launches to bring up propellant and cargo or by changing to mercury propellant.

  11. Reusable, extendible flight software for a planetary spacecraft prototype testbed

    NASA Technical Reports Server (NTRS)

    Krasner, Sanford M.

    1995-01-01

    As part of the 'Faster, Better, Cheaper' paradigm for NASA missions, the Jet Propulsion Laboratory (JPL) is developing a Flight System Testbed for prototyping and early integration of future planetary missions. This paper describes the development of a set of reusable, extendible spacecraft flight software to be used as a basis for prototypes in the testbed. This effort has focused on identification and implementation of functions which are common across multiple missions. This effort has also developed an intertask messaging system which supports modification of existing functions, additions of new functions, and porting to various computation and input/output (I/O) architectures. This paper also identifies a number of other JPL activities which support standardization and reusability of planetary spacecraft designs.

  12. Structures and materials technology issues for reusable launch vehicles

    NASA Technical Reports Server (NTRS)

    Dixon, S. C.; Tenney, D. R.; Rummler, D. R.; Wieting, A. R.; Bader, R. M.

    1985-01-01

    Projected space missions for both civil and defense needs require significant improvements in structures and materials technology for reusable launch vehicles: reductions in structural weight compared to the Space Shuttle Orbiter of up to 25% or more, a possible factor of 5 or more increase in mission life, increases in maximum use temperature of the external surface, reusable containment of cryogenic hydrogen and oxygen, significant reductions in operational costs, and possibly less lead time between technology readiness and initial operational capability. In addition, there is increasing interest in hypersonic airbreathing propulsion for launch and transmospheric vehicles, and such systems require regeneratively cooled structure. The technology issues are addressed, giving brief assessments of the state-of-the-art and proposed activities to meet the technology requirements in a timely manner.

  13. Towards automated support for extraction of reusable components

    NASA Technical Reports Server (NTRS)

    Abd-El-hafiz, S. K.; Basili, Victor R.; Caldiera, Gianluigi

    1992-01-01

    A cost effective introduction of software reuse techniques requires the reuse of existing software developed in many cases without aiming at reusability. This paper discusses the problems related to the analysis and reengineering of existing software in order to reuse it. We introduce a process model for component extraction and focus on the problem of analyzing and qualifying software components which are candidates for reuse. A prototype tool for supporting the extraction of reusable components is presented. One of the components of this tool aids in understanding programs and is based on the functional model of correctness. It can assist software engineers in the process of finding correct formal specifications for programs. A detailed description of this component and an example to demonstrate a possible operational scenario are given.

  14. Airframe Integration Trade Studies for a Reusable Launch Vehicle

    NASA Technical Reports Server (NTRS)

    Dorsey, John T.; Wu, Chauncey; Rivers, Kevin; Martin, Carl; Smith, Russell

    1999-01-01

    Future launch vehicles must be lightweight, fully reusable and easily maintained if low-cost access to space is to be achieved. The goal of achieving an economically viable Single-Stage-to-Orbit (SSTO) Reusable Launch Vehicle (RLV) is not easily achieved and success will depend to a large extent on having an integrated and optimized total system. A series of trade studies were performed to meet three objectives. First, to provide structural weights and parametric weight equations as inputs to configuration-level trade studies. Second, to identify, assess and quantify major weight drivers for the RLV airframe. Third, using information on major weight drivers, and considering the RLV as an integrated thermal structure (composed of thrust structures, tanks, thermal protection system, insulation and control surfaces), identify and assess new and innovative approaches or concepts that have the potential for either reducing airframe weight, improving operability, and/or reducing cost.

  15. Reusable solid rocket motor case - Optimum probabilistic fracture control

    NASA Technical Reports Server (NTRS)

    Hanagud, S.; Uppaluri, B.

    1979-01-01

    A methodology for the reliability analysis of a reusable solid rocket motor case is discussed in this paper. The analysis is based on probabilistic fracture mechanics and probability distribution for initial flaw sizes. The developed reliability analysis can be used to select the structural design variables of the solid rocket motor case on the basis of minimum expected cost and specified reliability bounds during the projected design life of the case. Effects on failure prevention plans such as nondestructive inspection and the material erosion between missions can also be considered in the developed procedure for selection of design variables. The reliability-based procedure that has been discussed in this paper can easily be modified to consider other similar structures of reusable space vehicle systems with different fracture control plans.

  16. Reusable solid rocket motor case - Optimum probabilistic fracture control

    NASA Technical Reports Server (NTRS)

    Hanagud, S.; Uppaluri, B.

    1979-01-01

    A methodology for the reliability analysis of a reusable solid rocket motor case is discussed in this paper. The analysis is based on probabilistic fracture mechanics and probability distribution for initial flaw sizes. The developed reliability analysis can be used to select the structural design variables of the solid rocket motor case on the basis of minimum expected cost and specified reliability bounds during the projected design life of the case. Effects on failure prevention plans such as nondestructive inspection and the material erosion between missions can also be considered in the developed procedure for selection of design variables. The reliability-based procedure that has been discussed in this paper can easily be modified to consider other similar structures of reusable space vehicle systems with different fracture control plans.

  17. Test Results for Entry Guidance Methods for Reusable Launch Vehicles

    NASA Technical Reports Server (NTRS)

    Hanson, John M.; Jones, Robert E.

    2003-01-01

    There are a number of approaches to advanced guidance and control (AG&C) that have the potential for achieving the goals of significantly increasing reusable launch vehicle (RLV) safety and reliability, and reducing the cost. This paper examines some approaches to entry guidance. An effort called Integration and Testing of Advanced Guidance and Control Technologies (ITAGCT) has recently completed a rigorous testing phase where these algorithms faced high-fidelity vehicle models and were required to perform a variety of representative tests. The algorithm developers spent substantial effort improving the algorithm performance in the testing. This paper lists the test cases used to demonstrate that the desired results are achieved, shows an automated test scoring method that greatly reduces the evaluation effort required, and displays results of the tests. Results show a significant improvement over previous guidance approaches. The two best-scoring algorithm approaches show roughly equivalent results and are ready to be applied to future reusable vehicle concepts.

  18. Structures and materials technology issues for reusable launch vehicles

    NASA Technical Reports Server (NTRS)

    Dixon, S. C.; Tenney, D. R.; Rummler, D. R.; Wieting, A. R.; Bader, R. M.

    1985-01-01

    Projected space missions for both civil and defense needs require significant improvements in structures and materials technology for reusable launch vehicles: reductions in structural weight compared to the Space Shuttle Orbiter of up to 25 percent or more, a possible factor of 5 or more increase in mission life, increases in maximum use temperature of the external surface, reusable containment of cryogenic hydrogen and oxygen, significant reductions in operational costs, and possibly less lead time between technology readiness and initial operational capability. In addition, there is increasing interest in hypersonic airbreathing propulsion for launch and transmospheric vehicles, and such systems require regeneratively cooled structure. The technology issues are addressed, giving brief assessments of the state-of-the-art and proposed activities to meet the technology requirements in a timely manner.

  19. Analyses of Noise from Reusable Solid Rocket Motor (RSRM) Firings

    NASA Technical Reports Server (NTRS)

    Gee, Kent L.; Kenny, R. Jeremy; Jerome, Trevor W.; Neilsen, Tracianne B.; Hobbs, Christopher M.; James, Michael M.

    2012-01-01

    NASA s Space Launch Vehicle (SLS) program has chosen the Reusable Solid Rocket Motor V (RSRMV) as the booster system for initial flights. Lift off acoustics continue to be a consideration in overall vehicle vibroacoustic evaluations and launch pad modifications. Work started with the Ares program to understand solid rocket noise mechanisms is continuing through SLS program in conjunction with BYU/Blue Ridge Research Consulting.

  20. A reusable, low-profile, cryogenic wire seal

    NASA Astrophysics Data System (ADS)

    Stewart, M. D., Jr.; Koutroulakis, G.; Kalechofsky, N.; Mitrović, V. F.

    2010-01-01

    We describe the design of a reusable indium wire seal which has a small profile and is leak tight to better than 1×10-10 std. cc/s from room temperature down to ≈ 50mK. The pressure necessary to deform the indium wire o-ring is provided by a screw-cap mating to threads on the outside of the cylindrical volume to be sealed.

  1. The Alcoa ram fastener: A reusable blind rivet

    NASA Technical Reports Server (NTRS)

    Dewalt, W. J.

    1972-01-01

    Results of tensile, shear, fatigue and accelerated weathering tests are presented for the ram fastener, a reusable, single unit blind rivet. The effects of variations in hole size, grip length and sheet thickness on strength properties of the fastener were determined. The test results show these fasteners to have strength characteristics suitable for light structural applications. Exposure to accelerated weathering did not impair their performance.

  2. ObjectSim - A Reusable Object Oriented DIS Visual Simulation

    DTIC Science & Technology

    1993-12-01

    Space Command, software organizations are exploring the use of entire reusable systems designed for a particular application domain. Using this...approach, a system implementor uses a tool or tools designed to build the system from a set of parameters. In the Space Command case, the tool allowed a...simulation requiring a space view, including satellites. From these discussions and time spent in the lab, I developed a set of high level basis

  3. A Reusable, Low-profile, Cryogenic Wire Seal

    PubMed Central

    Stewart, M. D.; Koutroulakis, G.; Kalechofsky, N.; Mitrović, V. F.

    2009-01-01

    We describe the design of a reusable Indium wire seal which has a small profile and is leak tight to better than 1×10−10 std. cc/sec. from room temperature down to ≈mK. The pressure necessary to deform the Indium wire o-ring is provided by a screw-cap mating to threads on the outside of the cylindrical volume to be sealed. PMID:20161550

  4. Training Plan Central Archive for Reusable Software (CARDS).

    DTIC Science & Technology

    1992-07-07

    TECHNOLOGY FOR ADAPTABLE, RELIABLE SYSTEMS (STARS) Training Plan Central Archive for Reusable Software (CARDS) STARS-AC-04101/001/00 07 July 1992 Data Type... Software Technology for Adaptable, Reliable Systems (STARS) program, is approved for release under Distribution "A" of the Scientific and Tech- nical...Course. Asset Source for Software Engineering Technology (ASSET), National Software Technology Repository. STARS Reuse Concept of Operation. Task US30

  5. Space shuttle orbiter reusable surface insulation flight results

    NASA Technical Reports Server (NTRS)

    Dotts, R. L.; Smith, J. A.; Tillian, D. J.

    1983-01-01

    The first five flights of the orbiter Columbia provided the initial data required to certify the operational performance of the reusable surface insulation (RSI) thermal protection system (TPS). The flight performance characteristics of the RIS TPS are discussed. The discussion is based primarily on postflight inspections and postflight interpretation of the flight instrumentation. TPS modifications of the future orbiters (OV-099, 103, and subs) are also discussed.

  6. Space Shuttle Orbiter - Reusable surface insulation flight performance

    NASA Technical Reports Server (NTRS)

    Dotts, R. L.; Tillian, D. J.; Smith, J. A.

    1982-01-01

    The first two flights of the Space Shuttle Orbiter have provided the initial data required for operational certification of the Thermal Protection System (TPS). The flight performance characteristics of the TPS reusable surface insulation (RSI) will be discussed. The discussion will be based on post-flight inspections of the RSI and post-flight interpretations of the flight instrumentation data. The flights to date indicate that the thermal and mechanical design requirements for the RSI system were met or exceeded.

  7. 3rd and Future Generation Reusable Launch Vehicle (RLV)

    NASA Image and Video Library

    1997-10-01

    This artist’s concept is of the X-33 Advanced Technology Demonstrator, a subscale prototype Reusable Launch Vehicle (RLV), in its 1997 configuration. Named the Venture Star, this vehicle manufactured by Lockheed Martin Skunk Works, is shown in orbit with a deployed payload. The Venture Star was one of the earliest versions of the RLV’s developed in attempt to replace the aging shuttle fleet. The X-33 program has been discontinued.

  8. Self-unloading, unmanned, reusable lunar lander project

    NASA Technical Reports Server (NTRS)

    Cowan, Kevin; Lewis, Ron; Mislinski, Philip; Rivers, Donna; Smith, Solar; Vasicek, Clifford; Verona, Matt

    1991-01-01

    A payload delivery system will be required to support the buildup and operation of a manned lunar base. In response, a self-unloading, unmanned, reusable lunar lander was conceptually designed. The lander will deliver a 7000 kg payload, with the same dimensions as a space station logistics module, from low lunar orbit to any location on the surface of the moon. The technical aspects of the design is introduced as well as the management structure and project cost.

  9. NASA's Reusable Launch Vehicle Technologies: A Composite Materials Overview

    NASA Technical Reports Server (NTRS)

    Clinton, R. G., Jr.; Cook, Steve; Effinger, Mike; Smith, Dennis; Swint, Shayne

    1999-01-01

    A materials overview of the NASA's Earth-to-Orbit Space Transportation Program is presented. The topics discussed are: Earth-to-Orbit Goals and Challenges; Space Transportation Program Structure; Generations of Reusable Launch Vehicles; Space Transportation Derived Requirements; X 34 Demonstrator; Fastrac Engine System; Airframe Systems; Propulsion Systems; Cryotank Structures; Advanced Materials, Fabrication, Manufacturing, & Assembly; Hot and Cooled Airframe Structures; Ceramic Matrix Composites; Ultra-High Temp Polymer Matrix Composites; Metal Matrix Composites; and PMC Lines Ducts and Valves.

  10. A Reusable, Distributed Repository for Configuration Management Policy Programming

    DTIC Science & Technology

    1998-09-01

    A Reusable, Distributed Repository for Configuration Management Policy Programming André van der Hoek, Antonio Carzaniga , Dennis Heimbigner, and...Hoek, Antonio Carzaniga , Dennis Heimbigner, and Alexander L. Wolf ABSTRACT Distributed configuration management is intended to support the activities of...Washington, D.C., 1990. [6] A. Carzaniga . DVS 1.2 Manual. Department of Computer Science, University of Colorado, Boulder, Colorado, June 1998. [7] S.-Y

  11. X-33 Reusable Launch Vehicle Demonstrator, Spaceport and Range

    NASA Technical Reports Server (NTRS)

    Letchworth, Gary F.

    2011-01-01

    The X-33 was a suborbital reusable spaceplane demonstrator, in development from 1996 to early 2001. The intent of the demonstrator was to lower the risk of building and operating a full-scale reusable vehicle fleet. Reusable spaceplanes offered the potential to lower the cost of access to space by an order of magnitude, compared with conventional expendable launch vehicles. Although a cryogenic tank failure during testing ultimately led to the end of the effort, the X-33 team celebrated many successes during the development. This paper summarizes some of the accomplishments and milestones of this X-vehicle program, from the perspective of an engineer who was a member of the team throughout the development. X-33 Program accomplishments include rapid, flight hardware design, subsystem testing and fabrication, aerospike engine development and testing, Flight Operations Center and Operations Control Center ground systems design and construction, rapid Environmental Impact Statement NEPA process approval, Range development and flight plan approval for test flights, and full-scale system concept design and refinement. Lessons from the X-33 Program may have potential application to new RLV and other aerospace systems being developed a decade later.

  12. New reusable elastomer electrodes for assessing body composition

    NASA Astrophysics Data System (ADS)

    Moreno, M.-V.; Chaset, L.; Bittner, P. A.; Barthod, C.; Passard, M.

    2013-04-01

    The development of telemedicine requires finding solutions of reusable electrodes for use in patients' homes. The objective of this study is to evaluate the relevance of reusable elastomer electrodes for measuring body composition. We measured a population of healthy Caucasian (n = 17). A measurement was made with a reference device, the Xitron®, associated with AgCl Gel electrodes (Gel) and another measurement with a multifrequency impedancemeter Z-Metrix® associated with reusable elastomer electrodes (Elast). We obtained a low variability with an average error of repeatability of 0.39% for Re and 0.32% for Rinf. There is a non significantly difference (P T-test > 0.1) about 200 ml between extracellular water Ve measured with Gel and Elast in supine and in standing position. For total body water Vt, we note a non significantly difference (P T-test > 0.1) about 100 ml and 2.2 1 respectively in supine and standing position. The results give low dispersion, with R2 superior to 0.90, with a 1.5% maximal error between Gel and Elast on Ve in standing position. It looks possible, taking a few precautions, using elastomer electrodes for assessing body composition.

  13. Operations Analysis of the 2nd Generation Reusable Launch Vehicle

    NASA Technical Reports Server (NTRS)

    Noneman, Steven R.; Smith, C. A. (Technical Monitor)

    2002-01-01

    The Space Launch Initiative (SLI) program is developing a second-generation reusable launch vehicle. The program goals include lowering the risk of loss of crew to 1 in 10,000 and reducing annual operations cost to one third of the cost of the Space Shuttle. The SLI missions include NASA, military and commercial satellite launches and crew and cargo launches to the space station. The SLI operations analyses provide an assessment of the operational support and infrastructure needed to operate candidate system architectures. Measures of the operability are estimated (i.e. system dependability, responsiveness, and efficiency). Operations analysis is used to determine the impact of specific technologies on operations. A conceptual path to reducing annual operations costs by two thirds is based on key design characteristics, such as reusability, and improved processes lowering labor costs. New operations risks can be expected to emerge. They can be mitigated with effective risk management with careful identification, assignment, tracking, and closure. SLI design characteristics such as nearly full reusability, high reliability, advanced automation, and lowered maintenance and servicing coupled with improved processes are contributors to operability and large operating cost reductions.

  14. RAMS approach for reusable launch vehicle advanced studies

    NASA Astrophysics Data System (ADS)

    Tatry, PH.; Deneu, F.; Simonotti, J. L.

    The emerging of reusable single stage to orbit concept as credible launchers in the turn of the century is changing some technical and technological approaches in the way of doing future launcher advanced studies. Among others (such as operations through the "aircraft-like operations" concept), the RAMS approach (reliability, availability, maintainability and safety) has to be implemented from the very beginning of a concept study, especially for the SSTOs ones in order to meet the "able" requirements (affordable, reusable, reliable, available and operable). Beyond the "traditional" considerations applied to expendable launchers and/or man rated space transportation systems, the RAMS involvement in reusable launcher advanced studies and concept trade-offs must allow to perform the best balance between costs, performance and related risks. For instance, in the framework of SSTOs key technologies identification studies performed at Aerospatiale, the RAMS have been involved from the beginning of the preliminary design task. This approach has shown that the assessment of the main propulsion failure risks and associated probabilities of occurrence have strongly affected the vehicle design within the mission management and technical aspects such as main propulsion specifications, ascent trajectory shaping and landing phase scenario (VTOVL configuration). This paper intends to describe this RAMS approach and addresses how it has been applied on trade-off on VTOVL concept.

  15. Biomass-derived nitrogen self-doped porous carbon as effective metal-free catalysts for oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Liu, Xiaojun; Zhou, Yucheng; Zhou, Weijia; Li, Ligui; Huang, Shaobin; Chen, Shaowei

    2015-03-01

    Biomass-derived nitrogen self-doped porous carbon was synthesized by a facile procedure based on simple pyrolysis of water hyacinth (eichhornia crassipes) at controlled temperatures (600-800 °C) with ZnCl2 as an activation reagent. The obtained porous carbon exhibited a BET surface area up to 950.6 m2 g-1, and various forms of nitrogen (pyridinic, pyrrolic and graphitic) were found to be incorporated into the carbon molecular skeleton. Electrochemical measurements showed that the nitrogen self-doped carbons possessed a high electrocatalytic activity for ORR in alkaline media that was highly comparable to that of commercial 20% Pt/C catalysts. Experimentally, the best performance was identified with the sample prepared at 700 °C, with the onset potential at ca. +0.98 V vs. RHE, that possessed the highest concentrations of pyridinic and graphitic nitrogens among the series. Moreover, the porous carbon catalysts showed excellent long-term stability and much enhanced methanol tolerance, as compared to commercial Pt/C. The performance was also markedly better than or at least comparable to the leading results in the literature based on biomass-derived carbon catalysts for ORR. The results suggested a promising route based on economical and sustainable biomass towards the development and engineering of value-added carbon materials as effective metal-free cathode catalysts for alkaline fuel cells.Biomass-derived nitrogen self-doped porous carbon was synthesized by a facile procedure based on simple pyrolysis of water hyacinth (eichhornia crassipes) at controlled temperatures (600-800 °C) with ZnCl2 as an activation reagent. The obtained porous carbon exhibited a BET surface area up to 950.6 m2 g-1, and various forms of nitrogen (pyridinic, pyrrolic and graphitic) were found to be incorporated into the carbon molecular skeleton. Electrochemical measurements showed that the nitrogen self-doped carbons possessed a high electrocatalytic activity for ORR in alkaline media

  16. Fluorine-doped carbon nanotubes as an efficient metal-free catalyst for destruction of organic pollutants in catalytic ozonation.

    PubMed

    Wang, Jing; Chen, Shuo; Quan, Xie; Yu, Hongtao

    2017-09-27

    Metal-free carbon materials have been presented to be potential alternatives to metal-based catalysts for heterogeneous catalytic ozonation, yet the catalytic performance still needs to be enhanced. Doping carbon with non-metallic heteroatoms (e.g., N, B, and F) could alter the electronic structure and electrochemical properties of original carbon materials, has been considered to be an effective method for improving the catalytic activity of carbon materials. Herein, fluorine-doped carbon nanotubes (F-CNTs) were synthesized via a facile method and characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and Raman spectroscopy. The as-synthesized F-CNTs exhibited notably enhanced catalytic activity towards catalytic ozonation for the degradation of organic pollutants. The oxalic acid removal efficiency of optimized F-CNTs was approximately two times as much as that of pristine CNTs, and even exceeded those of four conventional metal-based catalysts (ZnO, Al2O3, Fe2O3, and MnO2). The XPS and Raman studies confirmed that the covalent CF bonds were formed at the sp(3) C sites instead of sp(2) C sites on CNTs, not only resulting in high positive charge density of C atoms adjacent to F atoms, but remaining the delocalized π-system with intact carbon structure of F-CNTs, which then favored the conversion of ozone molecules (O3) into reactive oxygen species (ROS) and contributed to the high oxalic acid removal efficiency. Furthermore, electron spin resonance (ESR) studies revealed that superoxide radicals (O2(-)) and singlet oxygen ((1)O2) might be the dominant ROS that responsible for the degradation of oxalic acid in these catalytic systems. Copyright © 2017 Elsevier Ltd. All rights reserved.

  17. Al- or Si-decorated graphene oxide: A favorable metal-free catalyst for the N2O reduction

    NASA Astrophysics Data System (ADS)

    Esrafili, Mehdi D.; Sharifi, Fahimeh; Nematollahi, Parisa

    2016-11-01

    The structural and catalytic properties of Al- or Si-decorated graphene oxide (Al-/Si-GO) are studied by means of density functional theory calculations. The relatively large adsorption energy together with the small Alsbnd O or Sisbnd O binding distances indicate that the epoxy groups over the GO surface can strongly stabilize the single Al or Si atom. Hence, Al-GO and Si-GO are stable enough to be utilized in catalytic reduction of N2O by CO molecule. It is found that the adsorption and decomposition of N2O molecule over Si-GO is more favorable than over Al-GO, due to its larger adsorption energy (Eads) and charge transfer (qCT) values. On the other hand, the CO molecule is physically adsorbed over both surfaces, with relatively small Eads and qCT values. Therefore, at the presence of N2O and CO molecules as the reaction gas, the Al or Si atom of the surface should be dominantly covered by N2O molecule. Our results indicate that the N2O decomposition process can take place with a negligible activation energy over Al-/Si-GO surface, where the N2 molecule can be easily released from the surface. Then, the activated oxygen atom (Oads) which remains over the surface reacts with the CO molecule to form the CO2 molecule via the reaction Oads + CO → CO2. Based on the calculated activation energies, it is suggested that both Al-GO and Si-GO can be used as an efficient metal-free catalyst for the reduction of N2O molecule at ambient conditions.

  18. N- and S-doped mesoporous carbon as metal-free cathode catalysts for direct biorenewable alcohol fuel cells

    SciTech Connect

    Qiu, Yang; Huo, Jiajie; Jia, Fan; Shanks, Brent. H.; Li, Wenzhen

    2015-11-06

    Nitrogen and sulfur were simultaneously doped into the framework of mesoporous CMK-3 as metal-free catalysts for direct biorenewable alcohol fuel cells. Glucose, NH3, and thiophene were used as carbon, nitrogen and sulfur precursors, respectively, to prepare mesoporous N-S-CMK-3 with uniform mesopores and extra macropores, resulting in good O2 diffusion both in half cell and alcohol fuel cell investigations. Among all investigated CMK-3 based catalysts, N-S-CMK-3 prepared at 800 °C exhibited the highest ORR activity with the onset potential of 0.92 V vs. RHE, Tafel slope of 68 mV dec-1, and 3.96 electron transfer number per oxygen molecule in 0.1 M KOH. In addition, the alkaline membrane-based direct alcohol fuel cell (DAFC) with N-S-CMK-3 cathode displayed 88.2 mW cm-2 peak power density without obvious O2 diffusion issue, reaching 84% initial performance of that with a Pt/C cathode. The high catalyst durability and fuel-crossover tolerance led to stable performance of the N-S-CMK-3 cathode DAFC with 90.6 mW cm-2 peak power density after 2 h operation, while the Pt/C cathode-based DAFC lost 36.9% of its peak power density. In conclusion, the high ORR activity of N-S-CMK-3 can be attributed to the synergistic effect between graphitic-N and S (C–S–C structure), suggesting great potential to use N-S-CMK-3 as an alternative to noble metal catalysts in the fuel cell cathode.

  19. N- and S-doped mesoporous carbon as metal-free cathode catalysts for direct biorenewable alcohol fuel cells

    DOE PAGES

    Qiu, Yang; Huo, Jiajie; Jia, Fan; ...

    2015-11-06

    Nitrogen and sulfur were simultaneously doped into the framework of mesoporous CMK-3 as metal-free catalysts for direct biorenewable alcohol fuel cells. Glucose, NH3, and thiophene were used as carbon, nitrogen and sulfur precursors, respectively, to prepare mesoporous N-S-CMK-3 with uniform mesopores and extra macropores, resulting in good O2 diffusion both in half cell and alcohol fuel cell investigations. Among all investigated CMK-3 based catalysts, N-S-CMK-3 prepared at 800 °C exhibited the highest ORR activity with the onset potential of 0.92 V vs. RHE, Tafel slope of 68 mV dec-1, and 3.96 electron transfer number per oxygen molecule in 0.1 Mmore » KOH. In addition, the alkaline membrane-based direct alcohol fuel cell (DAFC) with N-S-CMK-3 cathode displayed 88.2 mW cm-2 peak power density without obvious O2 diffusion issue, reaching 84% initial performance of that with a Pt/C cathode. The high catalyst durability and fuel-crossover tolerance led to stable performance of the N-S-CMK-3 cathode DAFC with 90.6 mW cm-2 peak power density after 2 h operation, while the Pt/C cathode-based DAFC lost 36.9% of its peak power density. In conclusion, the high ORR activity of N-S-CMK-3 can be attributed to the synergistic effect between graphitic-N and S (C–S–C structure), suggesting great potential to use N-S-CMK-3 as an alternative to noble metal catalysts in the fuel cell cathode.« less

  20. Catalytic amplification based on hole-transporting materials as efficient metal-free electrocatalysts for non-enzymatic glucose sensing.

    PubMed

    Gu, Yue; Yuan, Rongrong; Yan, Xiaoyi; Li, Cong; Liu, Weilu; Chen, Ruixue; Tang, Liu; Zheng, Bo; Li, Yaru; Zhang, Zhiquan; Yang, Ming

    2015-08-19

    Hole-transporting materials with tunable structures and properties are mainly applied in organic light-emitting diodes as transport layer. But their catalytic properties as signal amplifiers in biological assays are seldom reported. In this paper, a starburst molecule, 4,4,4″-tri(N-carbazolyl)-triphenylamine (TCT), containing a triphenylamine as the central core and three carbazoles as the peripheral functional groups was designed and synthesized. Subsequently, the hole-transporting material based on the TCT polymer, poly(TCT) (PTCT), was achieved via a low-cost electrochemical method and exploited as an efficient metal-free electrocatalyst for non-enzymatic glucose detection. Here, this hole-transporting material served three purposes: electrochemical recognition (owing to hydrogen bonding interaction and the biomimetic microenvironment created by the polymer), electrocatalysis (owing to the hole-transporting capability of triphenylamine and the catalytic property of carbazole), and signal amplification (owing to energy migration along the conductive polymer backbone). The electrocatalytic and sensing performances of the sensor based on PTCT were evaluated in detail. Results revealed that the PTCT film could efficiently catalyze the oxidation of glucose at a less-positive potential (+0.20 V) in the absence of any enzymes. The response to glucose was linear in the concentration range of 1.0-6000 μM, and the detection limit was 0.20 μM. With good stability and selectivity, the proposed sensor could be feasibly applied to detect glucose in practical samples. The encouraging sensing performances suggest that the hole-transporting material is one of the promising biomimetic catalysts for electrocatalysis and relevant fields. Copyright © 2015 Elsevier B.V. All rights reserved.

  1. Three-dimensional nitrogen-doped graphene foam as metal-free catalyst for the hydrogenation reduction of p-nitrophenol.

    PubMed

    Liu, Jiangyong; Yan, Xiaodong; Wang, Lixia; Kong, Liming; Jian, Panming

    2017-07-01

    Developing metal-free catalysts for various applications has been the focus of high interest over the past decade, especially aiming to replace the expensive noble metal-based catalysts. Herein, a well-defined three-dimensional nitrogen-doped graphene foam (3D-NGF) is synthesized and employed as a metal-free catalyst for the hydrogenation reduction of p-Nitrophenol to p-Aminophenol. The apparent activation energy is calculated, and the reaction mechanism with 3D-NGF as the catalyst for the hydrogenation reduction of p-Nitrophenol is proposed. Importantly, the 3D-NGF demonstrates high catalytic activity and robust stability. The high activity can be ascribed to the synergistic effect between the nitrogen-doping induced change in electronic property and the 3D foam-like structure.

  2. Nitrogen and sulfur co-doped carbon with three-dimensional ordered macroporosity: An efficient metal-free oxygen reduction catalyst derived from ionic liquid

    NASA Astrophysics Data System (ADS)

    Wu, Hui; Shi, Liang; Lei, Jiaheng; Liu, Dan; Qu, Deyu; Xie, Zhizhong; Du, Xiaodi; Yang, Peng; Hu, Xiaosong; Li, Junsheng; Tang, Haolin

    2016-08-01

    The development of efficient and durable catalyst for oxygen reduction reaction (ORR) is critical for the practical application of proton exchange membrane fuel cell (PEMFC). A novel imidazole based ionic liquid is synthesized in this study and used subsequently for the preparation of a N and S co-doped metal-free catalyst with three dimensional ordered microstructure. The catalyst prepared at 1100 °C showed improved ORR catalytic performance and stability compared to commercial Pt/C catalyst. We demonstrate that the high graphitic N content and high degree of graphitization of the synthesized catalyst is responsible for its superb ORR activity. Our results suggest that the N and S co-doped metal-free catalyst reported here is a promising alternative to traditional ORR catalyst based on noble metal. Furthermore, the current study also demonstrate that importance of morphology engineering in the development of high performance ORR catalyst.

  3. Designing a Highly Active Metal-Free Oxygen Reduction Catalyst in Membrane Electrode Assemblies for Alkaline Fuel Cells: Effects of Pore Size and Doping-Site Position.

    PubMed

    Lee, Seonggyu; Choun, Myounghoon; Ye, Youngjin; Lee, Jaeyoung; Mun, Yeongdong; Kang, Eunae; Hwang, Jongkook; Lee, Young-Ho; Shin, Chae-Ho; Moon, Seung-Hyeon; Kim, Soo-Kil; Lee, Eunsung; Lee, Jinwoo

    2015-08-03

    To promote the oxygen reduction reaction of metal-free catalysts, the introduction of porous structure is considered as a desirable approach because the structure can enhance mass transport and host many catalytic active sites. However, most of the previous studies reported only half-cell characterization; therefore, studies on membrane electrode assembly (MEA) are still insufficient. Furthermore, the effect of doping-site position in the structure has not been investigated. Here, we report the synthesis of highly active metal-free catalysts in MEAs by controlling pore size and doping-site position. Both influence the accessibility of reactants to doping sites, which affects utilization of doping sites and mass-transport properties. Finally, an N,P-codoped ordered mesoporous carbon with a large pore size and precisely controlled doping-site position showed a remarkable on-set potential and produced 70% of the maximum power density obtained using Pt/C.

  4. Synthesis, characterization and electrical properties of peripherally tetra-aldazine substituted novel metal free phthalocyanine and its zinc(II) and nickel(II) complexes.

    PubMed

    Bayrak, Rıza; Dumludağ, Fatih; Akçay, Hakkı Türker; Değirmencioğlu, İsmail

    2013-03-15

    The novel phthalonitrile containing azine segment and its corresponding tetra aldazine substituted metal free- and metallo-phthalocyanines (Zn(II) and Ni(II)) were synthesized and characterized by IR, (1)H NMR, Mass, UV-Vis spectroscopy and elemental analysis and addition to these techniques for substituted phthalonitrile (13)C NMR have been used. In addition, dc and ac electrical properties of the films of these novel phthalocyanines were investigated as a function of temperature (295-523 K) and frequency (40-10(5)Hz). Activation energy values of the films of the phthalocyanines were calculated from straight portions of the Arrhenius plot (lnσ(dc)-1/T curves) as 0.70 eV, 0.93 eV and 0.91 eV for the films of metal free, nickel- and zinc-phthalocyanines, respectively. From impedance spectroscopy measurements, it is observed that bulk resistance decreases with increasing temperature indicating semiconductor property.

  5. Sulfur-doped graphene derived from cycled lithium-sulfur batteries as a metal-free electrocatalyst for the oxygen reduction reaction.

    PubMed

    Ma, Zhaoling; Dou, Shuo; Shen, Anli; Tao, Li; Dai, Liming; Wang, Shuangyin

    2015-02-02

    Heteroatom-doped carbon materials have been extensively investigated as metal-free electrocatalysts to replace commercial Pt/C catalysts in oxygen reduction reactions in fuel cells and Li-air batteries. However, the synthesis of such materials usually involves high temperature or complicated equipment. Graphene-based sulfur composites have been recently developed to prolong the cycling life of Li-S batteries, one of the most attractive energy-storage devices. Given the high cost of graphene, there is significant demand to recycle and reuse graphene from Li-S batteries. Herein, we report a green and cost-effective method to prepare sulfur-doped graphene, achieved by the continuous charge/discharge cycling of graphene-sulfur composites in Li-S batteries. This material was used as a metal-free electrocatalyst for the oxygen reduction reaction and shows better electrocatalytic activity than pristine graphene and better methanol tolerance durability than Pt/C.

  6. Metal-free annulation of arenes with 2-aminopyridine derivatives: the methyl group as a traceless non-chelating directing group.

    PubMed

    Manna, Srimanta; Matcha, Kiran; Antonchick, Andrey P

    2014-07-28

    A novel annulation reaction between 2-aminopyridine derivatives and arenes under metal-free conditions is described. The presented intermolecular transformation provided straightforward access to the important pyrido[1,2-a]benzimidazole scaffold under mild reaction conditions. The unprecedented application of the methyl group of methylbenzenes as a traceless, non-chelating, and highly regioselective directing group is reported. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Surface polyPEGylation of Eu3+ doped luminescent hydroxyapatite nanorods through the combination of ligand exchange and metal free surface initiated atom transfer radical polymerization

    NASA Astrophysics Data System (ADS)

    Zeng, Guangjian; Liu, Meiying; Heng, Chunning; Huang, Qiang; Mao, Liucheng; Huang, Hongye; Hui, Junfeng; Deng, Fengjie; Zhang, Xiaoyong; Wei, Yen

    2017-03-01

    The Eu3+ doped luminescent hydroxyapatite (HAp) nanorods with uniform size and morphology can be synthesized by hydrothermal route. However, these HAp nanorods are coated by hydrophobic oleylamine, which makes them difficult to be dispersed in aqueous solution and impede their biomedical applications. In this work, Eu3+ doped luminescent polymers functionalized HAp nanorods were prepared through the combination of ligand exchange reaction and metal free surface initiated atom transfer radical polymerization (ATRP) method. In this procedure, the amino group functionalized HAp nanorods were first prepared by ligand exchange reaction using adenosine monophosphate (AMP) as ligand. Then the Br-containing initiators (HAp-Br) were introduced onto the surface of HAp-AMP nanorods through the amidation reaction. Finally, polymers functionalized HAp nanorods were prepared by metal free ATRP method using poly(ethylene glycol) methacrylate (PEGMA) as monomer and 10-phenylphenothiazine (PTH) as organic photocatalyst. The properties of these obtained HAp nanocomposites (HAP-polyPEGMA nanorods) were characterized by means of transmission electron microscopy, Fourier transformed infrared spectroscopy, X-ray photoelectron spectroscopy and thermogravimetric analysis in detail. The cell imaging of these HAP-polyPEGMA nanorods was examined using laser scanning confocal microscope to evaluate their biomedical applications. We demonstrated for the first time that hydrophobic luminescent HAp nanorods can be functionalized with polyPEGMA through the combination of ligand exchange reaction and metal free surface initiated ATRP. As compared with the traditional ATRP, the metal free ATRP can overcome the toxic and fluorescence quenching effects of metal catalysts such as copper ions. More importantly, the strategy described in this work should also be utilized for fabrications of many other luminescent polymer nanocomposites due to its good monomer adoptability.

  8. Forming heterojunction: an effective strategy to enhance the photocatalytic efficiency of a new metal-free organic photocatalyst for water splitting

    PubMed Central

    Li, Hengshuai; Hu, Haiquan; Bao, Chunjiang; Guo, Feng; Zhang, Xiaoming; Liu, Xiaobiao; Hua, Juan; Tan, Jie; Wang, Aizhu; Zhou, Hongcai; Yang, Bo; Qu, Yuanyuan; Liu, Xiangdong

    2016-01-01

    Photocatalytic water splitting is a new technology for the conversion and utilization of solar energy and has a potential prospect. One important aspect of enhancing the photocatalytic efficiency is how to improve the electron-hole separation. Up to now, there is still no ideal strategy to improve the electron-hole separation. In this article, for metal-free organic photocatalysts, we propose a good strategy- forming heterojunction, which can effectively improve the electron-hole separation. We provide a metal-free organic photocatalyst g-C12N7H3 for water splitting. The stability of g-C12N7H3 has been investigated, the X-ray diffraction spectra has been simulated. Using first-principles calculations, we have systematically studied the electronic structure, band edge alignment, and optical properties for the g-C12N7H3. The results demonstrated that g-C12N7H3 is a new organocatalyst material for water splitting. In order to enhance the photocatalytic efficiency, we provided four strategies, i.e., multilayer stacking, raising N atoms, forming g-C9N10/g-C12N7H3 heterojunction, and forming graphene/g-C12N7H3 heterojunction. Our research is expected to stimulate experimentalists to further study novel 2D metal-free organic materials as visible light photocatalysts. Our strategies, especially forming heterojunction, will substantially help to enhance the photocatalytic efficiency of metal-free organic photocatalyst. PMID:27470223

  9. Metal-free, direct conversion of α-amino acids into α-keto γ-amino esters for the synthesis of α,γ-peptides.

    PubMed

    Hernández, D; Boto, A; Guzmán, D; Alvarez, E

    2017-09-05

    An efficient, metal-free synthesis of unusual α-keto γ-amino esters from α-amino acids is achieved by a radical scission-oxidation-addition of silyloxy acrylates procedure, where no purification of the reaction intermediates is needed. This protocol can be applied to the selective modification of the C-terminal position in peptides to give α,γ-hybrids.

  10. Metal-Free Radical [2+2+1] Carbocyclization of Benzene-Linked 1,n-Enynes: Dual C(sp(3))-H Functionalization Adjacent to a Heteroatom.

    PubMed

    Hu, Ming; Fan, Jian-Hong; Liu, Yu; Ouyang, Xuan-Hui; Song, Ren-Jie; Li, Jin-Heng

    2015-08-10

    A new metal-free oxidative radical [2+2+1] carbocyclization of benzene-linked 1,n-enynes with two C(sp(3))-H bonds adjacent to the same heteroatom is described. This method achieves two C(sp(3))-H oxidative functionalizations and an annulation, thus providing efficient and general access to a variety of fused five-membered carbocyclic hydrocarbons.

  11. Shape-Controlled Metal-Free Catalysts: Facet-Sensitive Catalytic Activity Induced by the Arrangement Pattern of Noncovalent Supramolecular Chains.

    PubMed

    Geng, Guangwei; Chen, Penglei; Guan, Bo; Jiang, Lang; Xu, Zhongfei; Di, Dawei; Tu, Zeyi; Hao, Weichang; Yi, Yuanping; Chen, Chuncheng; Liu, Minghua; Hu, Wenping

    2017-05-23

    Metal-free catalytic materials have recently received broad attention as promising alternatives to metal-involved catalysts. This is owing to their inherent capability to overcome the inevitable limitations of metal-involved catalysts, such as high sensitivity to poisoning, the limited reserves, high cost and scarcity of metals (especially noble metals), etc. However, the lack of shape-controlled metal-free catalysts with well-defined facets is a formidable bottleneck limiting our understandings on the underlying structure-activity relationship at atomic/molecular level, which thereby restrains their rational design. Here, we report that catalytically active crystals of a porphyrin, 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin, could be shaped into well-defined cubes and sheet-like tetradecahedrons (TDHD), which are exclusively and predominantly enclosed by {101} and {001} facets, respectively. Fascinatingly, compared to the cubes, the TDHDs display substantially enhanced catalytic activity toward water decontamination under visible-light irradiation, although both the architectures have identical crystalline structure. We disclose that such interesting shape-sensitive catalytic activity is ascribed to the distinct spatial separation efficiency of photogenerated electrons and holes induced by single-channel and multichannel charge transport pathways along noncovalent supramolecular chains, which are arranged as parallel-aligned and 2D network patterns, respectively. Our findings provide an ideal scientific platform to guide the rational design of next-generation metal-free catalysts of desired catalytic performances.

  12. Green Synthesis of InP/ZnS Core/Shell Quantum Dots for Application in Heavy-Metal-Free Light-Emitting Diodes.

    PubMed

    Kuo, Tsung-Rong; Hung, Shih-Ting; Lin, Yen-Ting; Chou, Tzu-Lin; Kuo, Ming-Cheng; Kuo, Ya-Pei; Chen, Chia-Chun

    2017-09-19

    Quantum dot light-emitting diodes (QD-LEDs) have been considered as potential display technologies with the characterizations of high color purity, flexibility, transparency, and cost efficiency. For the practical applications, the development of heavy-metal-free QD-LEDs from environment-friendly materials is the most important issue to reduce the impacts on human health and environmental pollution. In this work, heavy-metal-free InP/ZnS core/shell QDs with different fluorescence were prepared by green synthesis method with low cost, safe, and environment-friendly precursors. The InP/ZnS core/shell QDs with maximum fluorescence peak at ~ 530 nm, superior fluorescence quantum yield of 60.1%, and full width at half maximum of 55 nm were applied as an emission layer to fabricate multilayered QD-LEDs. The multilayered InP/ZnS core/shell QD-LEDs showed the turn-on voltage at ~ 5 V, the highest luminance (160 cd/m(2)) at 12 V, and the external quantum efficiency of 0.223% at 6.7 V. Overall, the multilayered InP/ZnS core/shell QD-LEDs reveal potential to be the heavy-metal-free QD-LEDs for future display applications.

  13. Picosecond spectroscopic studies of equilibrium structural fluctuations of native and partially unfolded states of Zinc II-substituted and metal-free cytochromes C

    NASA Astrophysics Data System (ADS)

    Tripathy, Jagnyaseni

    Picosecond time-resolved fluorescence spectroscopy was employed to characterize the equilibrium and non-equilibrium protein structural fluctuations in Zn II-substituted (ZnCytc) and metal-free (fbCytc) cytochromes c using dynamic fluorescence Stokes shift (FSS) and fluorescence anisotropy (FA) measurements. The intrinsic porphyrin chromophore is used as the probe for the structural fluctuations of the surrounding protein and solvent. The FSS experiments examine how the time scales detected from the dynamic solvation of a chromoprotein report changes in the character of motion. ZnCytc and fbCytc serve as limited, single-chromophore models for photosynthetic reaction center and light-harvesting proteins. The dynamic solvation of redox and light-harvesting chromophores in photosynthesis plays an important role in the quantum efficiency of electron transfer and energy transfer performed by these systems, respectively. The FSS response function of fbCytc in water is biexponential over the 100-ps--50-ns regime and the two time constants are 1.4 ns and 9.1 ns. ZnCytc under similar solution conditions shows a biexponential FSS response but with time constants of 0.2 ns and 1.5 ns. The two correlation times from the FSS response function correspond to motions of the hydrophobic core and the solvent-contact layer, respectively. Both FSS correlation times were lengthened and the solvation reorganization energy was reduced from 43 cm-1 to 33 cm-1 in the presence of 50% (v/v) glycerol. A Brownian diffusion model with thermally activated barrier crossings on the protein-folding energy landscape is used to interpret these results. The conclusion is that the mean-squared deviations of the fluctuations exhibited by fbCytc are perhaps a factor of ten larger than those in ZnCytc, which is consistent with the suggestion that fbCytc assumes a dynamic, partially unfolded structure with some of the characteristics of a molten globule. The nature of the motion associated with the

  14. Initial experience and evaluation of reusable insulin pen devices among patients with diabetes in emerging countries.

    PubMed

    Tschiedel, Balduino; Almeida, Oscar; Redfearn, Jennifer; Flacke, Frank

    2014-12-01

    Many individuals with type 2 diabetes in emerging countries are transitioning from vial-and-syringe insulin delivery to that of insulin pens (disposable or reusable). As with all insulin delivery methods, patient preferences and comfort are of utmost importance to optimize adherence to treatment. Patient-preferred characteristics for reusable insulin pens and barriers to appropriate injection, particularly in these regions, have not been widely reported in the clinical literature, highlighting a key information gap for clinicians considering these methods as part of a comprehensive diabetes management approach. Face-to-face interviews were conducted with people with type 1/2 diabetes, including insulin-naïve and established insulin users. After moderator demonstration, participants were evaluated on their ability to perform a six-step process to inject a 10-unit dose into a pad with the AllStar(®) (AS; Sanofi, Mumbai, India), HumaPen Ergo II(®) (HE2; Eli Lilly, Indianapolis, USA), and NovoPen 4(®) (NP4; Novo Nordisk, Bagsværd, Denmark) pens. Local pens were also tested in India, China and Brazil. A total of 503 people from India, Malaysia, Brazil, Egypt, and China participated. Participants completed the six-step process in an average, 2-3 min per pen. Participants ranked ease of overall use and ease of self-injection and dialing/reading dose as most important features for new insulin pens. When using the pens, the most difficult step was priming/safety testing, with 7-12% failing and 28-40% having difficulty; 6%, 18%, and 22% failed to hold the injection button down for the required period of time using AS, NP4, and HE2, respectively. Participants ranked AS significantly higher for nine of 12 ease-of-use features including three of the top four features considered the most important for reusable pens, while HE2 was ranked higher for two features. Local pens were ranked lowest. Priming the pen and injecting the dose imparted most difficulty for people with

  15. Electron paramagnetic resonance of the excited triplet state of metal-free and metal-substituted cytochrome c.

    PubMed Central

    Angiolillo, P J; Vanderkooi, J M

    1995-01-01

    The photoactivated metastable triplate states of the porphyrin (free-base, i.e., metal-free) zinc and tin derivatives of horse cytochrome c were investigated using electron paramagnetic resonance. Zero-field splitting parameters, line shape, and Jahn-Teller distortion in the temperature range 3.8-150 K are discussed in terms of porphyrin-protein interactions. The zero-field splitting parameters D for the free-base, Zn and Sn derivatives are 465 x 10(-4), 342 x 10(-4) and 353 x 10(-4) cm-1, respectively, and are temperature invariant over the temperature ranges studied. AN E value at 4 K of 73 x 10(-4) cm-1 was obtained for Zn cytochrome c, larger than any previously found for Zn porphyrins derivatives of hemeproteins, showing that the heme site of cytochrome c imposes an asymmetric field. Though the E value for Zn cytochrome c is large, the geometry of the site appears quite constrained, as indicated by a spectral line shape showing a single species. Intersystem crossing occurred predominantly to the T2 > zero-field spin sublevel. EPR line shape changes with respect to temperature of Zn cyt c are interpreted in terms of vibronic coupling, and a maximum Jahn-Teller crystal-field splitting of approximately 180 cm-1 is obtained. Sn cytochrome c in comparison with the Zn protein exhibits a photoactivated triplet line shape that is less well resolved in the X-Y region. The magnitude of E value is approximately 60 x 10(-4) cm-1 at 4 K; its value rapidly tends toward zero with increasing temperature, from which a value for the Jahn-Teller crystal-field splitting of > or = 40 cm-1 is estimated. In contrast to those for the metal cytochromes, the magnitude of E value for the free-base derivative was essentially zero at all temperatures studied. This finding is discussed as a consequence of an excited-state tautomerization process that occurs even at 4 K. PMID:7647253

  16. Historical problem areas: Lessons learned for expendable and reusable vehicle propulsion systems

    NASA Technical Reports Server (NTRS)

    Fester, Dale A.

    1991-01-01

    The following subject areas are covered: expendable launch vehicle lessons learned, upper stage/transfer vehicle lessons learned, shuttle systems - reuse, and reusable system issues and lessons learned.

  17. Structural Integrity and Durability of Reusable Space Propulsion Systems

    NASA Technical Reports Server (NTRS)

    1991-01-01

    A two-day conference on the structural integrity and durability of reusable space propulsion systems was held on 14 to 15 May 1991 at the NASA Lewis Research Center. Presentations were made by industry, university, and government researchers organized into four sessions: (1) aerothermodynamic loads; (2) instrumentation; (3) fatigue, fracture, and constitutive modeling; and (4) structural dynamics. The principle objectives were to disseminate research results and future plans in each of four areas. This publication contains extended abstracts and the visual material presented during the conference. Particular emphasis is placed on the Space Shuttle Main Engine (SSME) and the SSME turbopump.

  18. A reusable suture anchor for arthroscopy psychomotor skills training.

    PubMed

    Tillett, Edward D; Rogers, Rainie; Nyland, John

    2003-03-01

    For residents to adequately develop the early arthroscopy psychomotor skills required to better learn how to manage the improvisational situations they will encounter during actual patient cases, they need to experience sufficient practice repetitions within a contextually relevant environment. Unfortunately, the cost of suture anchors can be a practice repetition-limiting factor in learning arthroscopic knot-tying techniques. We describe a technique for creating inexpensive reusable suture anchors and provide an example of their application to repair the anterior glenoid labrum during an arthroscopy psychomotor skills laboratory training session.

  19. Technology Maturity Towards Highly Reusable Space Transportation Goals

    NASA Technical Reports Server (NTRS)

    Lyles, Garry

    1999-01-01

    The National Aeronautics and Space Administration's (NASA) Advanced Space Transportation Program (ASTP) has advanced key propulsion and launch vehicle systems technologies towards enabling the concepts identified by the Highly Reusable Space Transportation (HRST) Study as having significant potential for reducing the cost of access to space. The Marshall Space Flight Center (MSFC) manages the ASTP for the NASA Aero-Space Technology Enterprise. The HRST Study was conducted from 1995 through 1997 to evaluated launch concepts with the potential to reduce launch cost to $100 to $200 per pound of payload to low Earth orbit in the 2016 to 2022 timeframe. The HRST represents a generation of launch vehicles beyond the Lockheed-Martin VentureStar concept with a goal of another factor of ten reduction in launch cost below the next generation Reusable Launch Vehicle. Several concepts were developed and evaluated during the initial HRST studies. At the completion of the concept development phase in 1997, four task forces were formed to integrate the results of the study. These task forces were System Concept Definition, Operations Assessment. Cost Assessment and Technology Assessment. The Operations Assessment task force published its final report in November 1998. The Operations Assessment task force evaluated both single stage to orbit (SSTO) and two-stage to orbit (TSTO) concepts. SSTO concepts included horizontal takeoff and horizontal landing, vertical takeoff and vertical landing and vertical takeoff and horizontal landing. Horizontally launched concepts including launch assist options. SSTO concepts included airbreathing and all rocket as well as combination propulsion systems. The Operations Assessment considered the significance of performance margin, flight rate capability, reliability, launch assist, design optimization and technology development. These studies serve as a guide for the ASTP to prioritize technology development towards future highly reusable launch

  20. Aircraft Dynamic Modes of a Winged Reusable Rocket Plane (Preprint)

    DTIC Science & Technology

    2013-09-01

    response times for the dynamic modes of a winged reusable rocket plane. The vehicle used in this effort was XCOR Aerospace’s Lynx , which is being...dynamic aerodynamics of the Lynx . These inputs were then feed into the “A” matrix of the state space version of the equations of motion. 15. SUBJECT...was XCOR Aerospace’s Lynx which is being developed for the sub-orbital space tourism and microgravity payload market. The effort utilized CART3D and