Dissolution of Uranium(IV) Oxide in Solutions of Ammonium Carbonate and Hydrogen Peroxide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Smith, Steven C.; Peper, Shane M.; Douglas, Matthew

2009-09-12

Understanding the dissolution characteristics of uranium oxides is of fundamental scientific interest. Bench scale experiments were conducted to determine the optimal dissolution parameters of uranium(IV) oxide (UO2) powder in solutions of ammonium carbonate [(NH4)2CO3] and hydrogen peroxide (H2O2). Experimental parameters included variable peroxide and carbonate concentrations, and temperature. Results indicate the dissolution rate of UO2 in 1 M (NH4)2CO3 increases linearly with peroxide concentration ranging from 0.05 – 2 M (1:1 to 40:1 mol ratio H2O2:U), with no apparent maximum rate reached under the limited conditions used in our study. Temperature ranging studies show the dissolution rate of UO2 inmore » 1 M (NH4)2CO3 and 0.1 M H2O2 (2:1 mol ratio H2O2:U) increases linearly from 15 °C to 60 °C, again with no apparent maximum rate reached. Dissolution of UO2 in solutions with constant [H2O2] and [(NH4)2CO3] ranging from 0.5 to 2 M showed no difference in rate; however dissolution was significantly reduced in 0.05 M (NH4)2CO3 solution. The results of this study demonstrate the influence of [H2O2], [(NH4)2CO3], and temperature on the dissolution of UO2 in peroxide-containing (NH4)2CO3 solutions. Future studies are planned to elucidate the solution and solid state complexes in these systems.« less

Highly tunable porous organic polymer (POP) supports for metallocene-based ethylene polymerization

NASA Astrophysics Data System (ADS)

Wang, Xiong; Li, Zhenyou; Han, Xiaoyu; Han, Zhengang; Bai, Yongxiao

2017-10-01

Porous organic Polymers (POPs) can not only exhibit high specific surface area and pore volume, but also tunable pore size distribution. Herein, copolymers of 2-hydroxyethylmethylacrylate (HEMA) and divinylbenzene (DVB) with specific pore structure were synthesized via a dispersion polymerization strategy, and then immobilized metallocene catalysts with well-defined pore structure were obtained on the produced POP supports. The nitrogen sorption and Gel permeation chromatography (GPC) results demonstrate that the pore structure of the immobilized metallocene catalyst is highly dependent on the pore structure of the POPs, and the pore structure of metallocene catalysts or the POPs has a significant influence on the molecular chain growth of the produced polyethylene. By tuning the distribution of the active species scattered in the micro- and the narrow meso-pore range (roughly ≤4 nm), the chain growth of the polyolefin can be tailored effectively during the polymerization process, although differential scanning calorimetry (DSC) and temperature rising elution fractionation (TREF) results show that the chemical composition distributions (CCDs) of produced PE from the POPs-supported metallocene catalysts are not determined by polymerization activity or molecule chain length, but mainly by the active site species scattered in the supported catalysts. Scanning electron micrograph (SEM) shows that the produced polyethylene has highly porous fabric which consists of nanofiber and spherical beads of micron dimension.

Metallocenes--The First 25 Years

ERIC Educational Resources Information Center

Hunt, C. B.

1977-01-01

This article reviews the discovery of the first of the metallocenes and some of the developments which have taken place in the 25 years following. Applications to topics such as the solution of the polyphenylchromium problem and Alkene polymerisation, are discussed. Ferrocene is studied in detail. (MA)

Metallocene Catalytic Insertion Polymerization of 1-Silene to Polycarbosilanes

NASA Astrophysics Data System (ADS)

Tian, Yuelong; Ge, Min; Zhang, Weigang; Lv, Xiaoxu; Yu, Shouquan

2015-11-01

Metallocene of zirconium were used as a catalyst for an insertion polymerization of 1-methylsilene directly into pre-ceramic precursor polyzirconocenecarbosilane (PZCS) during dechlorination of dichlorodimethylesilane by sodium, which exhibits high catalytic effectiveness with the maximum conversion ratio of polycarbosilane up to 91%. The average molecular weights of polymers synthesized are less than 1400, all with very narrow polymolecularities. The mechanism of catalytic polymerization was assumed to be similar to a coordination insertion polymerization of 1-olefins by metallocenes. The obtained PZCS show high ceramic yields with formation of composite ceramics of ZrC-SiC, which are novel polymeric precursors of ultra-high temperature ceramic (UHTC) fiber and composite.

Metallocene Catalytic Insertion Polymerization of 1-Silene to Polycarbosilanes.

PubMed

Tian, Yuelong; Ge, Min; Zhang, Weigang; Lv, Xiaoxu; Yu, Shouquan

2015-11-06

Metallocene of zirconium were used as a catalyst for an insertion polymerization of 1-methylsilene directly into pre-ceramic precursor polyzirconocenecarbosilane (PZCS) during dechlorination of dichlorodimethylesilane by sodium, which exhibits high catalytic effectiveness with the maximum conversion ratio of polycarbosilane up to 91%. The average molecular weights of polymers synthesized are less than 1400, all with very narrow polymolecularities. The mechanism of catalytic polymerization was assumed to be similar to a coordination insertion polymerization of 1-olefins by metallocenes. The obtained PZCS show high ceramic yields with formation of composite ceramics of ZrC-SiC, which are novel polymeric precursors of ultra-high temperature ceramic (UHTC) fiber and composite.

On the Discovery, Biological Effects, and Use of Cisplatin and Metallocenes in Anticancer Chemotherapy

PubMed Central

Gómez-Ruiz, Santiago; Maksimović-Ivanić, Danijela; Mijatović, Sanja; Kaluđerović, Goran N.

2012-01-01

The purpose of this paper is to summarize mode of action of cisplatin on the tumor cells, a brief outlook on the metallocene compounds as antitumor drugs as well as the future tendencies for the use of the latter in anticancer chemotherapy. Molecular mechanisms of cisplatin interaction with DNA, DNA repair mechanisms, and cellular proteins are discussed. Molecular background of the sensitivity and resistance to cisplatin, as well as its influence on the efficacy of the antitumor immune response was evaluated. Furthermore, herein are summarized some metallocenes (titanocene, vanadocene, molybdocene, ferrocene, and zirconocene) with high antitumor activity. PMID:22844263

Preparation, characterization, and catalytic activity of zirconocene bridged on surface of silica gel

NASA Astrophysics Data System (ADS)

El Majdoub, Lotfia; Shi, Yasai; Yuan, Yuan; Zhou, Annan; Abutartour, Abubaker; Xu, Qinghong

2015-10-01

Zirconocene catalyst supported on silica gel was prepared for olefin polymerization by surface modification of calcined silica with SiCl4, and the reaction between the modified silica and cyclopentadienyl sodium and ZrCl4. The catalyst was characterized by using Fourier-transform infrared (FT-IR) spectrometer, thermogravimetric (TG), and differential scanning calorimetric (DSC) analytic spectrometer. It was found that the metallocene structure could be formed and connected on silica surface by chemical bond. Initial catalytic tests showed that the supported metallocene was catalytically active (methylaluminoxane as a cocatalyst), producing polymer with higher molecular weight than the metallocene just immobilized on the surface of silica gel.

Rhodium-catalyzed enantioselective intramolecular C-H silylation for the syntheses of planar-chiral metallocene siloles.

PubMed

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

2015-06-01

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

Facile Reductive Silylation of UO22+ to Uranium(IV) Chloride.

PubMed

Kiernicki, John J; Zeller, Matthias; Bart, Suzanne C

2017-01-19

General reductive silylation of the UO 2 2+ cation occurs readily in a one-pot, two-step stoichiometric reaction at room temperature to form uranium(IV) siloxides. Addition of two equivalents of an alkylating reagent to UO 2 X 2 (L) 2 (X=Cl, Br, I, OTf; L=triphenylphosphine oxide, 2,2'-bipyridyl) followed by two equivalents of a silyl (pseudo)halide, R 3 Si-X (R=aryl, alkyl, H; X=Cl, Br, I, OTf, SPh), cleanly affords (R 3 SiO) 2 UX 2 (L) 2 in high yields. Support is included for the key step in the process, reduction of U VI to U V . This procedure is applicable to a wide range of commercially available uranyl salts, silyl halides, and alkylating reagents. Under this protocol, one equivalent of SiCl 4 or two equivalents of Me 2 SiCl 2 results in direct conversion of the uranyl to uranium(IV) tetrachloride. Full spectroscopic and structural characterization of the siloxide products is reported. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Metallocene catalyst containing bulky organic group

DOEpatents

Marks, T.J.; Ja, L.; Yang, X.

1996-03-26

An ionic metallocene catalyst for olefin polymerization which comprises: (1) a cyclopentadienyl-type ligand, a Group IVB transition metal, and alkyl, aryl, or hydride substituents, as a cation, and (2) a weakly coordinating anion comprising boron substituted with halogenated, such as tetrafluoro-aryl substituents preferably containing silylalkyl substitution, such as para-silyl t-butyldimethyl.

Synthesis and Characterization of Cerium(IV) Metallocenes

DOE PAGES

Sutton, Andrew; Clark, David Lewis; Scott, Brian Lindley; ...

2015-12-11

In this study, by applying a salt metathesis approach between Ce(OtBu 3) 2(NO 3) 2(THF) 2 and the potassium salts of mono- and ditrimethylsilyl substituted cyclopentadienes, we were able to isolate two new Ce(IV) metallocenes, including to the best of our knowledge, the first structurally characterized bis-cyclopentadiene Ce(IV) compound.

Metallocene catalyst containing bulky organic group

DOEpatents

Marks, Tobin J.; Ja, Li; Yang, Xinmin

1996-03-26

An ionic metallocene catalyst for olefin polymerization which comprises: (1) a cyclopentadienyl-type ligand, a Group IVB transition metal, and alkyl, aryl, or hydride substituents, as a cation, and (2) a weakly coordinating anion comprising boron substituted with halogenated, such as tetra fluoro, aryl substituents preferably containing silylalkyl substitution, such as para-silyl t-butyldimethyl.

Specific Interactions of Antitumor Metallocenes with Deoxydinucleoside Monophosphates

NASA Astrophysics Data System (ADS)

Eberle, Rahel P.; Hari, Yvonne; Schürch, Stefan

2017-09-01

Bent metallocenes Cp2MCl2 (M = Ti, V, Nb, Mo) are known to exhibit cytotoxic activity against a variety of cancer types. Though the mechanism of action is not fully understood yet, the accumulation of the metal ions in the nucleus points towards DNA as one of the primary targets. A set of eight deoxydinucleoside monophosphates was used to study the adduct yields with metallocenes and cisplatin. The binding affinities are reflected by the relative intensities of the adducts and were found to follow the order of Pt > V > Ti > Mo (no adducts were detected with Nb). High-resolution tandem mass spectrometry was applied to locate the binding patterns in the deoxydinucleoside monophosphates. Whereas cisplatin binds to the soft nitrogen atoms in the purine nucleobases, the metallocenes additionally interact with the hard phosphate oxygen, which is in good agreement with the hard and soft (Lewis) acids and bases (HSAB) concept. However, the binding specificities were found to be unique for each metallocene. The hard Lewis acids titanium and vanadium predominantly bind to the deprotonated phosphate oxygen, whereas molybdenum, an intermediate Lewis acid, preferentially interacts with the nucleobases. Nucleobases comprise alternative binding sites for titanium and vanadium, presumably oxygen atoms for the first and nitrogen atoms for the latter. In summary, the intrinsic binding behavior of the different metallodrugs is reflected by the gas-phase dissociation of the adducts. Consequently, MS/MS can provide insights into therapeutically relevant interactions between metallodrugs and their cellular targets. [Figure not available: see fulltext.

Quantum transport of the single metallocene molecule

NASA Astrophysics Data System (ADS)

Yu, Jing-Xin; Chang, Jing; Wei, Rong-Kai; Liu, Xiu-Ying; Li, Xiao-Dong

2016-10-01

The Quantum transport of three single metallocene molecule is investigated by performing theoretical calculations using the non-equilibrium Green's function method combined with density functional theory. We find that the three metallocen molecules structure become stretched along the transport direction, the distance between two Cp rings longer than the other theory and experiment results. The lager conductance is found in nickelocene molecule, the main transmission channel is the electron coupling between molecule and the electrodes is through the Ni dxz and dyz orbitals and the s, dxz, dyz of gold. This is also confirmed by the highest occupied molecular orbital resonance at Fermi level. In addition, negative differential resistance effect is found in the ferrocene, cobaltocene molecules, this is also closely related with the evolution of the transmission spectrum under applied bias.

Activation of C-H bonds by rare-earth metallocene-butyl complexes.

PubMed

Grindell, Richard; Day, Benjamin M; Guo, Fu-Sheng; Pugh, Thomas; Layfield, Richard A

2017-09-05

The stable metallocene-butyl complexes [(Cp Me ) 2 M( n Bu)] 2 (M = Y, Dy) were synthesized and their reactivity towards to ferrocene and bulky N-heterocyclic carbenes investigated. Selective mono-deprotonation of ferrocene and a benzylic methyl group of IMes were observed, whereas a control reaction of (Cp Me ) 3 M with IMes resulted in a normal-to-abnormal NHC rearrangement.

Metallocene Antimalarials: The Continuing Quest

PubMed Central

Blackie, Margaret A. L.; Chibale, Kelly

2008-01-01

Over the last decade, a significant body of research has been developed around the inclusion of a metallocene moiety into known antimalarial compounds. Ferroquine is the most successful of these compounds. Herein, we describe our contribution to metallocene antimalarials. Our approach has sought to introduce diversity sites in the side chain of ferroquine in order to develop a series of ferroquine derivatives. The replacement of the ferrocenyl moiety with ruthenocene has given rise to ruthenoquine and a modest series of analogues. The reaction of ferroquine and selected analogues with Au(PPh3)NO3, Au(C6F5)(tht), and [Rh(COD)Cl2] has resulted in a series of heterobimetallic derivatives. In all cases, compounds have been evaluated for in vitro antiplasmodial activity in both chloroquine-sensitive and chloroquine-resistant strains of Plasmodium falciparum. Preliminary structure-activity relationships have been delineated. PMID:18274662

Efficient palladium-catalyzed asymmetric allylic alkylation of ketones and aldehydes.

PubMed

Zhao, Xiaohu; Liu, Delong; Xie, Fang; Liu, Yangang; Zhang, Wanbin

2011-03-21

Palladium-catalyzed asymmetric allylic alkylation of ketones, via enamines generated in situ as nucleophiles, were carried out smoothly with chiral metallocene-based P,N-ligands. Under the same conditions, however, reactions of aldehydes could hardly be observed. Subsequently, this obstacle was resolved by using chiral metallocene-based P,P-ligands. Both ketones and aldehydes afforded excellent enantioselectivities with up to 98% ee and 94% ee, respectively.

Synthesis, characterization and photophysical properties of ferrocenyl and mixed sandwich cobaltocenyl ester linked meso-triaryl corrole dyads

NASA Astrophysics Data System (ADS)

Achary, B. Shivaprasad; Ramya, A. R.; Trivedi, Rajiv; Bangal, P. R.; Giribabu, L.

We report here the design and synthesis of corrole-metallocene dyads consisting of a metallocene (either ferrocene (Dyad 1) or mixed sandwich η5-[C5H4(COOH)]Co(η4-C4Ph4) (Dyad 2)) connected via an ester linkage at meso phenyl position. Both the dyads were characterized by 1H NMR, MALDI-TOF, UV-visible, fluorescence spectroscopies (steady-state, picosecond time-resolved), femtosecond transient absorption spectroscopy (fs-TA) and electrochemical methods. The absorption spectra of these dyads showed slight broadening and splitting of the Soret band that indicates a weak ground state interaction between the corrole macrocycle and metallocene part of the present donor-acceptor (D-A) system. However, in both the dyad systems, fluorescence emission of the corrole was quenched in polar solvents as compared to its parent compound 10-(4-hydroxyphenyl)-5,15-bis-(pentafluorophenyl ) corrole (Ph-Corr). The quenching was more pronounced in ferrocene derivatives than in cobaltocenyl derivatives. Transient absorption studies confirm the absence of photoinduced electron transfer from metallocene to correl for these dyad systems and the quenching of singlet state of corrole is found to enhance intersystem crossing due to heavy atom effect. Corrole-ferrocene and corrole-mixed sandwich η5-[C5H4(COOH)]Co(η4-C4Ph4) dyads have been designed, synthesized and characterized by various spectroscopic techniques. Emission intensitiy of both dyads were quenched in polar solvents whereas transient absorption studies indicates that the quenching coule be due to the heavy atom effect.

The use of functionalized zirconocenes as precursors to silica-supported zirconocene olefin polymerization catalysts

NASA Astrophysics Data System (ADS)

Cheng, Xu

2001-07-01

Me3Si substituents adjacent to Cp2MCl2 (M = Ti, Zr, Hf) are converted to BrMe2Si groups using BBr 3. The high reactivity of the Si-Br bonds toward nucleophiles such as water suggested that these substituents could react with hydroxylated silica surfaces, immobilizing the metallocenes. This dissertation concerns the syntheses of electrophile-functionalized zirconocene dihalide complexes and their use as precursors to silica-supported metallocene olefin polymerization catalysts. First we extended the metallocene "functionalization" chemistry to obtain substituents bearing more than one electrophilic bond. (Me3Sn) 2C5H4 combined with CpZrCl3 in toluene to afford (eta5-Me3Sn-C5H4)CpZrCl 2 (A). Reactions of A with electrophiles (E-X = Cl2B-Cl, I-Cl, and I-I) afforded (eta5-XMe 2Sn-C5H4)CpZrCl2 (and E-Me) cleanly. The reaction of A with BBr3 afforded either (eta5-BrMe2Sn-C5H4)CpZrBr2 (25 °C, 10 min) or (eta5-Br2MeSn-C5H 4)CpZrBr2 (25 °C, 15 h). Ph2MeSi-C5H 4Li combined with ZrCl4•2THF to afford (eta 5-Ph2MeSi-C5H4)2ZrCl 2 (B). The reaction of B with BCl3 led to incomplete cleavage of the Ph-Si bonds, however treatment of B with BBr3 afforded (eta5-Br2MeSi-C 5H4)2ZrBr2 (C) efficiently. X-ray crystal structures of (eta5-ClMe2Sn-C 5H4)CpZrCl2•1/2toluene, (eta 5-Br2MeSn-C5H4)CpZrBr2•THF, B, and C were obtained. Metallocene C reacts with water to afford an oligosiloxane-supported zirconocene dibromide. Spectroscopic characterization suggested a stereoregular structure in which the metallocene units have meso symmetry. The oligomeric substance showed high activity for homogeneous ethylene polymerization. Supported metallocene olefin polymerization catalysts were prepared by combining a functionalized metallocene precursor (Cp2ZrBr 2 bearing either BrMe2Si or Br2MeSi groups) and partially dehydroxylated silica. The activities of the immobilized zirconocene catalysts decreased and the stabilities increased with increasing number of tethers. The immobilized catalyst prepared from (eta5-Br 2MeSi-C5H4)2ZrBr2, which is assumed to form two "double-tethers" to silica, was significantly more active than the catalyst prepared from [eta5-1,3-(BrMe 2Si)2C5H3]2ZrBr2, which is assumed to form four "single-tethers" to silica. Catalyst leaching was observed in all the immobilized zirconocene catalysts. Finally we report model studies on the stability of the Si-O-Si bonds toward methylaluminoxane (MAO). The reaction of (eta5-BrMe 2Si-C5H4)CpZrBr2 with tBuMe 2SiOH results in the formation of Si-O-Si bonds; addition of NEt 3 results in further reaction to afford Si-O-Zr bonds. The reaction of Me3Si-O-SiMe3 with MAO showed that Si-O-Si bonds can be cleaved under the conditions of our polymerization reactions.

Vibrational overtone spectra of metallocenes: effect of the coordinating metal on the CH bond lengths

NASA Astrophysics Data System (ADS)

Billinghurst, Brant E.; Gough, Kathleen M.

2003-03-01

The first through third overtone spectra of ferrocene, ruthenocene, nickelocene, cobaltocene, dicyclopentadienyl magnesium and sodium cyclopentadienyl are examined with particular attention to the CH stretching of the cyclopentadienyl. Using semi-empirical correlations between CH bond length and CH stretching frequencies in each overtone region, we have determined that the type of metal atom within a metallocene complex has little effect on the CH bond length in the cyclopentadienyl. The only exception is cobaltocene where there is evidence that the Jahn-Teller effect results in several different CH bond lengths. Evidence that bis(cyclopentadienyl) magnesium is not ionic has been observed.

Reactivity of uranium(iii) with H2E (E = S, Se, Te): synthesis of a series of mononuclear and dinuclear uranium(iv) hydrochalcogenido complexes.

PubMed

Franke, Sebastian M; Rosenzweig, Michael W; Heinemann, Frank W; Meyer, Karsten

2015-01-01

We report the syntheses, electronic properties, and molecular structures of a series of mono- and dinuclear uranium(iv) hydrochalcogenido complexes supported by the sterically demanding but very flexible, single N-anchored tris(aryloxide) ligand ( Ad ArO) 3 N) 3- . The mononuclear complexes [(( Ad ArO) 3 N)U(DME)(EH)] (E = S, Se, Te) can be obtained from the reaction of the uranium(iii) starting material [(( Ad ArO) 3 N)U III (DME)] in DME via reduction of H 2 E and the elimination of 0.5 equivalents of H 2 . The dinuclear complexes [{(( Ad ArO) 3 N)U} 2 (μ-EH) 2 ] can be obtained by dissolving their mononuclear counterparts in non-coordinating solvents such as benzene. In order to facilitate the work with the highly toxic gases, we created concentrated THF solutions that can be handled using simple glovebox techniques and can be stored at -35 °C for several weeks.

Catalytic activity during copolymerization of ethylene and 1-hexene via mixed TiO2/SiO2-supported MAO with rac-Et[Ind]2ZrCl2 metallocene catalyst.

PubMed

Jongsomjit, Bunjerd; Ngamposri, Sutti; Praserthdam, Piyasan

2005-07-14

Activities during ethylene/1-hexene copolymerization were found to increase using the mixed titania/silica-supported MAO with rac-Et[Ind]2ZrCl2 metallocene catalyst. Energy Dispersive X-ray spectorcopy (EDX) indicated that the titania was apparently located on the outer surface of silica and acted as a spacer to anchor MAO to the silica surface. IR spectra revealed the Si-O-Ti stretching at 980 cm(-1) with low content of titania. The presence of anchored titania resulted in less steric hindrance and less interaction due to supporting effect.

Novel Potent Metallocenes against Liver Stage Malaria

PubMed Central

Matos, Joana; da Cruz, Filipa P.; Cabrita, Élia; Gut, Jiri; Nogueira, Fátima; do Rosário, Virgílio E.; Moreira, Rui; Rosenthal, Philip J.; Prudêncio, Miguel

2012-01-01

Novel conjugates of the antimalarial drug primaquine (compound 1) with ferrocene, named primacenes, have been synthesized and screened for their activities against blood stage and liver stage malaria in vitro and host-vector transmission in vivo. Both transmission-blocking and blood-schizontocidal activities of the parent drug were conserved only in primacenes bearing a basic aliphatic amine group. Liver stage activity did not require this structural feature, and all metallocenes tested were comparable to or better than primaquine in this regard. Remarkably, the replacement of primaquine's aliphatic chain by hexylferrocene, as in compound 7, led to a ∼45-fold-higher level activity against liver stage parasitemia than that of primaquine. PMID:22155838

Morphological, rheological and mechanical characterization of polypropylene nanocomposite blends.

PubMed

Rosales, C; Contreras, V; Matos, M; Perera, R; Villarreal, N; García-López, D; Pastor, J M

2008-04-01

In the present work, the effectiveness of styrene/ethylene-butylene/styrene rubbers grafted with maleic anhydride (MA) and a metallocene polyethylene (mPE) as toughening materials in binary and ternary blends with polypropylene and its nanocomposite as continuous phases was evaluated in terms of transmission electron microscopy (TEM), scanning electron microscopy (SEM), oscillatory shear flow and dynamic mechanical thermal analysis (DMA). The flexural modulus and heat distortion temperature values were determined as well. A metallocene polyethylene and a polyamide-6 were used as dispersed phases in these binary and ternary blends produced via melt blending in a corotating twin-screw extruder. Results showed that the compatibilized blends prepared without clay are tougher than those prepared with the nanocomposite of PP as the matrix phase and no significant changes in shear viscosity, melt elasticity, flexural or storage moduli and heat distortion temperature values were observed between them. However, the binary blend with a nanocomposite of PP as matrix and metallocene polyethylene phase exhibited better toughness, lower shear viscosity, flexural modulus, and heat distortion temperature values than that prepared with polyamide-6 as dispersed phase. These results are related to the degree of clay dispersion in the PP and to the type of morphology developed in the different blends.

Synthesis and use of (perfluoroaryl) fluoro-aluminate anion

DOEpatents

Marks, T.J.; Chen, Y.X.

1998-12-29

A trityl perfluorophenyl alumninate such as tris(2,2{prime},2{double_prime}nonafluorobiphenyl) fluoroaluminate (PBA{sup {minus}}) and its role as a cocatalyst in metallocene-mediated olefin polymerization is disclosed. 4 figs.

Environmental and taxonomic bacterial diversity of anaerobic uranium(IV) bio-oxidation.

PubMed

Weber, Karrie A; Thrash, J Cameron; Van Trump, J Ian; Achenbach, Laurie A; Coates, John D

2011-07-01

Microorganisms in diverse terrestrial surface and subsurface environments can anaerobically catalyze the oxidative dissolution of uraninite. While a limited quantity (∼5 to 12 μmol liter(-1)) of uranium is oxidatively dissolved in pure culture studies, the metabolism is coupled to electron transport, providing the potential of uraninite to support indigenous microbial populations and to solubilize uranium.

Biogenic formation and growth of uraninite (UO₂).

PubMed

Lee, Seung Yeop; Baik, Min Hoon; Choi, Jong Won

2010-11-15

Biogenic UO₂ (uraninite) nanocrystals may be formed as a product of a microbial reduction process in uranium-enriched environments near the Earth's surface. We investigated the size, nanometer-scale structure, and aggregation state of UO₂ formed by iron-reducing bacterium, Shewanella putrefaciens CN32, from a uranium-rich solution. Characterization of biogenic UO₂ precipitates by high-resolution transmission electron microscopy (HRTEM) revealed that the UO₂ nanoparticles formed were highly aggregated by organic polymers. Nearly all of the nanocrystals were networked in more or less 100 nm diameter spherical aggregates that displayed some concentric UO₂ accumulation with heterogeneity. Interestingly, pure UO₂ nanocrystals were piled on one another at several positions via UO₂-UO₂ interactions, which seem to be intimately related to a specific step in the process of growing large single crystals. In the process, calcium that was easily complexed with aqueous uranium(VI) appeared not to be combined with bioreduced uranium(IV), probably due to its lower binding energy. However, when phosphate was added to the system, calcium was found to be easily associated with uranium(IV), forming a new uranium phase, ningyoite. These results will extend the limited knowledge of microbial uraniferous mineralization and may provide new insights into the fate of aqueous uranium complexes.

A homologous series of regioselectively tetradeprotonated group 8 metallocenes: new inverse crown ring compounds synthesized via a mixed sodium-magnesium tris(diisopropylamide) synergic base.

PubMed

Andrikopoulos, Prokopis C; Armstrong, David R; Clegg, William; Gilfillan, Carly J; Hevia, Eva; Kennedy, Alan R; Mulvey, Robert E; O'Hara, Charles T; Parkinson, John A; Tooke, Duncan M

2004-09-22

Subjecting ferrocene, ruthenocene, or osmocene to the synergic amide base sodium-magnesium tris(diisopropylamido) affords a unique homologous series of metallocene derivatives of general formula [(M(C(5)H(3))(2))Na(4)Mg(4)(i-Pr(2)N)(8)] (where M = Fe (1), Ru (2), or Os (3)). X-ray crystallographic studies of 1-3 reveal a common molecular "inverse crown" structure comprising a 16-membered [(NaNMgN)(4)](4+) "host" ring and a metallocenetetraide [M(C(5)H(3))(2)](4-) "guest" core, the cleaved protons of which are lost selectively from the 1, 1', 3, and 3'-positions. Variable-temperature NMR spectroscopic studies indicate that 1, 2, and 3 each exist as two distinct interconverting conformers in arene solution, the rates of exchange of which have been calculated using coalescence and EXSY NMR measurements.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kuzmin, Stanislav L.; Wesolowski, Michal J.; Duley, Walter W.

A new type of metal-organic composition consisting of clusters of nanoparticles has been synthesised by laser irradiation of metallocene/benzene solutions. The metallocene molecules in this reaction become the source of the metal. Exposure to high-energy femtosecond laser pulses dehydrogenate benzene molecules and initiate the high-temperature high-pressure conditions that results in the synthesis of new materials. Irradiation experiments have been carried out on ferrocene/benzene and on other solutions. With ferrocene the synthesis of a new compound has been confirmed by X-ray powder diffraction as the peaks detected do not correspond to any known substance in the Crystallography Open Database. Theoretical simulationmore » of the periodic structure of this new carbide predicts that it has hexagonal symmetry and a unit cell with a = 3.2A and c =2.8A. The exact structure is still uncertain but may be determined from scanning tunneling microscope (STM) studies.« less

Ring opening polymerisation of lactide with uranium(iv) and cerium(iv) phosphinoaryloxide complexes.

PubMed

Sinclair, Fern; Hlina, Johann A; Wells, Jordann A L; Shaver, Michael P; Arnold, Polly L

2017-08-22

The C 3 -symmetric uranium(iv) and cerium(iv) complexes Me 3 SiOM(OAr P ) 3 , M = U (1), Ce (2), OAr P = OC 6 H 2 -6- t Bu-4-Me-2-PPh 2 , have been prepared and the difference between these 4f and 5f congeners as initiators for the ring opening polymerisation (ROP) of l-lactide is compared. The poorly controlled reactivity of the homoleptic analogue U(OAr P ) 4 (3) demonstrates the importance of the M-OSiMe 3 initiating group. The incorporation of a nickel atom in 1 to form the U-Ni heterobimetallic complex Me 3 SiOU(OAr P ) 3 Ni (4) may be the first example of the use of the inverse trans influence to switch the reactivity of a complex. This would imply the formation of the U-Ni bond strengthens the U-OSiMe 3 bond to such an extent that the ROP catalysis is switched off. Changing the conditions to immortal polymerisation dramatically increases polymerisation rates, and switches the order, with the Ce complex now faster than the U analogue, suggesting ligand protonolysis to afford a more open coordination sphere. For the ROP of rac-lactide, uranium complex 1 promotes heterotacticity at the highest levels of stereocontrol yet reported for an actinide complex.

Synthesis and use of (perfluoroaryl) fluoro-aluminate anion

DOEpatents

Marks, Tobin J.; Chen, You-Xian

2001-01-01

A trityl perfluorophenyl alumninate such as tris(2,2',2"-nonafluorobiphenyl)-fluoroaluminate (PBA.sup..crclbar.) and its role as a cocatalyst in metallocene-mediated olefin polymerization is disclosed. Gallium and indium analogs are also disclosed, as are analogs with different anyl groups or different numbers of flourine atoms thereon.

Organo-Lewis acid as cocatalyst for cationic homogeneous Ziegler-Natta olefin polymerizations

DOEpatents

Marks, Tobin J.; Chen, You-Xian

2001-01-01

Organo-Lewis acids of the formula BR'R".sub.2 wherein B is boron, R' is fluorinated biphenyl, and R" is a fluorinated phenyl, fluorinated biphenyl, or fluorinated polycyclic fused ring group, and cationic metallocene complexes formed therewith. Such complexes are useful as polymerization catalysts.

Organo-Lewis acid as cocatalyst for cationic homogeneous Ziegler-Natta olefin polymerizations

DOEpatents

Marks, Tobin J.; Chen, You-Xian

2002-01-01

Organo-Lewis acids of the formula BR'R".sub.2 wherein B is boron, R' is fluorinated biphenyl, and R" is a fluorinated phenyl, fluorinated biphenyl, or fluorinated polycyclic fused ring group, and cationic metallocene complexes formed therewith. Such complexes are useful as polymerization catalysts.

Manual Solid-Phase Peptide Synthesis of Metallocene-Peptide Bioconjugates

ERIC Educational Resources Information Center

Kirin, Srecko I.; Noor, Fozia; Metzler-Nolte, Nils; Mier, Walter

2007-01-01

A simple and relatively inexpensive procedure for preparing a biologically active peptide using solid phase peptide synthesis (SPPS) is described. Fourth-year undergraduate students have gained firsthand experience from the solid-phase synthesis techniques and they have become familiar with modern analytical techniques based on the particular…

Mild hydrothermal crystal growth of new uranium(IV) fluorides, Na3.13Mg1.43U6F30 and Na2.50Mn1.75U6F30: Structures, optical and magnetic properties

NASA Astrophysics Data System (ADS)

Yeon, Jeongho; Smith, Mark D.; Tapp, Joshua; Möller, Angela; zur Loye, Hans-Conrad

2016-04-01

Two new uranium(IV) fluorides, Na3.13Mg1.43U6F30 (1) and Na2.50Mn1.75U6F30 (2), were synthesized through an in situ mild hydrothermal route, and were structurally characterized by single crystal X-ray diffraction. The compounds exhibit complex crystal structures composed of corner- or edge-shared UF9 and MF6 (M=Mg, Mn) polyhedra, forming hexagonal channels in the three-dimensional framework, in which ordered or disordered divalent metal and sodium atoms reside. The large hexagonal voids contain the nearly regular M(II)F6 octahedra and sodium ions, whereas the small hexagonal cavities include M(II) and sodium ions on a mixed-occupied site. Magnetic susceptibility measurements yielded effective magnetic moments of 8.36 and 11.6 μB for 1 and 2, respectively, confirming the presence and oxidation states of U(IV) and Mn(II). The large negative Weiss constants indicate the spin gap between a triplet and a singlet state in the U(IV). Magnetization data as a function of applied fields revealed that 2 exhibits paramagnetic behavior due to the nonmagnetic singlet ground state of U(IV) at low temperature. UV-vis diffuse reflectance and X-ray photoelectron spectroscopy data were also analyzed.

Uranium(IV) adsorption by natural organic matter in anoxic sediments

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bone, Sharon E.; Dynes, James J.; Cliff, John

Uranium is an important carbon-free fuel source and environmental contaminant that accumulates in the tetravalent state, U(IV), in anoxic sediments, such as ore deposits, marine basins, and contaminated aquifers. However, little is known about the speciation of U(IV) in low-temperature geochemical environments, inhibiting the development of a conceptual model of U behavior. Until recently, U(IV) was assumed to exist predominantly as the sparingly soluble mineral uraninite (UO 2+x) in anoxic sediments; however, studies now show that this is not often the case. Yet a model of U(IV) speciation in the absence of mineral formation under field-relevant conditions has not yetmore » been developed. Uranium(IV) speciation controls its reactivity, particularly its susceptibility to oxidative mobilization, impacting its distribution and toxicity. Here we show adsorption to organic carbon and organic carbon-coated clays dominate U(IV) speciation in an organic-rich natural substrate under field-relevant conditions. Whereas previous research assumed that U(IV) speciation is dictated by the mode of reduction (i.e., whether reduction is mediated by microbes or by inorganic reductants), our results demonstrate that mineral formation can be diminished in favor of adsorption, regardless of reduction pathway. Projections of U transport and bioavailability, and thus its threat to human and ecosystem health, must consider U(IV) adsorption to organic matter within the sediment environment.« less

Uranium(IV) adsorption by natural organic matter in anoxic sediments

DOE PAGES

Bone, Sharon E.; Dynes, James J.; Cliff, John; ...

2017-01-09

Uranium is an important carbon-free fuel source and environmental contaminant that accumulates in the tetravalent state, U(IV), in anoxic sediments, such as ore deposits, marine basins, and contaminated aquifers. However, little is known about the speciation of U(IV) in low-temperature geochemical environments, inhibiting the development of a conceptual model of U behavior. Until recently, U(IV) was assumed to exist predominantly as the sparingly soluble mineral uraninite (UO 2+x) in anoxic sediments; however, studies now show that this is not often the case. Yet a model of U(IV) speciation in the absence of mineral formation under field-relevant conditions has not yetmore » been developed. Uranium(IV) speciation controls its reactivity, particularly its susceptibility to oxidative mobilization, impacting its distribution and toxicity. Here we show adsorption to organic carbon and organic carbon-coated clays dominate U(IV) speciation in an organic-rich natural substrate under field-relevant conditions. Whereas previous research assumed that U(IV) speciation is dictated by the mode of reduction (i.e., whether reduction is mediated by microbes or by inorganic reductants), our results demonstrate that mineral formation can be diminished in favor of adsorption, regardless of reduction pathway. Projections of U transport and bioavailability, and thus its threat to human and ecosystem health, must consider U(IV) adsorption to organic matter within the sediment environment.« less

Unprecedented reduction of the uranyl ion [UO2]2+ into a polyoxo uranium(IV) cluster: synthesis and crystal structure of the first f-element oxide with a M6(micro3-O)8 core.

PubMed

Berthet, Jean-Claude; Thuéry, Pierre; Ephritikhine, Michel

2005-07-21

The smooth comproportionation reaction of the U(VI) and U(III) complexes UO2(OTf)2 and U(OTf)3, afforded the hexanuclear U(IV) oxide cluster [U6(micro3-O)8(micro2-OTf)8(py)8], a rare example of a metal oxide with a M6(micro3-O)8 core.

Pentadienyl chemistry of the heavy alkaline-earth metals revisited.

PubMed

Reiners, Matthias; Fecker, Ann Christin; Freytag, Matthias; Jones, Peter G; Walter, Marc D

2014-05-14

Open-metallocenes of the heavy alkaline-earth metals [(η(5)-Pdl')2M(thf)n] (M = Ca (1), Sr (2), n = 1; M = Ba (3), n = 2; Pdl' = 2,4-tBu2C5H5) are readily prepared by salt-metathesis between MI2 and KPdl' and characterized by NMR spectroscopy and X-ray diffraction studies.

Illustrating Catalysis with Interlocking Building Blocks: Correlation between Structure of a Metallocene Catalyst and the Stereoregularity of Polypropylene

ERIC Educational Resources Information Center

Horikoshi, Ryo; Kobayashi, Yoji; Kageyama, Hiroshi

2013-01-01

Catalysis with transition-metal complexes is a part of the inorganic chemistry curriculum and a challenging topic for upper-level undergraduate and graduate students. A hands-on teaching aid has been developed for use during conventional lectures to help students understand these catalytic reactions. A unique method of illustrating the…

Polyorganometallosiloxane-2- or -4-pyridine coatings

DOEpatents

Sugama, Toshifumi

1997-01-01

A new family of polyorganometallosiloxane-2- or -4-pyridine compounds are provided for corrosion resistant coatings on light metals such as aluminum, magnesium, zinc, steel and their allows. The novel compounds contain backbones modified by metal alkoxides, metallocenes and metallophthalocyanates where the metal is Zr, Ti, Mo, V, Hf, Nb, Si, B and combinations thereof. Methods of making the new compounds are also provided.

Polyorganometallosiloxane-2- or -4-pyridine coatings

DOEpatents

Sugama, T.

1997-12-30

A new family of polyorganometallosiloxane-2- or -4-pyridine compounds are provided for corrosion resistant coatings on light metals such as aluminum, magnesium, zinc, steel and their alloys. The novel compounds contain backbones modified by metal alkoxides, metallocenes and metallophthalocyanates where the metal is Zr, Ti, Mo, V, Hf, Nb, Si, B and combinations thereof. Methods of making the new compounds are also provided. 13 figs.

Synthesis, characterization, and reactivity of pentamethylcyclopentadienyl complexes of divalent cobalt and nickel

DOE Office of Scientific and Technical Information (OSTI.GOV)

Smith, Michael Edward

1993-10-01

The thesis is divided into the following 4 chapters: synthesis, characterization, and reactivity of trinuclear pentamethylcyclopentadienyl cobalt and nickel clusters with triply-bridging methylidyne groups; chemical and physical properties of pentamethylcyclopentadienyl acetylacetonate complexes of Co(II) and Ni(II); synthesis, characterization, and reactivity of pentamethylcyclopentadienyl halide complexes of Co and Ni; and crystallographic studies of distortions in metallocenes with C 5-symmetrical cyclopentadienyl rings.

The preparation of nanosized polyethylene particles via novel heterogeneous non-metallocene catalyst (m-CH3PhO)TiCl3/CNTs/AlEt3

NASA Astrophysics Data System (ADS)

Wang, J.; Guo, J. P.; Yi, J. J.; Huang, Q. G.; Li, H. M.; Li, Y. F.; Gao, K. J.; Yang, W. T.

2014-08-01

This paper reports the preparation of coral-shaped topological morphology nascent polyethylene (PE) particles promoted by the novel heterogeneous non-metallocene catalyst (m-CH3PhO)TiCl3/carbon nanotubes (CNTs), with AlEt3 used as a cocatalyst. Scanning electron microscope (SEM), high resolution transmission electron microscope (HR-TEM) and inductively coupled plasma (ICP) emission spectroscopy were used to determine the morphology of the catalyst particles and the content of (m-CH3PhO)TiCl3. The carbon nanotube surface was treated with Grignard Reagent prior to reacting with (m-CH3PhO)TiCl3. The catalyst system could effectively catalyze ethylene polymerization and ethylene with 1- hexene copolymerization, the catalytic activity could reach up to 5.8 kg/((gTi)h). Morphology of the obtained polymer particles by SEM and HR-TEM technique revealed that the nascent polyethylene particles looked like coral shape in micro-size. The multiwalled carbon nanotubes (MWCNTs) supported catalysts polymerized ethylene to form polymer nanocomposite in situ. The microscopic examination of this nanocomposite revealed that carbon nanoparticles in PE matrix had a good distribution and the cryogenically fractured surface was ductile-like when polymerization time was 2 min.

News from Online: Industrial Chemicals and Polymers

NASA Astrophysics Data System (ADS)

Sweeney Judd, Carolyn

1999-02-01

Paper or plastic? I am asked this question every time I go grocery shopping. Asked another way, the question is, "Which polymer do you want?" To learn about polymers, go shopping at a great site from the University of Southern Mississippi, The Macrogalleria, a cyberwonderland of polymer fun at http://www.psrc.usm.edu/macrog/index.html . Plan to spend some time here. Bring along Chime and Shockwave plug-ins or download them from The Macrogalleria. The Macrogalleria shopping mall is divided into five levels. On the first level, Polymers are Everywhere at http:/ /www.psrc.usm.edu/macrog/floor1.html, you can visit stores selling sporting goods, food, and clothing. Learn about natural polymers in shoes and in French fries at http://www.psrc.usm.edu/macrog/natupoly.html . Find out about nylon in toothbrushes at http://www.psrc.usm.edu/macrog/nylon.html and about carbon fibers in tennis racquets at http://www.psrc.usm.edu/macrog /carfib.html-great graphics and even better chemistry. Skip up to level three for How They Work at http:/ /www.psrc.usm.edu/macrog/floor3.html. Take a look at the history of rubber on The Cross-linking Page at http:/ /www.psrc.usm.edu/macrog/xlink.html. Move on to level four for Makin' Polymers at http://www.psrc.usm.edu/macrog /floor4.html. Let's go right to the Ziegler-Natta Vinyl Polymerization at http://www.psrc.usm.edu/macrog/ziegler.html . Don't miss the humor in the initial explanation of the process. This page is excellent-with graphics, reactions, and a movie of a polymerization ( http://www.psrc.usm.edu/macrog/movies/zns.html ). This movie is worth seeing several times. Next take a look at another catalyst metallocene at http:/ /www.psrc.usm.edu/macrog/mcene.html. Explanations, graphics, and mechanisms help make this site worth visiting and great for teaching. Several people contributed to The Macrogalleria, with major contributions from Mark Michalovic of the University of Southern Mississippi. Grants were from POLYED, a joint committee of the American Chemical Society Divisions of Polymer Chemistry and Polymeric Materials: Science and Engineering and General Electric Corporation. The POLYED site, http:/ /chemdept.uwsp.edu/polyed/index.htm, is hosted by the University of Wisconsin at Stevens Point. This National Center for Polymer Education is another good place to go for information. More education is available at the Ziegler Research Group Home Page at http://www.chem.ucalgary.ca/groups/ziegler/index.html . Go to Metallocene as Olefin Polymerization Catalysis: An Introduction ( http://www.chem.ucalgary.ca/groups/ziegler/met_intro.html ) for historical accounts of metallocene and Ziegler-Natta catalysts. Movies are available here too. This Canadian site is well-documented and educational. Back at the University of Wisconsin-Madison, The Why Files site at http://whyfiles.news.wisc.edu helps bring important chemical and technology news to the public. Go to the archived files of October 1997 ( http://whyfiles.news.wisc.edu/shorties/catalyst.html ) to find information about the importance of low-temperature metallocene catalysts. The Why Files received funding from the National Science Foundation. Go here for science information in an easy-to-read format. One of the driving forces toward better catalysis is the attempt to reach 100% product, combining efficiency with lowered pollution. Companies can look to the Environmental Protection Agency for information: Environsense at http://es.epa.gov/ is pledged to offer "Common Sense Solutions to Environmental Problems". So where can we get these polymers? The American Chemical Society can help. Go to Chemcylopedia at http://pubs.acs.org/chemcy99/ for great information. Both purchasers and users of chemicals can benefit from this site. Searches can be made on the chemical or on the supplier. Information provided includes CAS Registry Numbers and special shipping requirements as well as potential applications. Do you remember that we started with paper? Let's end with information about making paper. Go to http://www.sci.fi /~saarives/pulpmfl.htm for Ahlstrom Machinery's Typical Offerings for Chemical Pulp Mills. Now this is a chemically rich plant that is worth the trip. Carolyn Sweeney Judd teaches at Houston Community College System, 1300 Holman, Houston, TX 77004; phone: 713/718-6315; email: cjudd@tenet.edu. World Wide Web Addresses The Macrogalleria http://www.psrc.usm.edu/macrog/index.html Polymers Are Everywhere http://www.psrc.usm.edu/macrog/floor1.html Natural Polymers http://www.psrc.usm.edu/macrog/natupoly.html Nylon http://www.psrc.usm.edu/macrog/nylon.html Carbon Fibers http://www.psrc.usm.edu/macrog/carfib.html How They Work http://www.psrc.usm.edu/macrog/floor3.html The Cross-linking Page http://www.psrc.usm.edu/macrog/xlink.html Makin' Polymers http://www.psrc.usm.edu/macrog/floor4.html Ziegler-Natta Vinyl Polymerization http://www.psrc.usm.edu/macrog/ziegler.html Syndiotactic Ziegler-Natta Polymerization (movie, Shockwave plug-in required for viewing) at http://www.psrc.usm.edu/macrog/movies/zns.html Metallocene Catalysis Polymerization http://www.psrc.usm.edu/macrog/mcene.html POLYED Welcome Page http://chemdept.uwsp.edu/polyed/index.htm Ziegler Research Group Home Page http://www.chem.ucalgary.ca/groups/ziegler/index.html Metallocene as Olefin Polymerization Catalysis: An Introduction at http://www.chem.ucalgary.ca/groups/ziegler/met_intro.html The Why Files http://whyfiles.news.wisc.edu Low-Temperature Metallocene Catalysts http://whyfiles.news.wisc.edu/shorties/catalyst.html Environsense http://es.epa.gov/ Chemcylopedia 99 http://pubs.acs.org/chemcy99/ Ahlstrom Machinery's Typical Offerings for Chemical Pulp Mills at http://www.sci.fi/~saarives/pulpmfl.htm access date for all sites: December 1998

Bonding and Mobility of Alkali Metals in Helicenes.

PubMed

Barroso, Jorge; Murillo, Fernando; Martínez-Guajardo, Gerardo; Ortíz-Chi, Filiberto; Pan, Sudip; Fernández-Herrera, María A; Merino, Gabriel

2018-06-04

In this work, we analyze the interaction of alkali metal cations with [6]- and [14]helicene and the cation mobility of therein. We found that the distortion of the carbon skeleton is the cause that some of the structures that are local minima for the smallest cations are not energetically stable for K+, Rb+, and Cs+. Also, the most favorable complexes are those where the cation is interacting with two rings forming a metallocene-like structure, except for the largest cation Cs+, where the distortion provoked by the size of the cation desestabilizes the complex. As far as mobility is concerned, the smallest cations, particularly Na+, are the ones that can move most efficiently. In [6]helicene, the mobility is limited by the capture of the cation forming the metallocene-like structure. In larger helicenes, the energy barriers for the cation to move are similar both inside and outside the helix. However, complexes with the cation between two layers are more energetically favored so that the movement will be preferred in that region. The bonding analysis reveals that interactions with no less than 50% of orbitalic contribution are taking place for the series of E+-[6]helicene. Particularly, the complexes of Li+ stand out showing a remarkably orbitalic character bonding (72.5 - 81.6%). © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Constrained Geometry Organotitanium Catalysts Supported on Nanosized Silica for Ethylene (co)Polymerization.

PubMed

Li, Kuo-Tseng; Wu, Ling-Huey

2017-05-05

Supported olefin polymerization catalysts can prevent reactor-fouling problems and produce uniform polymer particles. Constrained geometry complexes (CGCs) have less sterically hindered active sites than bis-cyclopentadienyl metallocene catalysts. In the literature, micrometer-sized silica particles were used for supporting CGC catalysts, which might have strong mass transfer limitations. This study aims to improve the activity of supported CGC catalysts by using nanometer-sized silica. Ti[(C₅Me₄)SiMe₂(N t Bu)]Cl₂, a "constrained-geometry" titanium catalyst, was supported on MAO-treated silicas (nano-sized and micro-sized) by an impregnation method. Ethylene homo-polymerization and co-polymerization with 1-octene were carried out in a temperature range of 80-120 °C using toluene as the solvent. Catalysts prepared and polymers produced were characterized. For both catalysts and for both reactions, the maximum activities occurred at 100 °C, which is significantly higher than that (60 °C) reported before for supported bis-cyclopentadienyl metallocene catalysts containing zirconium, and is lower than that (≥140 °C) used for unsupported Ti[(C₅Me₄)SiMe₂(N t Bu)]Me₂ catalyst. Activities of nano-sized catalyst were 2.6 and 1.6 times those of micro-sized catalyst for homopolymerization and copolymerization, respectively. The former produced polymers with higher crystallinity and melting point than the latter. In addition, copolymer produced with nanosized catalyst contained more 1-octene than that produced with microsized catalyst.

Metallocene-Containing Homopolymers and Heterobimetallic Block Copolymers via Photoinduced RAFT Polymerization

PubMed Central

Yang, Peng; Pageni, Parasmani; Kabir, Mohammad Pabel; Zhu, Tianyu; Tang, Chuanbing

2017-01-01

We report the synthesis of cationic cobaltocenium and neutral ferrocene containing homopolymers mediated by photoinduced reversible addition-fragmentation chain transfer (RAFT) polymerization with a photocatalyst fac-[Ir(ppy)3]. The homopolymers were further used as macromolecular chain transfer agents to synthesize diblock copolymers via chain extension. Controlled/“living” feature of photoinduced RAFT polymerization was confirmed by kinetic studies even without prior deoxygenation. A light switch between ON and OFF provided a spatiotemporal control of polymerization. PMID:29276651

The Role of Solvent Reorganization Dynamics in Electron-Transfer Processes. Theory-Experiment Comparisons for Electrochemical and Homogeneous Electron Exchange Involving Metallocene Redox Couples

DTIC Science & Technology

1985-08-01

Kodak) by crystallization from acetone; it was recrystallized twice from ethanol and dried in a vacuum oven. Tetraethylamonium perchlorate (TEAP) (G...the electrooxidation of in(Cp’) 2 , which yielded significantly smaller reverse (cathodic) currents in the most strongly coordinating solvents (DMX...DM50) at slower scan rates (< 0.5 V sec-1). Nevertheless, satisfactory a.c. polarograms were obtained for each of these system=. 5 4 Temperature

Polyolefin Nanocomposites with Enhanced Photostability Weathering Effect on Morphology and Mechanical Properties

NASA Astrophysics Data System (ADS)

Panda, Bishnu P.; Mohanty, Smita; Nayak, Sanjay K.

2014-09-01

This research aims to study the effect of accelerated weathering conditions on the photodegradation characteristics for fibrillar silicate clay-filled Polypropylene (PP) nanocomposites in the presence of metallocene linear low density polyethylene (m-LLDPE). Silane-treated attapulgite (ATP) clay along with ethylene octene elastomer-grafted maleic anhydride (POE-g-MAH) was used to compatibilize both blend and nanocomposite system. The result showed that developed PP/m-LLDPE nanocomposites displayed good UV resistance with little change in retained stress-at-break and elongation-at-break values. Balanced loss of toughness values noted maintaining higher fracture toughness values for nanocomposites containing 5 phr ATP clay. Infrared analysis was used to detect progress of degradation followed by change in carbonyl index revealed predominated chain scission in late irradiation, while crosslinking was dominant for initial irradiation period. An increase in crystallinity during UV exposure (chemi-crystallization) was detected with exposure time for all compositions and virtually independent of initial structure of the polymer. The highest value of crystallization observed for PP and the lowest one for nanocomposites containing 5 phr of ATP clay revealed good oxidation stability. Surface morphology revealed induced degradation throughout cross-section of PP, while severity of the surface degradation was significantly reduced for developed nanocomposites.

Electrochemistry in supercritical fluids

PubMed Central

Branch, Jack A.; Bartlett, Philip N.

2015-01-01

A wide range of supercritical fluids (SCFs) have been studied as solvents for electrochemistry with carbon dioxide and hydrofluorocarbons (HFCs) being the most extensively studied. Recent advances have shown that it is possible to get well-resolved voltammetry in SCFs by suitable choice of the conditions and the electrolyte. In this review, we discuss the voltammetry obtained in these systems, studies of the double-layer capacitance, work on the electrodeposition of metals into high aspect ratio nanopores and the use of metallocenes as redox probes and standards in both supercritical carbon dioxide–acetonitrile and supercritical HFCs. PMID:26574527

Dialkyl dicyanofumarates and dicyanomaleates as versatile building blocks for synthetic organic chemistry and mechanistic studies

PubMed Central

Heimgartner, Heinz

2017-01-01

The scope of applications of dialkyl dicyanofumarates and maleates as highly functionalized electron-deficient dipolarophiles, dienophiles and Michael acceptors is summarized. The importance for the studies on reaction mechanisms of cycloadditions is demonstrated. Multistep reactions with 1,2-diamines and β-aminoalcohols leading to diverse five- and six-membered heterocycles are discussed. Applications of dialkyl dicyanofumarates as oxidizing agents in the syntheses of disulfides and diselenides are described. The reactions with metallocenes leading to charge-transfer complexes with magnetic properties are also presented. PMID:29114328

Redox polymer electrodes for advanced batteries

DOEpatents

Gregg, Brian A.; Taylor, A. Michael

1998-01-01

Advanced batteries having a long cycle lifetime are provided. More specifically, the present invention relates to electrodes made from redox polymer films and batteries in which either the positive electrode, the negative electrode, or both, comprise redox polymers. Suitable redox polymers for this purpose include pyridyl or polypyridyl complexes of transition metals like iron, ruthenium, osmium, chromium, tungsten and nickel; porphyrins (either free base or metallo derivatives); phthalocyanines (either free base or metallo derivatives); metal complexes of cyclams, such as tetraazacyclotetradecane; metal complexes of crown ethers and metallocenes such as ferrocene, cobaltocene and ruthenocene.

Redox polymer electrodes for advanced batteries

DOEpatents

Gregg, B.A.; Taylor, A.M.

1998-11-24

Advanced batteries having a long cycle lifetime are provided. More specifically, the present invention relates to electrodes made from redox polymer films and batteries in which either the positive electrode, the negative electrode, or both, comprise redox polymers. Suitable redox polymers for this purpose include pyridyl or polypyridyl complexes of transition metals like iron, ruthenium, osmium, chromium, tungsten and nickel; porphyrins (either free base or metallo derivatives); phthalocyanines (either free base or metallo derivatives); metal complexes of cyclams, such as tetraazacyclotetradecane; metal complexes of crown ethers and metallocenes such as ferrocene, cobaltocene and ruthenocene. 2 figs.

Reaction kinetics and product distributions in photoelectrochemical cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Koval, C.A.

1992-01-01

Hot electron reaction studies at p-InP/CH[sub 3]CN interface revealed essential/desirable features for redox systems used to investigate hot carriers in photoelectrocehmical cells. Reduction of dibromoethylbenzene (DBEB) in presence of metallocene couples is being studied using rotating rink disk electrodes of n-and p-InP disks and Pt rings. At highly doped p-InP electrodes, reduction of DBEB can be very efficient (>30%). A minielectrochemical cell was used to investigate electron transfer at nonilluminated n-WSe[sub 2]/dimethylferrocene[sup +/0] interfaces.

Characterization of B-H agostic compounds involved in the dehydrogenation of amine-boranes by group 4 metallocenes.

PubMed

Zhu, Jingwen; Zins, Emilie-Laure; Alikhani, Mohammad Esmaïl

2016-12-01

For over a decade, amine-borane has been considered as a potential chemical hydrogen vector in the context of a search for cleaner energy sources. When catalyzed by organometallic complexes, the reaction mechanisms currently considered involve the formation of β-BH agostic intermediates. A thorough understanding of these intermediates may constitute a crucial step toward the identification of ideal catalysts. Topological approaches such as QTAIM and ELF revealed to be particularly suitable for the description of β-agostic interactions. When studying model catalysts, accurate theoretical calculations may be carried out. However, for a comparison with experimental data, calculations should also be carried out on large organo-metallic species, often including transition metals belonging to the second or the third row. In such a case, DFT methods are particularly attractive. Unfortunately, triple-ζ all electrons basis sets are not easily available for heavy transition metal elements. Thus, a subtle balance should be reached between the affordable level of calculations and the required accuracy of the electronic description of the systems. Herein we propose the use of B3LYP functional in combination with the LanL2DZ pseudopotential for the metal atom and 6-311++G(2d,2p) basis set for the other atoms, followed by a single point using the DKH2 relativistic Hamiltonian in combination with the B3LYP/DZP-DKH level, as a "minimum level of theory" leading to a consistent topological description of the interaction within the ELF and QTAIM framework, in the context of isolated (gas-phase) group 4 metallocene catalysts.

A systematic computational study of electronic effects on hydrogen sensitivity of olefin polymerization catalysts (abstract only).

PubMed

Coussens, Betty B; Budzelaar, Peter H M; Friederichs, Nic

2008-02-13

One of the important product parameters of polyolefins is their molecular weight (distribution). A common way to control this parameter is to add molecular hydrogen during the polymerization, which then acts as a chain transfer agent. The factors governing the hydrogen sensitivity of olefin polymerization catalysts are poorly understood and have attracted little attention from computational chemists. To explore the electronic factors determining hydrogen sensitivity we performed density functional calculations on a wide range of simple model systems including some metallocenes and a few basic models of heterogeneous catalysts. As a quantitative measure for hydrogen sensitivity we used the ratio of (i) the rate constant for chain transfer to hydrogen to (ii) the rate constant for ethene insertion, k(h)/k(p) (see the scheme below), and as a measure of electrophilicity we used the energy of complexation to the probe molecule ammonia. [Formula: see text] For isolated species in the gas phase, complexation energies appear to dominate the chemistry. Ethene complexes more strongly than hydrogen and with increasing electrophilicity of the metal centre this difference grows; the hydrogen sensitivity decreases accordingly. Although many factors (like catalyst dormancy and deactivation issues) complicate the comparison with experiment, this result seems to agree both in broad terms with the experimental lower hydrogen sensitivity of heterogeneous catalysts, and more specifically with the increased hydrogen sensitivity of highly alkylated or fused metallocenes. The opposite conclusion reached by Blom (see Blom et al 2002 Macromol. Chem. Phys. 203 381-7) is due to the use of a very different measure of electrophilicity, rather than to different experimental data.

Reaction kinetics and product distributions in photoelectrochemical cells. Technical progress report, March 15, 1992--March 14, 1993

DOE Office of Scientific and Technical Information (OSTI.GOV)

Koval, C.A.

1992-12-01

Hot electron reaction studies at p-InP/CH{sub 3}CN interface revealed essential/desirable features for redox systems used to investigate hot carriers in photoelectrocehmical cells. Reduction of dibromoethylbenzene (DBEB) in presence of metallocene couples is being studied using rotating rink disk electrodes of n-and p-InP disks and Pt rings. At highly doped p-InP electrodes, reduction of DBEB can be very efficient (>30%). A minielectrochemical cell was used to investigate electron transfer at nonilluminated n-WSe{sub 2}/dimethylferrocene{sup +/0} interfaces.

UV induced surface modification on improving the cytocompatibility of metallocene polyethylene.

PubMed

Jaganathan, Saravana K; Prasath, Mani M

2018-01-01

Demand for medical implants is rising day by day as the world becomes the place for more diseased and older people. Accordingly, in this research, metallocene polyethylene (mPE), a commonly used polymer was treated with UV rays for improving its biocompatibility. Scanning electron microscopy (SEM) images confirmed the formation of crests and troughs, which depicts the improvement of surface roughness of mPE substrates caused by UV etching. Accordingly, the contact angle measurements revealed that the wettability of mPE-2.5 J/cm2 (68.09º) and mPE-5 J/cm2 (57.93º) samples were found to be increased compared to untreated mPE (86.84º) indicating better hydrophilicity. Further, the UV treated surface exhibited enhanced blood compatibility as determined in APTT (untreated mPE- 55.3 ± 2.5 s, mPE-2.5 J/cm2 - 76.7 ± 4.1 s and mPE-5 J/cm2 - 112.3 ± 2 s) and PT (untreated mPE - 24.7 ± 1.5 s, mPE- 2.5 J/cm2 - 34.3 ± 1.1 s and mPE-5 J/cm2 - 43 ± 2 s) assay. Moreover, the treated mPE-2.5 J/cm2 (4.88%) and mPE-5 J/cm2 (1.79%) showed decreased hemolytic percentage compared to untreated mPE (15.40%) indicating better safety to red blood cells. Interestingly, the changes in physicochemical properties of mPE are directly proportional to the dosage of the UV rays. UV modified mPE surfaces were found to be more compatible as identified through MTT assay, photomicrograph and SEM images of the seeded 3T3 cell population. Hence UV-modified surface of mPE may be successfully exploited for medical implants.

Determination of the oxidation state of uranium in apatite and phosphorite deposits

USGS Publications Warehouse

Clarke, R.S.; Altschuler, Z.S.

1958-01-01

Geological and mineralogical evidence indicate that the uranium present in apatite may proxy for calcium in the mineral structure as U(IV). An experimental investigation was conducted and chemical evidence was obtained that establishes the presence of U(IV) in apatite. The following analytical procedure was developed for the determination of U(IV). Carbonatefluorapatite is dissolved in 1.5 M orthophosphoric acid at a temperature of 5??C or slightly below and fluorapatite is dissolved in cold 1.2 M hydrochloric acid (approximately 5??C) containing 1.5 g of hydroxylamine hydrochloride per 100 ml. Uranium(IV) is precipitated by cupferron using titanium as a carrier. The uranium in the precipitate is separated by use of the ethyl acetate extraction procedure and determined fluorimetrically. The validity and the limitations of the method have been established by spike experiments. ?? 1958.

Uranium removal from a contaminated effluent using a combined microbial and nanoparticle system.

PubMed

Baiget, Mar; Constantí, Magda; López, M Teresa; Medina, Francesc

2013-09-25

Reduction of soluble uranium(VI) to insoluble uranium(IV) for remediating a uranium-contaminated effluent (EF-03) was examined using a biotic and abiotic integrated system. Shewanella putrefaciens was first used and reduced U(VI) in a synthetic medium but not in the EF-03 effluent sample. Subsequently the growth of autochthonous microorganisms was stimulated with lactate. When lactate was supported on active carbon 77% U(VI) was removed in 4 days. Separately, iron nanoparticles that were 50 nm in diameter reduced U(VI) by 60% in 4 hours. The efficiency of uranium(VI) removal was improved to 96% in 30 min by using a system consisting of lactate and iron nanoparticles immobilized on active carbon. Lactate also stimulated the growth of potential uranium-reducing microorganisms in the EF-03 sample. This system can be efficiently used for the bioremediation of uranium-contaminated effluents. Copyright © 2013 Elsevier B.V. All rights reserved.

Synthesis of Actinide Fluoride Complexes Using Trimethyltin Fluoride as a Mild and Selective Fluorinating Reagent

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kagan, Benjamin D.; Lichtscheidl, Alejandro G.; Erickson, Karla A.

Trimethyltin fluoride (Me₃SnF) is a mild and selective reagent for the installation of actinide fluoride bonds as demonstrated by the room temperature synthesis of a variety of organometallic and inorganic thorium(IV), uranium(IV), and uranium(V) fluoride complexes ((1,2,4-tBu₃C₅H₂)₂ThF₂, (C₅Me₅)₂U(F)(O-2,6-iPr₂C₆H₃), U(F)(O-2,6-tBu₂C₆H₃)₃, U(F)[N(SiMe₃)₂]₃ (C₅Me₅)₂UF₂(L) (L = O=PMe₃, O=PPh₃, O=PCy₃), and (C₅Me₅)₂U(F)(=N-2,6-iPr₂C₆H₃)) from their corresponding chloride, bromide, and iodide analogues. From these reactions, the new (C₅Me₅)₂UF₂(L) (L = O=PPh₃, O=PCy₃) uranium fluoride complexes were isolated and characterized by NMR spectroscopy and X-ray crystallography.

Synthesis of Actinide Fluoride Complexes Using Trimethyltin Fluoride as a Mild and Selective Fluorinating Reagent

DOE PAGES

Kagan, Benjamin D.; Lichtscheidl, Alejandro G.; Erickson, Karla A.; ...

2017-11-07

Trimethyltin fluoride (Me₃SnF) is a mild and selective reagent for the installation of actinide fluoride bonds as demonstrated by the room temperature synthesis of a variety of organometallic and inorganic thorium(IV), uranium(IV), and uranium(V) fluoride complexes ((1,2,4-tBu₃C₅H₂)₂ThF₂, (C₅Me₅)₂U(F)(O-2,6-iPr₂C₆H₃), U(F)(O-2,6-tBu₂C₆H₃)₃, U(F)[N(SiMe₃)₂]₃ (C₅Me₅)₂UF₂(L) (L = O=PMe₃, O=PPh₃, O=PCy₃), and (C₅Me₅)₂U(F)(=N-2,6-iPr₂C₆H₃)) from their corresponding chloride, bromide, and iodide analogues. From these reactions, the new (C₅Me₅)₂UF₂(L) (L = O=PPh₃, O=PCy₃) uranium fluoride complexes were isolated and characterized by NMR spectroscopy and X-ray crystallography.

Direct Electrodeposition of UO2 from Uranyl Bis(trifluoromethanesulfonyl)imide Dissolved in 1-Ethyl-3-methylimidazolium Bis(trifluoromethanesulfonyl)imide Room Temperature Ionic Liquid System

DOE PAGES

Freiderich, John W.; Wanigasekara, Eranda P.; Sun, Xiao-Guang; ...

2013-11-11

Our study demonstrates a direct electrodeposition of UO 2 at a Pt cathode from a solution of uranyl bis(trifluoromethanesulfonyl)imide [UO 2(NTf 2) 2)] in a bulk room-temperature ionic liquid (RTIL), 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (EMIM +NTf 2 –). Cyclic voltammetry (CV) studies revealed two reduction waves corresponding to the conversion of uranium(VI) to uranium(IV), and a mechanism for the overall electroreduction is proposed. A controlled-potential experiment was performed, holding the reduction potential at–1.0 V for 24 h to obtain a brown-black deposit of UO 2 on the Pt cathode. The Faradaic efficiency of the reduction process was determined to be >80%. Themore » UO 2deposit was characterized by powder X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS).« less

Fast Oxidation Processes in a Naturally Reduced Aquifer Zone Caused by Dissolved Oxygen

NASA Astrophysics Data System (ADS)

Davis, J. A.; Jemison, N. E.; Williams, K. H.; Hobson, C.; Bush, R. P.

2014-12-01

The occurrence of naturally reduced zones is quite common in alluvial aquifers in the western U.S.A. due to the burial of woody debris in flood plains. The naturally reduced zones are heterogeneously dispersed in such aquifers and are characterized by high concentrations of organic carbon and reduced phases, including iron sulfides and reduced forms of metals, including uranium(IV). The persistence of high concentrations of dissolved uranium(VI) at uranium-contaminated aquifers on the Colorado Plateau has been attributed to slow oxidation of insoluble uranium(IV) mineral phases that are found in association with these natural reducing zones, although there is little understanding of the relative importance of various potential oxidants. Three field experiments were conducted within an alluvial aquifer adjacent to the Colorado River near Rifle, CO wherein groundwater associated with naturally reduced zones was pumped into a gas-impermeable tank, mixed with a conservative tracer (Br-), bubbled with a gas phase composed of 97% O2 and 3% CO2, and then returned to the subsurface in the same well from which it was withdrawn. Within minutes of re-injection of the oxygenated groundwater, dissolved uranium(VI) concentrations increased from less than 1 μM to greater than 2.5 μM, demonstrating that oxygen can be an important oxidant for uranium in these field systems if supplied to the naturally reduced zones. Small concentrations of nitrate were also observed in the previously nitrate-free groundwater, and Fe(II) decreased to the detection limit. These results contrast with other laboratory and field results in which oxygen was introduced to systems containing high concentrations of mackinawite (FeS) rather than the more crystalline iron sulfides found in aged, naturally reduced zones. The flux of oxygen to the naturally reduced zones in the alluvial aquifers occurs mainly through interactions between groundwater and gas phases at the water table, and seasonal variations of the water table at the Rifle, CO site may play an important role in introducing oxygen into the system. Although oxygen was introduced directly to the naturally reduced zones in these experiments, delivery of oxidants to the system may normally be controlled by other oxidative pathways in which oxygen plays an indirect role.

Oxidation of naturally reduced uranium in aquifer sediments by dissolved oxygen and its potential significance to uranium plume persistence

NASA Astrophysics Data System (ADS)

Davis, J. A.; Smith, R. L.; Bohlke, J. K.; Jemison, N.; Xiang, H.; Repert, D. A.; Yuan, X.; Williams, K. H.

2015-12-01

The occurrence of naturally reduced zones is common in alluvial aquifers in the western U.S.A. due to the burial of woody debris in flood plains. Such reduced zones are usually heterogeneously dispersed in these aquifers and characterized by high concentrations of organic carbon, reduced mineral phases, and reduced forms of metals, including uranium(IV). The persistence of high concentrations of dissolved uranium(VI) at uranium-contaminated aquifers on the Colorado Plateau has been attributed to slow oxidation of insoluble uranium(IV) mineral phases found in association with these reducing zones, although there is little understanding of the relative importance of various potential oxidants. Four field experiments were conducted within an alluvial aquifer adjacent to the Colorado River near Rifle, CO, wherein groundwater associated with the naturally reduced zones was pumped into a gas-impermeable tank, mixed with a conservative tracer (Br-), bubbled with a gas phase composed of 97% O2 and 3% CO2, and then returned to the subsurface in the same well from which it was withdrawn. Within minutes of re-injection of the oxygenated groundwater, dissolved uranium(VI) concentrations increased from less than 1 μM to greater than 2.5 μM, demonstrating that oxygen can be an important oxidant for uranium in such field systems if supplied to the naturally reduced zones. Dissolved Fe(II) concentrations decreased to the detection limit, but increases in sulfate could not be detected due to high background concentrations. Changes in nitrogen species concentrations were variable. The results contrast with other laboratory and field results in which oxygen was introduced to systems containing high concentrations of mackinawite (FeS), rather than the more crystalline iron sulfides found in aged, naturally reduced zones. The flux of oxygen to the naturally reduced zones in the alluvial aquifers occurs mainly through interactions between groundwater and gas phases at the water table. Seasonal variations of the water table at the Rifle, CO site may play an important role in introducing oxygen into the system. Although oxygen was introduced directly to the naturally reduced zones in these experiments, delivery of oxidants to the system may also be controlled by other oxidative pathways in which oxygen plays an indirect role.

Chloro-, methyl-, and (tetrahydroborato)tris((hexamethyldisilyl)amido)thorium(IV) and -uranium(IV). Crystal structure of (tetrahydroborato)tris((hexamethyldisilyl)amido)thorium(IV)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Turner, H.W.; Andersen, R.A.; Zalkin, A.

1979-05-01

Reaction of sodium (hexamethyldisilyl)amide with thorium tetrachloride or uranium tetrachloride yields chlorotris-((hexamethyldisilyl)amido)thorium(IV) or -uranium(IV), respectively. The chloroamides of thorium or uranium react with dimethylmagnesium or methyllithium yielding the methyl derivatives MeTh(N(SiMe/sub 3/)/sub 2/)/sub 3/ or MeU(N(SiMe/sub 3/)/sub 2/)/sub 3/, respectively. The chloro compounds yield BH/sub 4/M(N(SiMe/sub 3/)/sub 2/)/sub 3/ upon reaction with lithium tetrahydroborate, where M is thorium or uranium. Infrared spectra of the tetrahydroborate derivatives suggest that BH/sub 4/ is bonded in a tridentate fashion in both compounds, the metal atoms being six-coordinate. Single-crystal X-ray analysis of the thorium borohydride confirms the infrared result. The white BH/sub 4/Th(N(Si(CH/sub 3/))/submore » 2/)/sub 3/ crystals are rhombohedral with cell dimensions a/sub r/ = 11.137 A and ..cap alpha../sub r/ = 113.61/sup 0/; the triply primitive hexagonal cell has a/sub h/ = 18.640 (3) A c/sub h/ = 8.604 (1) A, V = 2489 A/sup 3/, Z = 3, and D/sub x/ = 1.40 g/cm/sup 3/, space group R3m. The structure was refined by full-matrix least squares to a conventional R factor of 0.031 for 1014 data. The Th atom is on a threefold axis 2.32 A from three nitrogen atoms and 2.61 A from the boron atom, a distance which represents a triple bridge bond between Th and B. The three (dimethylsilyl)amide ligands are disordered by a mirror plane parallel to the threefold axis. CH/sub 3/Th(N(Si(CH/sub 3/)/sub 3/)/sub 2/)/sub 3/ is isomorphous with BH/sub 4/Th(N(Si(CH/sub 3/)/sub 3/)/sub 2/)/sub 3/ with cell dimensions a/sub h/ = 18.68 (1) A and c/sub h/ = 8.537 (6) A. The diffraction data yielded integral'' = 12.16 +- 0.33 e for the imaginary scattering term for Th with Cu K..cap alpha.. radiation.« less

Development and blood compatibility assessment of electrospun polyvinyl alcohol blended with metallocene polyethylene and plectranthus amboinicus (PVA/mPE/PA) for bone tissue engineering.

PubMed

Qi, Jie; Zhang, Huang; Wang, Yingzhou; Mani, Mohan Prasath; Jaganathan, Saravana Kumar

2018-01-01

Currently, the design of extracellular matrix (ECM) with nanoscale properties in bone tissue engineering is challenging. For bone tissue engineering, the ECM must have certain properties such as being nontoxic, highly porous, and should not cause foreign body reactions. In this study, the hybrid scaffold based on polyvinyl alcohol (PVA) blended with metallocene polyethylene (mPE) and plectranthus amboinicus (PA) was fabricated for bone tissue engineering via electrospinning. The fabricated hybrid nanocomposites were characterized by scanning electron microscopy (SEM), Fourier transform and infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), contact angle measurement, and atomic force microscopy (AFM). Furthermore, activated partial thromboplastin time (APTT), prothrombin time (PT), and hemolytic assays were used to investigate the blood compatibility of the prepared hybrid nanocomposites. The prepared hybrid nanocomposites showed reduced fiber diameter (238±45 nm) and also increased porosity (87%) with decreased pore diameter (340±86 nm) compared with pure PVA. The interactions between PVA, mPE, and PA were identified by the formation of the additional peaks as revealed in FTIR. Furthermore, the prepared hybrid nanocomposites showed a decreased contact angle of 51°±1.32° indicating a hydrophilic nature and exhibited lower thermal stability compared to pristine PVA. Moreover, the mechanical results revealed that the electrospun scaffold showed an improved tensile strength of 3.55±0.29 MPa compared with the pristine PVA (1.8±0.52 MPa). The prepared hybrid nanocomposites showed delayed blood clotting as noted in APTT and PT assays indicating better blood compatibility. Moreover, the hemolysis assay revealed that the hybrid nanocomposites exhibited a low hemolytic index of 0.6% compared with pure PVA, which was 1.6% suggesting the safety of the developed nanocomposite to red blood cells (RBCs). The prepared nanocomposites exhibited better physico-chemical properties, sufficient porosity, mechanical strength, and blood compatibility, which favors it as a valuable candidate in bone tissue engineering for repairing the bone defects.

Metallocene-based antimalarials: an exploration into the influence of the ferrocenyl moiety on in vitro antimalarial activity in chloroquine-sensitive and chloroquine-resistant strains of Plasmodium falciparum.

PubMed

Blackie, Margaret A L; Beagley, Paul; Croft, Simon L; Kendrick, Howard; Moss, John R; Chibale, Kelly

2007-10-15

To establish the role of the ferrocenyl moiety in the antiplasmodial activity of ferroquine, compounds in which this moiety is replaced by the corresponding ruthenium-based moieties were synthesized and evaluated. In both the sensitive (D10) and resistant (K1) strains of Plasmodium falciparum, ruthenoquine analogues showed comparable potency to ferroquine. This suggests that a probable role of the ferrocenyl fragment is to serve simply as a hydrophobic spacer group. In addition, ferroquine analogues with different aromatic substituents were synthesized and evaluated. Unexpectedly high activity for quinoline compounds lacking the 7-chloro substituent suggests the ferrocenyl moiety may have an additive and/or synergistic effect.

Photoproduction of Hydrogen by Decamethylruthenocene Combined with Electrochemical Recycling.

PubMed

Rivier, Lucie; Peljo, Pekka; Vannay, Laurent A C; Gschwend, Grégoire C; Méndez, Manuel A; Corminboeuf, Clémence; Scanlon, Micheál D; Girault, Hubert H

2017-02-20

The photoinduced hydrogen evolution reaction (HER) by decamethylruthenocene, Cp 2 *Ru II (Cp*=C 5 Me 5 ), is reported. The use of a metallocene to photoproduce hydrogen is presented as an alternative strategy to reduce protons without involving an additional photosensitizer. The mechanism was investigated by (spectro)electrochemical and spectroscopic (UV/Vis and 1 H NMR) measurements. The photoactivated hydride involved was characterized spectroscopically and the resulting [Cp 2 *Ru III ] + species was electrochemically regenerated in situ on a fluorinated tin oxide electrode surface. A promising internal quantum yield of 25 % was obtained. Optimal experimental conditions- especially the use of weakly coordinating solvent and counterions-are discussed. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Catalyst system for the polymerization of alkenes to polyolefins

DOEpatents

Miller, Stephen A.; Bercaw, John E.

2002-01-01

The invention provides metallocene catalyst systems for the controlled polymerization of alkenes to a wide variety of polyolefins and olefin coplymers. Catalyst systems are provided that specifically produce isotactic, syndiotactic and steroblock polyolefins. The type of polymer produced can be controlled by varying the catalyst system, specifically by varying the ligand substituents. Such catalyst systems are particularly useful for the polymerization of polypropylene to give elastomeric polypropylenes. The invention also provides novel elastomeric polypropylene polymers characterized by dyad (m) tacticities of about 55% to about 65%, pentad (mmmm) tacticities of about 25% to about 35%, molecular weights (M.sub.w)in the range of about 50,000 to about 2,000,000, and have mmrm+rrmr peak is less than about 5%.

Catalyst system for the polymerization of alkenes to polyolefins

DOEpatents

Miller, Stephen A.; Bercaw, John E.

2004-02-17

The invention provides metallocene catalyst systems for the controlled polymerization of alkenes to a wide variety of polyolefins and olefin coplymers. Catalyst systems are provided that specifically produce isotactic, syndiotactic and steroblock polyolefins. The type of polymer produced can be controlled by varying the catalyst system, specifically by varying the ligand substituents. Such catalyst systems are particularly useful for the polymerization of polypropylene to give elastomeric polypropylenes. The invention also provides novel elastomeric polypropylene polymers characterized by dyad (m) tacticities of about 55% to about 65%, pentad (mmmm) tacticities of about 25% to about 35%, molecular weights (M.sub.W) in the range of about 50,000 to about 2,000,000, and have mmrm+rrmr peak is less than about 5%.

Ca(BH 4) 2 as a simple tool for the preparation of thorium and uranium metallocene borohydride complexes: First synthesis and crystal structure of (C 5Me 5) 2Th(η 3-H 3BH) 2

DOE PAGES

Erickson, Karla A.; Scott, Brian Lindley; Kiplinger, Jaqueline Loetsch

2017-01-18

Here, calcium borohydride allows for the high-yielding synthesis of (C 5Me 5)2An(η 3-H 3BH) 2 (An = Th, U) by reaction with (C 5Me 5) 2AnCl 2 (An = Th, U). While a preparative synthesis of (C 5Me 5) 2U(η 3-H 3BH) 2 has been previously reported in the literature using K(C 5Me 5) and U(BH 4) 4, the use of Ca(BH 4) 2 is higher yielding and mild. Full characterization of the novel compound (C 5Me 5) 2Th(η 3-H 3BH) 2 is presented.

Ca(BH 4) 2 as a simple tool for the preparation of thorium and uranium metallocene borohydride complexes: First synthesis and crystal structure of (C 5Me 5) 2Th(η 3-H 3BH) 2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Erickson, Karla A.; Scott, Brian Lindley; Kiplinger, Jaqueline Loetsch

Here, calcium borohydride allows for the high-yielding synthesis of (C 5Me 5)2An(η 3-H 3BH) 2 (An = Th, U) by reaction with (C 5Me 5) 2AnCl 2 (An = Th, U). While a preparative synthesis of (C 5Me 5) 2U(η 3-H 3BH) 2 has been previously reported in the literature using K(C 5Me 5) and U(BH 4) 4, the use of Ca(BH 4) 2 is higher yielding and mild. Full characterization of the novel compound (C 5Me 5) 2Th(η 3-H 3BH) 2 is presented.

Oligomerization of 2-chloroallyl alcohol by 2-pyridinecarboxylate complex of chromium(III) - new highly active and selective catalyst.

PubMed

Drzeżdżon, Joanna; Sikorski, Artur; Chmurzyński, Lech; Jacewicz, Dagmara

2018-06-05

The new 2-pyridinecarboxylate (2-pic) complex of chromium(III) has been designed and synthesized as a new highly active and selective oligomerization catalyst. The crystal structure of the new compound has been determined by X-ray diffraction. The composition and purity of [Cr(2-pic) 2 (OH 2 ) 2 ]NO 3 have been confirmed by several spectroscopic methods and the elemental analysis. Furthermore, the new complex has been investigated towards its catalytic activity for the oligomerization of 2-chloro-2-propen-1-ol under the atmospheric pressure and at room temperature. It has turned out that the novel catalyst exhibits a very high catalytic activity. Consequently, [Cr(2-pic) 2 (OH 2 ) 2 ]NO 3 belongs to a new generation of non-metallocene catalysts.

Mild hydrothermal crystal growth of new uranium(IV) fluorides, Na{sub 3.13}Mg{sub 1.43}U{sub 6}F{sub 30} and Na{sub 2.50}Mn{sub 1.75}U{sub 6}F{sub 30}: Structures, optical and magnetic properties

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yeon, Jeongho; Smith, Mark D.; Tapp, Joshua

Two new uranium(IV) fluorides, Na{sub 3.13}Mg{sub 1.43}U{sub 6}F{sub 30} (1) and Na{sub 2.50}Mn{sub 1.75}U{sub 6}F{sub 30} (2), were synthesized through an in situ mild hydrothermal route, and were structurally characterized by single crystal X-ray diffraction. The compounds exhibit complex crystal structures composed of corner- or edge-shared UF{sub 9} and MF{sub 6} (M=Mg, Mn) polyhedra, forming hexagonal channels in the three-dimensional framework, in which ordered or disordered divalent metal and sodium atoms reside. The large hexagonal voids contain the nearly regular M(II)F{sub 6} octahedra and sodium ions, whereas the small hexagonal cavities include M(II) and sodium ions on a mixed-occupied site.more » Magnetic susceptibility measurements yielded effective magnetic moments of 8.36 and 11.6 µ{sub B} for 1 and 2, respectively, confirming the presence and oxidation states of U(IV) and Mn(II). The large negative Weiss constants indicate the spin gap between a triplet and a singlet state in the U(IV). Magnetization data as a function of applied fields revealed that 2 exhibits paramagnetic behavior due to the nonmagnetic singlet ground state of U(IV) at low temperature. UV–vis diffuse reflectance and X-ray photoelectron spectroscopy data were also analyzed. - Graphical abstract: Two new quaternary U(IV) fluorides, Na{sub 3.13}Mg{sub 1.43}U{sub 6}F{sub 30} and Na{sub 2.50}Mn{sub 1.75}U{sub 6}F{sub 30}, were crystallized via an in situ reduction step of U(VI) to U(IV) under mild hydrothermal conditions. The compounds show complex crystal structures based on the 3-D building block of U{sub 6}F{sub 30}. Magnetic property measurements revealed that the U(IV) exhibits a nonmagnetic singlet ground state at low temperature with a spin gap. - Highlights: • Na{sub 3.13}Mg{sub 1.43}U{sub 6}F{sub 30} and Na{sub 2.50}Mn{sub 1.75}U{sub 6}F{sub 30} have been synthesized and characterized. • The U(IV) fluorides exhibit complex three-dimensional crystal structures. • The optical properties were investigated. • Magnetic susceptibility data were collected.« less

Supported metallocene catalysts by surface organometallic chemistry. Synthesis, characterization, and reactivity in ethylene polymerization of oxide-supported mono- and biscyclopentadienyl zirconium alkyl complexes: establishment of structure/reactivity relationships.

PubMed

Jezequel, M; Dufaud, V; Ruiz-Garcia, M J; Carrillo-Hermosilla, F; Neugebauer, U; Niccolai, G P; Lefebvre, F; Bayard, F; Corker, J; Fiddy, S; Evans, J; Broyer, J P; Malinge, J; Basset, J M

2001-04-18

The reactions of CpZr(CH(3))(3), 1, and Cp(2)Zr(CH(3))(2), 2, with partially dehydroxylated silica, silica-alumina, and alumina surfaces have been carried out with careful identification of the resulting surface organometallic complexes in order to probe the relationship between catalyst structure and polymerization activity. The characterization of the supported complexes has been achieved in most cases by in situ infrared spectroscopy, surface microanalysis, qualitative and quantitative analysis of evolved gases during surface reactions with labeled surface, solid state (1)H and (13)C NMR using (13)C-enriched compounds, and EXAFS. 1 and 2 react with silica(500) and silica-alumina(500) by simple protonolysis of one Zr-Me bond by surface silanols with formation of a single well-defined neutral compound. In the case of silica-alumina, a fraction of the supported complexes exhibits some interactions with electronically unsaturated surface aluminum sites. 1 and 2 also react with the hydroxyl groups of gamma-alumina(500), leading to several surface structures. Correlation between EXAFS and (13)C NMR data suggests, in short, two main surface structures having different environments for the methyl group: [Al](3)-OZrCp(CH(3))(2) and [Al](2)-OZrCp(CH(3))(mu-CH(3))-[Al] for the monoCp series and [Al](2)-OZrCp(2)(CH(3)) and [Al]-OZrCp(2)(mu-CH(3))-[Al] for the bisCp series. Ethylene polymerization has been carried out with all the supported complexes under various reaction conditions. Silica-supported catalysts in the absence of any cocatalyst exhibited no activity whatsoever for ethylene polymerization. When the oxide contained Lewis acidic sites, the resulting surface species were active. The activity, although improved by the presence of additional cocatalysts, remained very low by comparison with that of the homogeneous metallocene systems. This trend has been interpreted on the basis of various possible parameters, including the (p-pi)-(d-pi) back-donation of surface oxygen atoms to the zirconium center.

Linking Chaotic Advection with Subsurface Biogeochemical Processes

NASA Astrophysics Data System (ADS)

Mays, D. C.; Freedman, V. L.; White, S. K.; Fang, Y.; Neupauer, R.

2017-12-01

This work investigates the extent to which groundwater flow kinematics drive subsurface biogeochemical processes. In terms of groundwater flow kinematics, we consider chaotic advection, whose essential ingredient is stretching and folding of plumes. Chaotic advection is appealing within the context of groundwater remediation because it has been shown to optimize plume spreading in the laminar flows characteristic of aquifers. In terms of subsurface biogeochemical processes, we consider an existing model for microbially-mediated reduction of relatively mobile uranium(VI) to relatively immobile uranium(IV) following injection of acetate into a floodplain aquifer beneath a former uranium mill in Rifle, Colorado. This model has been implemented in the reactive transport code eSTOMP, the massively parallel version of STOMP (Subsurface Transport Over Multiple Phases). This presentation will report preliminary numerical simulations in which the hydraulic boundary conditions in the eSTOMP model are manipulated to simulate chaotic advection resulting from engineered injection and extraction of water through a manifold of wells surrounding the plume of injected acetate. This approach provides an avenue to simulate the impact of chaotic advection within the existing framework of the eSTOMP code.

Tuning the Oxidation State, Nuclearity, and Chemistry of Uranium Hydrides with Phenylsilane and Temperature: The Case of the Classic Uranium(III) Hydride Complex [(C 5 Me 5) 2U(μ-H)] 2

DOE PAGES

Pagano, Justin K.; Dorhout, Jacquelyn M.; Czerwinski, Kenneth R.; ...

2016-03-18

Here, this work demonstrates that the oxidation state and chemistry of uranium hydrides can be tuned with temperature and the stoichiometry of phenylsilane. The trivalent uranium hydride [(C 5Me 5) 2U–H] x (5) was found to be comprised of an equilibrium mixture of U(III) hydrides in solution at ambient temperature. A single U(III) species can be selectively prepared by treating (C 5Me5)2UMe2 (4) with 2 equiv of phenylsilane at 50 °C. The U(III) system is a potent reducing agent and displayed chemistry distinct from the U(IV) system [(C 5Me 5) 2U(H)(μ-H)] 2 (2), which was harnessed to prepare a varietymore » of organometallic complexes, including (C 5Me 5) 2U(dmpe)(H) (6), and the novel uranium(IV) metallacyclopentadiene complex (C 5Me 5) 2U(C 4Me 4) (11).« less

Synthesis, characterization, and reactivity of the first uranium metallocene 1,2 bis(diphenylphosphino)acetylene complexes.

DOE PAGES

Pagano, Justin Kane; Scott, Brian Lindley; Kiplinger, Jaqueline Loetsch

2018-06-09

Two new uranium metallacyclopropenes, (C 5Me 4R) 2U(η 2-Ph 2PC=CPPh 2) (R = Me, Et) were prepared by reducing the corresponding (C 5Me 4R) 2UCl 2 complexes with KC 8 in the presence of 1,2-bis(diphenylphosphino)acetylene (Ph 2P–C≡C–PPh 2). Both compounds were fully characterized by a combination of elemental analysis and multinuclear NMR, UV–visible–NIR, and IR spectroscopies. Differences in the electronic spectra of these novel compounds and the known (C 5Me 5) 2U(η 2-Me 3SiC=CSiMe 3) are discussed. Finally, also presented is the solid-state structure of (C 5Me 4Et) 2U(η 2-Ph 2PC=CPPh 2), which reveals significant distortions of the coordinated 1,2-bis(diphenylphosphino)acetylenemore » (Ph 2P–C≡C–PPh 2) ligand.« less

Synthesis, characterization, and reactivity of the first uranium metallocene 1,2 bis(diphenylphosphino)acetylene complexes.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pagano, Justin Kane; Scott, Brian Lindley; Kiplinger, Jaqueline Loetsch

Two new uranium metallacyclopropenes, (C 5Me 4R) 2U(η 2-Ph 2PC=CPPh 2) (R = Me, Et) were prepared by reducing the corresponding (C 5Me 4R) 2UCl 2 complexes with KC 8 in the presence of 1,2-bis(diphenylphosphino)acetylene (Ph 2P–C≡C–PPh 2). Both compounds were fully characterized by a combination of elemental analysis and multinuclear NMR, UV–visible–NIR, and IR spectroscopies. Differences in the electronic spectra of these novel compounds and the known (C 5Me 5) 2U(η 2-Me 3SiC=CSiMe 3) are discussed. Finally, also presented is the solid-state structure of (C 5Me 4Et) 2U(η 2-Ph 2PC=CPPh 2), which reveals significant distortions of the coordinated 1,2-bis(diphenylphosphino)acetylenemore » (Ph 2P–C≡C–PPh 2) ligand.« less

A Heterobimetallic Complex With an Unsupported Uranium(III)-Aluminum(I) Bond: (CpSiMe3)3U-AlCp* (Cp* = C5Me5)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Minasian, Stefan; Krinsky Ph.D., Jamin; Williams, Valerie

2008-07-23

The discovery of molecular metal-metal bonds has been of fundamental importance to the understanding of chemical bonding. For the actinides, examples of unsupported metal-metal bonds are relatively uncommon, consisting of Cp{sub 3}U-SnPh{sub 3}, and several actinide-transition metal complexes. Traditionally, bonding in the f-elements has been described as electrostatic; however, elucidating the degree of covalency is a subject of recent research. In carbon monoxide complexes of the trivalent uranium metallocenes, decreased {nu}{sub CO} values relative to free CO suggest that the U(III) atom acts as a {pi}-donor. Ephritikhine and coworkers have demonstrated that {pi}-accepting ligands can differentiate trivalent lanthanide and actinidemore » ions, an effect that renders this chemistry of interest in the context of nuclear waste separation technology.« less

Synthesis and reactivity of bis(tetramethylcyclopentadienyl) yttrium metallocenes including the reduction of Me(3)SiN(3) to [(Me(3)Si)(2)N](-) with [(C(5)Me(4)H)(2)Y(THF)](2)(mu-eta(2):eta(2)-N(2)).

PubMed

Lorenz, Sara E; Schmiege, Benjamin M; Lee, David S; Ziller, Joseph W; Evans, William J

2010-07-19

The metallocene precursors needed to provide the tetramethylcyclopentadienyl yttrium complexes (C(5)Me(4)H)(3)Y, [(C(5)Me(4)H)(2)Y(THF)](2)(mu-eta(2):eta(2)-N(2)), and [(C(5)Me(4)H)(2)Y(mu-H)](2) for reactivity studies have been synthesized and fully characterized, and their reaction chemistry has led to an unexpected conversion of an azide to an amide. (C(5)Me(4)H)(2)Y(mu-Cl)(2)K(THF)(x), 1, synthesized from YCl(3) and KC(5)Me(4)H reacts with allylmagnesium chloride to make (C(5)Me(4)H)(2)Y(eta(3)-C(3)H(5)), 2, which is converted to [(C(5)Me(4)H)(2)Y][(mu-Ph)(2)BPh(2)], 3, with [Et(3)NH][BPh(4)]. Complex 3 reacts with KC(5)Me(4)H to form (C(5)Me(4)H)(3)Y, 4. The reduced dinitrogen complex, [(C(5)Me(4)H)(2)Y(THF)](2)(mu-eta(2):eta(2)-N(2)), 5, can be synthesized from either [(C(5)Me(4)H)(2)Y](2)[(mu-Ph)(2)BPh(2)], 3, or (C(5)Me(4)H)(3)Y, 4, with potassium graphite under a dinitrogen atmosphere. The (15)N labeled analogue, [(C(5)Me(4)H)(2)Y(THF)](2)(mu-eta(2):eta(2)-(15)N(2)), 5-(15)N, has also been prepared, and the (15)N NMR data have been compared to previously characterized reduced dinitrogen complexes. Complex 2 reacts with H(2) to form the corresponding hydride, [(C(5)Me(4)H)(2)Y(mu-H)](2), 6. Complex 5 displays similar reactivity to that of the analogous [(C(5)Me(4)H)(2)Ln(THF)](2)(mu-eta(2):eta(2)-N(2)) complexes (Ln = La, Lu), with substrates such as phenazine, anthracene, and CO(2). In addition, 5 reduces Me(3)SiN(3) to form (C(5)Me(4)H)(2)Y[N(SiMe(3))(2)], 7.

Carbon K-edge X-ray absorption spectroscopy and time-dependent density functional theory examination of metal-carbon bonding in metallocene dichlorides.

PubMed

Minasian, Stefan G; Keith, Jason M; Batista, Enrique R; Boland, Kevin S; Kozimor, Stosh A; Martin, Richard L; Shuh, David K; Tyliszczak, Tolek; Vernon, Louis J

2013-10-02

Metal-carbon covalence in (C5H5)2MCl2 (M = Ti, Zr, Hf) has been evaluated using carbon K-edge X-ray absorption spectroscopy (XAS) as well as ground-state and time-dependent hybrid density functional theory (DFT and TDDFT). Differences in orbital mixing were determined experimentally using transmission XAS of thin crystalline material with a scanning transmission X-ray microscope (STXM). Moving down the periodic table (Ti to Hf) has a marked effect on the experimental transition intensities associated with the low-lying antibonding 1a1* and 1b2* orbitals. The peak intensities, which are directly related to the M-(C5H5) orbital mixing coefficients, increase from 0.08(1) and 0.26(3) for (C5H5)2TiCl2 to 0.31(3) and 0.75(8) for (C5H5)2ZrCl2, and finally to 0.54(5) and 0.83(8) for (C5H5)2HfCl2. The experimental trend toward increased peak intensity for transitions associated with 1a1* and 1b2* orbitals agrees with the calculated TDDFT oscillator strengths [0.10 and 0.21, (C5H5)2TiCl2; 0.21 and 0.73, (C5H5)2ZrCl2; 0.35 and 0.69, (C5H5)2HfCl2] and with the amount of C 2p character obtained from the Mulliken populations for the antibonding 1a1* and 1b2* orbitals [8.2 and 23.4%, (C5H5)2TiCl2; 15.3 and 39.7%, (C5H5)2ZrCl2; 20.1 and 50.9%, (C5H5)2HfCl2]. The excellent agreement between experiment, theory, and recent Cl K-edge XAS and DFT measurements shows that C 2p orbital mixing is enhanced for the diffuse Hf (5d) and Zr (4d) atomic orbitals in relation to the more localized Ti (3d) orbitals. These results provide insight into how changes in M-Cl orbital mixing within the metallocene wedge are correlated with periodic trends in covalent bonding between the metal and the cyclopentadienide ancillary ligands.

Oil-in-oil emulsions: a unique tool for the formation of polymer nanoparticles.

PubMed

Klapper, Markus; Nenov, Svetlin; Haschick, Robert; Müller, Kevin; Müllen, Klaus

2008-09-01

Polymer latex particles are nanofunctional materials with widespread applications including electronics, pharmaceuticals, photonics, cosmetics, and coatings. These materials are typically prepared using waterborne heterogeneous systems such as emulsion, miniemulsion, and suspension polymerization. However, all of these processes are limited to water-stable catalysts and monomers mainly polymerizable via radical polymerization. In this Account, we describe a method to overcome this limitation: nonaqueous emulsions can serve as a versatile tool for the synthesis of new types of polymer nanoparticles. To form these emulsions, we first needed to find two nonmiscible nonpolar/polar aprotic organic solvents. We used solvent mixtures of either DMF or acetonitrile in alkanes and carefully designed amphiphilic block and statistical copolymers, such as polyisoprene- b-poly(methyl methacrylate) (PI- b-PMMA), as additives to stabilize these emulsions. Unlike aqueous emulsions, these new emulsion systems allowed the use of water-sensitive monomers and catalysts. Although polyaddition and polycondensation reactions usually lead to a large number of side products and only to oligomers in the aqueous phase, these new conditions resulted in high-molecular-weight, defect-free polymers. Furthermore, conducting nanoparticles were produced by the iron(III)-induced synthesis of poly(ethylenedioxythiophene) (PEDOT) in an emulsion of acetonitrile in cyclohexane. Because metallocenes are sensitive to nitrile and carbonyl groups, the acetonitrile and DMF emulsions were not suitable for carrying out metallocene-catalyzed olefin polymerization. Instead, we developed a second system, which consists of alkanes dispersed in perfluoroalkanes. In this case, we designed a new amphipolar polymeric emulsifier with fluorous and aliphatic side chains to stabilize the emulsions. Such heterogeneous mixtures facilitated the catalytic polymerization of ethylene or propylene to give spherical nanoparticles of high molecular weight polyolefins. These nonaqueous systems also allow for the combination of different polymerization techniques to obtain complex architectures such as core-shell structures. Previously, such structures primarily used vinylic monomers, which greatly limited the number of polymer combinations. We have demonstrated how nonaqueous emulsions allow the use of a broad variety of hydrolyzable monomers and sensitive catalysts to yield polyester, polyurethane, polyamide, conducting polymers, and polyolefin latex particles in one step under ambient reaction conditions. This nonpolar emulsion strategy dramatically increases the chemical palette of polymers that can form nanoparticles via emulsion polymerization.

In situ spectroscopy and spectroelectrochemistry of uranium in high-temperature alkali chloride molten salts.

PubMed

Polovov, Ilya B; Volkovich, Vladimir A; Charnock, John M; Kralj, Brett; Lewin, Robert G; Kinoshita, Hajime; May, Iain; Sharrad, Clint A

2008-09-01

Soluble uranium chloride species, in the oxidation states of III+, IV+, V+, and VI+, have been chemically generated in high-temperature alkali chloride melts. These reactions were monitored by in situ electronic absorption spectroscopy. In situ X-ray absorption spectroscopy of uranium(VI) in a molten LiCl-KCl eutectic was used to determine the immediate coordination environment about the uranium. The dominant species in the melt was [UO 2Cl 4] (2-). Further analysis of the extended X-ray absorption fine structure data and Raman spectroscopy of the melts quenched back to room temperature indicated the possibility of ordering beyond the first coordination sphere of [UO 2Cl 4] (2-). The electrolytic generation of uranium(III) in a molten LiCl-KCl eutectic was also investigated. Anodic dissolution of uranium metal was found to be more efficient at producing uranium(III) in high-temperature melts than the cathodic reduction of uranium(IV). These high-temperature electrolytic processes were studied by in situ electronic absorption spectroelectrochemistry, and we have also developed in situ X-ray absorption spectroelectrochemistry techniques to probe both the uranium oxidation state and the uranium coordination environment in these melts.

Catalytic Dehydrogenation of Dimethylamine Borane by Highly Active Thorium and Uranium Metallocene Complexes

DOE PAGES

Erickson, Karla A.; Kiplinger, Jaqueline L.

2017-05-19

In the thorium and uranium complexes (C 5Me 5) 2AnMe 2, [(C 5Me 5) 2An(H)(μ-H)] 2 (An = Th, U) and [(C 5Me 5) 2U(H)] 2 dehydrogenate dimethylamine borane (Me2NH·BH3) at room temperature. Upon mild heating at 45 °C, turnover frequencies (TOFs) of 400 h –1 are obtained, which is comparable to some of the fastest Me 2NH·BH 3 dehydrogenation catalysts known in the literature. We propose a β-hydride elimination mechanism for dehydrogenation because of the observation of Me 2N=BH 2, Me 2N=BMe 2, and Me 2N=BHMe in the 11B NMR spectra of catalytic and stoichiometric reactions. The similar catalyticmore » metrics between the actinide dimethyl and hydride complexes with Me 2NH·BH 3 indicate that the actinide hydride complexes are the active catalysts in this chemistry.« less

Catalytic Dehydrogenation of Dimethylamine Borane by Highly Active Thorium and Uranium Metallocene Complexes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Erickson, Karla A.; Kiplinger, Jaqueline L.

In the thorium and uranium complexes (C 5Me 5) 2AnMe 2, [(C 5Me 5) 2An(H)(μ-H)] 2 (An = Th, U) and [(C 5Me 5) 2U(H)] 2 dehydrogenate dimethylamine borane (Me2NH·BH3) at room temperature. Upon mild heating at 45 °C, turnover frequencies (TOFs) of 400 h –1 are obtained, which is comparable to some of the fastest Me 2NH·BH 3 dehydrogenation catalysts known in the literature. We propose a β-hydride elimination mechanism for dehydrogenation because of the observation of Me 2N=BH 2, Me 2N=BMe 2, and Me 2N=BHMe in the 11B NMR spectra of catalytic and stoichiometric reactions. The similar catalyticmore » metrics between the actinide dimethyl and hydride complexes with Me 2NH·BH 3 indicate that the actinide hydride complexes are the active catalysts in this chemistry.« less

Plasticized chitosan/polyolefin films produced by extrusion.

PubMed

Matet, Marie; Heuzey, Marie-Claude; Ajji, Abdellah; Sarazin, Pierre

2015-03-06

Plasticized chitosan and polyethylene blends were produced through a single-pass extrusion process. Using a twin-screw extruder, chitosan plasticization was achieved in the presence of an acetic acid solution and glycerol, and directly mixed with metallocene polyethylene, mPE, to produce a masterbatch. Different dilutions of the masterbatch (2, 5 and 10 wt% of plasticized chitosan), in the presence of ethylene vinyl acetate, EVA, were subsequently achieved in single screw film extrusion. Very small plasticized chitosan domains (number average diameter <5 μm) were visible in the polymeric matrix. The resulting films presented a brown color and increasing haze with chitosan plasticized content. Mechanical properties of the mPE films were affected by the presence of plasticized chitosan, but improvement was observed as a result of some compatibility between mPE and chitosan in the presence of EVA. Finally the incorporation of plasticized chitosan affected mPE water vapor permeability while oxygen permeability remained constant. Copyright © 2014 Elsevier Ltd. All rights reserved.

Oxidative Uranium Release from Anoxic Sediments under Diffusion-Limited Conditions.

PubMed

Bone, Sharon E; Cahill, Melanie R; Jones, Morris E; Fendorf, Scott; Davis, James; Williams, Kenneth H; Bargar, John R

2017-10-03

Uranium (U) contamination occurs as a result of mining and ore processing; often in alluvial aquifers that contain organic-rich, reduced sediments that accumulate tetravalent U, U(IV). Uranium(IV) is sparingly soluble, but may be mobilized upon exposure to nitrate (NO 3 - ) and oxygen (O 2 ), which become elevated in groundwater due to seasonal fluctuations in the water table. The extent to which oxidative U mobilization can occur depends upon the transport properties of the sediments, the rate of U(IV) oxidation, and the availability of inorganic reductants and organic electron donors that consume oxidants. We investigated the processes governing U release upon exposure of reduced sediments to artificial groundwater containing O 2 or NO 3 - under diffusion-limited conditions. Little U was mobilized during the 85-day reaction, despite rapid diffusion of groundwater within the sediments and the presence of nonuraninite U(IV) species. The production of ferrous iron and sulfide in conjunction with rapid oxidant consumption suggested that the sediments harbored large concentrations of bioavailable organic carbon that fueled anaerobic microbial respiration and stabilized U(IV). Our results suggest that seasonal influxes of O 2 and NO 3 - may cause only localized mobilization of U without leading to export of U from the reducing sediments when ample organic carbon is present.

Uranium(IV) adsorption by natural organic matter in anoxic sediments

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bone, Sharon E.; Dynes, James J.; Cliff, John

2017-01-09

Uranium is an important fuel source and a global environmental contaminant. It accumulates in the tetravalent state, U(IV), in anoxic sediments, including ore deposits, marine basins, and contaminated aquifers. However, very little is known about the speciation of U(IV) in low temperature geochemical environments, inhibiting the development of a conceptual model of U behavior. Until recently, U(IV) was assumed to exist predominantly as the sparingly soluble mineral uraninite (UO 2) in anoxic sediments; yet studies now show that UO 2 is not often dominant in these environments. However, a model of U(IV) speciation under environmentally relevant conditions has not yetmore » been developed. Here we show that complexes of U(IV) adsorb on organic carbon and organic carbon-coated clays in an organic-rich natural substrate under field-relevant conditions. Whereas previous research assumed that the U(IV) product depended on the reduction pathway, our results demonstrate that UO 2 formation can be inhibited simply by decreasing the U:solid ratio. Thus, it is the number and type of surface ligands that controls U(IV) speciation subsequent to U(VI) reduction. Projections of U transport and bioavailability, and thus its threat to human and ecosystem health, must consider retention of U(IV) ions within the local sediment environment.« less

The Effect of Temperature on Kinetics and Diffusion Coefficients of Metallocene Derivatives in Polyol-Based Deep Eutectic Solvents

PubMed Central

Bahadori, Laleh; Chakrabarti, Mohammed Harun; Manan, Ninie Suhana Abdul; Hashim, Mohd Ali; Mjalli, Farouq Sabri; AlNashef, Inas Muen; Brandon, Nigel

2015-01-01

The temperature dependence of the density, dynamic viscosity and ionic conductivity of several deep eutectic solvents (DESs) containing ammonium-based salts and hydrogen bond donvnors (polyol type) are investigated. The temperature-dependent electrolyte viscosity as a function of molar conductivity is correlated by means of Walden’s rule. The oxidation of ferrocene (Fc/Fc+) and reduction of cobaltocenium (Cc+/Cc) at different temperatures are studied by cyclic voltammetry and potential-step chronoamperometry in DESs. For most DESs, chronoamperometric transients are demonstrated to fit an Arrhenius-type relation to give activation energies for the diffusion of redox couples at different temperatures. The temperature dependence of the measured conductivities of DES1 and DES2 are better correlated with the Vogel-Tamman-Fulcher equation. The kinetics of the Fc/Fc+ and Cc+/Cc electrochemical systems have been investigated over a temperature range from 298 to 338 K. The heterogeneous electron transfer rate constant is then calculated at different temperatures by means of a logarithmic analysis. The glycerol-based DES (DES5) appears suitable for further testing in electrochemical energy storage devices. PMID:26642045

Kinetics of initiation, propagation, and termination for the [rac-(C(2)H(4)(1-indenyl)(2))ZrMe][MeB(C(6)F(5))(3)]-catalyzed polymerization of 1-hexene.

PubMed

Liu, Z; Somsook, E; White, C B; Rosaaen, K A; Landis, C R

2001-11-14

Metallocene-catalyzed polymerization of 1-alkenes offers fine control of critical polymer attributes such as molecular weight, polydispersity, tacticity, and comonomer incorporation. Enormous effort has been expended on the synthesis and discovery of new catalysts and activators, but elementary aspects of the catalytic processes remain unclear. For example, it is unclear how the catalyst is distributed among active and dormant sites and how this distribution influences the order in monomer for the propagation rates, for which widely varying values are reported. Similarly, although empirical relationships between average molecular weights and monomer have been established for many systems, the underlying mechanisms of chain termination are unclear. Another area of intense interest concerns the role of ion-pairing in controlling the activity and termination mechanisms of metallocene-catalyzed polymerizations. Herein we report the application of quenched-flow kinetics, active site counting, polymer microstructure analysis, and molecular weight distribution analysis to the determination of fundamental rate laws for initiation, propagation, and termination for the polymerization of 1-hexene in toluene solution as catalyzed by the contact ion-pair, [rac-(C(2)H(4)(1-indenyl)(2))ZrMe][MeB(C(6)F(5))(3)] (1) over the temperature range of -10 to 50 degrees C. Highly isotactic (>99% mmmm) poly-1-hexene is produced with no apparent enchained regioerrors. Initiation and propagation processes are first order in the concentrations of 1-hexene and 1 but independent of excess borane or the addition of the contact ion-pair [PhNMe(3)][MeB(C(6)F(5))(3)]. Active site counting and the reaction kinetics provide no evidence of catalyst accumulation in dormant or inactive sites. Initiation is slower than propagation by a factor of 70. The principal termination process is the formation of unsaturates of two types: vinylidene end groups that arise from termination after a 1,2 insertion and vinylene end groups that follow 2,1 insertions. The rate law for the former termination process is independent of the 1-hexene concentration, whereas the latter is first order. Analysis of (13)C-labeled polymer provides support for a mechanism of vinylene end group formation that is not chain transfer to monomer. Deterministic modeling of the molecular weight distributions using the fundamental rate laws and kinetic constants demonstrates the robustness of the kinetic analysis. Comparisons of insertion frequencies with estimated limits on the rates of ion-pair symmetrization obtained by NMR suggest that ion-pair separation prior to insertion is not required, but the analysis requires assumptions that cannot be validated.

What a difference a 5f element makes: trivalent and tetravalent uranium halide complexes supported by one and two bis[2-(diisopropylphosphino)-4-methylphenyl]amido (PNP) ligands.

PubMed

Cantat, Thibault; Scott, Brian L; Morris, David E; Kiplinger, Jaqueline L

2009-03-02

The coordination behavior of the bis[2-(diisopropylphosphino)-4-methylphenyl]amido ligand (PNP) toward UI3(THF)4 and UCl4 has been investigated to access new uranium(III) and uranium(IV) halide complexes supported by one and two PNP ligands. The reaction between (PNP)K (6) and 1 equiv of UI3(THF)4 afforded the trivalent halide complex (PNP)UI2(4-tBu-pyridine)2 (7) in the presence of 4-tert-butylpyridine. The same reaction carried out with UCl4 and no donor ligand gave [(PNP)UCl3]2 (8), in which the uranium coordination sphere in the (PNP)UCl3 unit is completed by a bridging chloride ligand. When UCl4 is reacted with 1 equiv (PNP)K (6) in the presence of THF, trimethylphosphine oxide (TMPO), or triphenylphosphineoxide (TPPO), the tetravalent halide complexes (PNP)UCl3(THF) (9), (PNP)UCl3(TMPO)2 (10), and (PNP)UCl3(TPPO) (11), respectively, are formed in excellent yields. The bis(PNP) complexes of uranium(III), (PNP)2UI (12), and uranium(IV), (PNP)2UCl2 (13), were easily isolated from the analogous reactions between 2 equiv of 6 and UI3(THF)4 or UCl4, respectively. Complexes 12 and 13 represent the first examples of complexes featuring two PNP ligands coordinated to a single metal center. Complexes 7-13 have been characterized by single-crystal X-ray diffraction and 1H and 31P NMR spectroscopy. The X-ray structures demonstrate the ability of the PNP ligand to adopt new coordination modes upon coordination to uranium. The PNP ligand can adopt both pseudo-meridional and pseudo-facial geometries when it is kappa3-(P,N,P) coordinated, depending on the steric demand at the uranium metal center. Additionally, its hemilabile character was demonstrated with an unusual kappa2-(P,N) coordination mode that is maintained in both the solid-state and in solution. Comparison of the structures of the mono(PNP) and bis(PNP) complexes 7, 9, 11-13 with their respective C5Me5 analogues 1-4 undoubtedly show that a more sterically congested environment is provided by the PNP ligand. The electronic influence of replacing the C5Me5 ligands with PNP was investigated using electronic absorption spectroscopy and electrochemistry. For 12 and 13, a chemically reversible wave corresponding to the UIV/UIII redox transformation comparable to that for 3 and 4 was observed. However, a 350 mV shift of this couple to more negative potentials was observed on substitution of the bis(C5Me5) by the bis(PNP) framework, therefore pointing to a greater electronic density at the metal center in the PNP complexes. The UV-visible region of the electronic spectra for the mono(PNP) and bis(PNP) complexes appear to be dominated by PNP ligand-based transitions that are shifted to higher energy in the uranium complexes than in the simple ligand anion (6) spectrum, for both the UVI and UIII oxidation states. The near IR region in complexes 1-4 and 7, 9, 11-13 is dominated by f-f transitions derived from the 5f3 and 5f2 valence electronic configuration of the metal center. Though complexes of both ligand sets exhibit similar intensities in their f-f bands, a somewhat larger ligand-field splitting was observed for the PNP system, consistent with its higher electron donating ability.

Experimental and molecular dynamics simulation study of the sublimation energetics of cyclopentadienyltricarbonylmanganese (Cymantrene).

PubMed

Picciochi, Ricardo; Canongia Lopes, José N; Diogo, Hermínio P; Minas da Piedade, Manuel E

2008-10-16

The standard molar enthalpy of sublimation of monoclinic cyclopentadienyltricarbonylmanganese, Mn(eta (5)-C 5H 5)(CO) 3, at 298.15 K, was determined as Delta sub H m (o)[Mn(eta (5)-C 5H 5)(CO) 3] = 75.97 +/- 0.37 kJ x mol (-1) from Knudsen effusion and Calvet-drop microcalorimetry measurements, thus considerably improving the very large inaccuracy (>10 kJ x mol (-1)) of the published data. The obtained value was used to assess the extension of the OPLS-based all-atom force field we previously developed for iron metallocenes to manganese organometallic compounds. The modified force field was able to reproduce the volumetric properties (density and unit-cell volume) of crystalline Mn(eta (5)-C 5H 5)(CO) 3 with a deviation of 0.6% and the experimentally determined enthalpy of sublimation with an accuracy of 1 kJ x mol (-1). The interaction (epsilon) and atomic-diameter (sigma) parameters of the Lennard-Jones (12-6) potential function used to calculate dispersion contributions within the framework of the force field were found to be transferable from iron to manganese.

Investigation of the electronic ground states for a reduced pyridine(diimine) uranium series: evidence for a ligand tetraanion stabilized by a uranium dimer.

PubMed

Anderson, Nickolas H; Odoh, Samuel O; Williams, Ursula J; Lewis, Andrew J; Wagner, Gregory L; Lezama Pacheco, Juan; Kozimor, Stosh A; Gagliardi, Laura; Schelter, Eric J; Bart, Suzanne C

2015-04-15

The electronic structures of a series of highly reduced uranium complexes bearing the redox-active pyridine(diimine) ligand, (Mes)PDI(Me) ((Mes)PDI(Me) = 2,6-(2,4,6-Me3-C6H2-N═CMe)2C5H3N) have been investigated. The complexes, ((Mes)PDI(Me))UI3(THF) (1), ((Mes)PDI(Me))UI2(THF)2 (2), [((Mes)PDI(Me))UI]2 (3), and [((Mes)PDI(Me))U(THF)]2 (4), were examined using electronic and X-ray absorption spectroscopies, magnetometry, and computational analyses. Taken together, these studies suggest that all members of the series contain uranium(IV) centers with 5f (2) configurations and reduced ligand frameworks, specifically [(Mes)PDI(Me)](•/-), [(Mes)PDI(Me)](2-), [(Mes)PDI(Me)](3-) and [(Mes)PDI(Me)](4-), respectively. In the cases of 2, 3, and 4 no unpaired spin density was found on the ligands, indicating a singlet diradical ligand in monomeric 2 and ligand electron spin-pairing through dimerization in 3 and 4. Interaction energies, representing enthalpies of dimerization, of -116.0 and -144.4 kcal mol(-1) were calculated using DFT for the monomers of 3 and 4, respectively, showing there is a large stabilization gained by dimerization through uranium-arene bonds. Highlighted in these studies is compound 4, bearing a previously unobserved pyridine(diimine) tetraanion, that was uniquely stabilized by backbonding between uranium cations and the η(5)-pyridyl ring.

Hydrothermal synthesis of (C6N2H14)2(UVI2UIVO4F12), a mixed-valent one-dimensional uranium oxyfluoride.

PubMed

Allen, S; Barlow, S; Halasyamani, P S; Mosselmans, J F; O'Hare, D; Walker, S M; Walton, R I

2000-08-21

A new hybrid organic-inorganic mixed-valent uranium oxyfluoride, (C6N2H14)2(U3O4F12), UFO-17, has been synthesized under hydrothermal conditions using uranium dioxide as the uranium source, hydrofluoric acid as mineralizer, and 1,4-diazabicyclo[2.2.2]octane as template. The single-crystal X-ray structure was determined. Crystals of UFO-17 belonged to the orthorhombic space group Cmcm (no. 63), with a = 14.2660(15) A, b = 24.5130(10) A, c = 7.201(2) A, and Z = 4. The structure reveals parallel uranium-containing chains of two types: one type is composed of edge-sharing UO2F5 units; the other has a backbone of edge-sharing UF8 units, each sharing an edge with a pendant UO2F5 unit. Bond-valence calculations suggest the UF8 groups contain UIV, while the UO2F5 groups contain UVI. EXAFS data give results consistent with the single-crystal X-ray structure determination, while comparison of the uranium LIII-edge XANES of UFO-17 with that of related UIV and UVI compounds supports the oxidation-state assignment. Variable-temperature magnetic susceptibility measurements on UFO-17 and a range of related hybrid organic-inorganic uranium(IV) and uranium(VI) fluorides and oxyfluorides further support the formulation of UFO-17 as a mixed-valent UIV/UVI compound.

Dimers of nineteen-electron sandwich compounds: crystal and electronic structures, and comparison of reducing strengths.

PubMed

Mohapatra, Swagat K; Fonari, Alexandr; Risko, Chad; Yesudas, Kada; Moudgil, Karttikay; Delcamp, Jared H; Timofeeva, Tatiana V; Brédas, Jean-Luc; Marder, Seth R; Barlow, Stephen

2014-11-17

The dimers of some Group 8 metal cyclopentadienyl/arene complexes and Group 9 metallocenes can be handled in air, yet are strongly reducing, making them useful n-dopants in organic electronics. In this work, the X-ray molecular structures are shown to resemble those of Group 8 metal cyclopentadienyl/pentadienyl or Group 9 metal cyclopentadienyl/diene model compounds. Compared to those of the model compounds, the DFT HOMOs of the dimers are significantly destabilized by interactions between the metal and the central CC σ-bonding orbital, accounting for the facile oxidation of the dimers. The lengths of these CC bonds (X-ray or DFT) do not correlate with DFT dissociation energies, the latter depending strongly on the monomer stabilities. Ru and Ir monomers are more reducing than their Fe and Rh analogues, but the corresponding dimers also exhibit much higher dissociation energies, so the estimated monomer cation/neutral dimer potentials are, with the exception of that of [RhCp2 ]2 , rather similar (-1.97 to -2.15 V vs. FeCp2 (+/0) in THF). The consequences of the variations in bond strength and redox potentials for the reactivity of the dimers are discussed. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nanoparticles prepared by the sol gel method and their use in the formation of nanocomposites with polypropylene

NASA Astrophysics Data System (ADS)

Moncada, E.; Quijada, R.; Retuert, J.

2007-08-01

Hybrid layered aluminosilicate nanoparticles (HLNP) containing octadecylamine (ODA) as the organic part, and silica nanoparticles with spherical morphology containing ODA (HSNP) or without ODA (SNP) were prepared by the sol-gel method and used for the formation of nanocomposites with polypropylene. The polypropylene matrices, of different molecular weight and polydispersity, were prepared using polymers obtained via Ziegler-Natta or metallocene catalysts. A strong influence of the morphology and the presence of ODA on the surface of the nanoparticles was found on the formation and characteristics of the nanocomposites. The mechanical properties and thermal stability of these materials were determined and compared with those of nanocomposites prepared with 2:1 phylosilicate clays such as montmorillonite and hectorite in similar polymer matrices. X-ray diffraction, transmission electron microscopy, and the study of mechanical properties showed that the use of HLNP allows nanocomposites with considerably improved mechanical properties to be obtained, compared with nanocomposites prepared with exfoliated clays. In the case of nanocomposites prepared with spherical particles functionalized with ODA (HSNP), materials with high specific strength combined with high elongation before rupture were obtained. The thermal stabilization of polypropylene matrices containing the synthesized nanoparticles (HLNP, HSNP or SNP) occurs about 50 °C higher than that attained with clays.

Experimental and molecular dynamics simulation study of the sublimation and vaporization energetics of iron metalocenes. crystal structures of Fe(eta5-C5H4CH3)2 and Fe[(eta5-(C5H5)(eta5-C5H4CHO)].

PubMed

Lousada, Claudio M; Pinto, Susana S; Lopes, José N Canongia; da Piedade, M Fatima Minas; Diogo, Hermínio P; da Piedade, Manuel E Minas

2008-04-03

The standard molar enthalpies of sublimation of ferrocene, 1,1'-dimethylferrocene, decamethylferrocene, ferrocenecarboxaldehyde and alpha-methylferrocenemethanol, and the enthalpy of vaporization of N,N-dimethyl(aminomethyl)ferrocene, at 298.15 K, were determined by Calvet-drop microcalorimetry and/or the Knudsen effusion method. The obtained values were used to assess and refine our previously developed force field for metallocenes. The modified force field was able to reproduce the deltasubHdegreesm and deltavapHdegreesm values of the test-set with an accuracy better than 5 kJ.mol-1, except for decamethylferrocene, in which case the deviation between the calculated and experimental deltasubHdegreesm values was 16.1 kJ.mol-1. The origin of the larger error found in the prediction of the sublimation energetics of decamethylferrocene, and which was also observed in the estimation of structural properties (e.g., density and unit cell dimensions), is discussed. Finally, the crystal structures of Fe(eta5-C5H4CH3)2 and Fe[(eta5-(C5H5)(eta5-C5H4CHO)] at 293 and 150 K, respectively, are reported.

Physical properties of superbulky lanthanide metallocenes: synthesis and extraordinary luminescence of [Eu(II)(Cp(BIG))2] (Cp(BIG) = (4-nBu-C6H4)5-cyclopentadienyl).

PubMed

Harder, Sjoerd; Naglav, Dominik; Ruspic, Christian; Wickleder, Claudia; Adlung, Matthias; Hermes, Wilfried; Eul, Matthias; Pöttgen, Rainer; Rego, Daniel B; Poineau, Frederic; Czerwinski, Kenneth R; Herber, Rolfe H; Nowik, Israel

2013-09-09

The superbulky deca-aryleuropocene [Eu(Cp(BIG))2], Cp(BIG) = (4-nBu-C6H4)5-cyclopentadienyl, was prepared by reaction of [Eu(dmat)2(thf)2], DMAT = 2-Me2N-α-Me3Si-benzyl, with two equivalents of Cp(BIG)H. Recrystallizyation from cold hexane gave the product with a surprisingly bright and efficient orange emission (45% quantum yield). The crystal structure is isomorphic to those of [M(Cp(BIG))2] (M = Sm, Yb, Ca, Ba) and shows the typical distortions that arise from Cp(BIG)⋅⋅⋅Cp(BIG) attraction as well as excessively large displacement parameter for the heavy Eu atom (U(eq) = 0.075). In order to gain information on the true oxidation state of the central metal in superbulky metallocenes [M(Cp(BIG))2] (M = Sm, Eu, Yb), several physical analyses have been applied. Temperature-dependent magnetic susceptibility data of [Yb(Cp(BIG))2] show diamagnetism, indicating stable divalent ytterbium. Temperature-dependent (151)Eu Mössbauer effect spectroscopic examination of [Eu(Cp(BIG))2] was examined over the temperature range 93-215 K and the hyperfine and dynamical properties of the Eu(II) species are discussed in detail. The mean square amplitude of vibration of the Eu atom as a function of temperature was determined and compared to the value extracted from the single-crystal X-ray data at 203 K. The large difference in these two values was ascribed to the presence of static disorder and/or the presence of low-frequency torsional and librational modes in [Eu(Cp(BIG))2]. X-ray absorbance near edge spectroscopy (XANES) showed that all three [Ln(Cp(BIG))2] (Ln = Sm, Eu, Yb) compounds are divalent. The XANES white-line spectra are at 8.3, 7.3, and 7.8 eV, for Sm, Eu, and Yb, respectively, lower than the Ln2O3 standards. No XANES temperature dependence was found from room temperature to 100 K. XANES also showed that the [Ln(Cp(BIG))2] complexes had less trivalent impurity than a [EuI2(thf)x] standard. The complex [Eu(Cp(BIG))2] shows already at room temperature strong orange photoluminescence (quantum yield: 45 %): excitation at 412 nm (24,270 cm(-1)) gives a symmetrical single band in the emission spectrum at 606 nm (νmax =16495 cm(-1), FWHM: 2090 cm(-1), Stokes-shift: 2140 cm(-1)), which is assigned to a 4f(6)5d(1) → 4f(7) transition of Eu(II). These remarkable values compare well to those for Eu(II)-doped ionic host lattices and are likely caused by the rigidity of the [Eu(Cp(BIG))2] complex. Sharp emission signals, typical for Eu(III), are not visible. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

An Organolanthanide Building Block Approach to Single-Molecule Magnets.

PubMed

Harriman, Katie L M; Murugesu, Muralee

2016-06-21

Single-molecule magnets (SMMs) are highly sought after for their potential application in high-density information storage, spintronics, and quantum computing. SMMs exhibit slow relaxation of the magnetization of purely molecular origin, thus making them excellent candidates towards the aforementioned applications. In recent years, significant focus has been placed on the rare earth elements due to their large intrinsic magnetic anisotropy arising from the near degeneracy of the 4f orbitals. Traditionally, coordination chemistry has been utilized to fabricate lanthanide-based SMMs; however, heteroatomic donor atoms such as oxygen and nitrogen have limited orbital overlap with the shielded 4f orbitals. Thus, control over the anisotropic axis and induction of f-f interactions are limited, meaning that the performance of these systems can only extend so far. To this end, we have placed considerable attention on the development of novel SMMs whose donor atoms are conjugated hydrocarbons, thereby allowing us to perturb the crystal field of lanthanide ions through the use of an electronic π-cloud. This approach allows for fine tuning of the anisotropic axis of the molecule, allowing this method the potential to elicit SMMs capable of reaching much larger values for the two vital performance measurements of an SMM, the energy barrier to spin reversal (Ueff), and the blocking temperature of the magnetization (TB). In this Account, we describe our efforts to exploit the inherent anisotropy of the late 4f elements; namely, Dy(III) and Er(III), through the use of cyclooctatetraenyl (COT) metallocenes. With respect to the Er(III) derivatives, we have seen record breaking success, reaching blocking temperatures as high as 14 K with frozen solution magnetometry. These results represent the first example of such a high TB being observed for a system with only a single spin center, formally known as a single-ion magnet (SIM). Our continued interrelationship between theoretical and experimental chemistry allows us to shed light on the mechanisms and electronic properties that govern the slow relaxation dynamics inherent to this unique set of SMMs, thus providing insight into the role by which both symmetry and crystal field effects contribute to the magnetic properties. As we look to the future success of such materials in practical devices, we must gain an understanding of how the 4f elements communicate magnetically, a subject upon which there is still limited knowledge. As such, we have described our work on coupling mononuclear metallocenes to generate new dinuclear SMMs. Through a building block approach, we have been able to gain access to new double,- triple- and quadruple-decker complexes that possess remarkable properties; exhibiting TB of 12 K and Ueff above 300 K. Our goal is to develop a fundamental platform from which to study 4f coupling, while maintaining and enhancing the strict axiality of the anisotropy of the 4f ions. This Account will present a successful strategy employed in the production of novel and high-performing SMMs, as well as a clear overview of the lessons learned throughout.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Weydert, M.; Brennan, J.G.; Andersen, R.A.

Reaction of (MeC{sub 5}H{sub 4}){sub 3}UX (X = Cl, MeC{sub 5}H{sub 4}) with t-BuLi affords the tertiary alkyl complex (MeC{sub 5}H{sub 4}){sub 3}U(t-Bu). Despite uranium(IV) generally being the preferred oxidation state in organometallic systems, (MeC{sub 5}H{sub 4}){sub 3}U(t-Bu) reacts with Lewis bases (L = PMe{sub 3}, THF, RCN, RNC) to yield the reduced uranium(III) base adducts (MeC{sub 5}H{sub 4}){sub 3}U(L). Carbon monoxide undergoes migratory insertion into the metal tertiary alkyl bond. The resulting acyl derivative decomposes at 90{degree}C to yield insoluble uranium-containing products and a mixture of tert-butyltoluenes by ring expansion of a methylcyclopentadienyl ligand. Ethylene also undergoes migratory insertionmore » into the metal tertiary alkyl bond. No subsequent insertion of ethylene into the metal carbon bond takes place after the first equivalent has inserted. In marked contrast, reaction of various (MeC{sub 5}H{sub 4}){sub 3}ThX (X = Cl, I, MeC{sub 5}H{sub 4}, O-2,6-Me{sub 2}C{sub 6}H{sub 3}, OTs) compounds with t-BuLi gave intractable materials. However, reaction of the cationic species [(RC{sub 5}H{sub 4}){sub 3}Th](BPh{sub 4}) (R = Me{sub 3}Si, t-Bu) with t-BuLi yields the new thorium hydrides (RC{sub 5}H{sub 4}){sub 3}ThH. 40 refs., 2 figs.« less

Geochemical control on uranium(IV) mobility in a mining-impacted wetland.

PubMed

Wang, Yuheng; Bagnoud, Alexandre; Suvorova, Elena; McGivney, Eric; Chesaux, Lydie; Phrommavanh, Vannapha; Descostes, Michael; Bernier-Latmani, Rizlan

2014-09-02

Wetlands often act as sinks for uranium and other trace elements. Our previous work at a mining-impacted wetland in France showed that a labile noncrystalline U(IV) species consisting of U(IV) bound to Al-P-Fe-Si aggregates was predominant in the soil at locations exhibiting a U-containing clay-rich layer within the top 30 cm. Additionally, in the porewater, the association of U(IV) with Fe(II) and organic matter colloids significantly increased U(IV) mobility in the wetland. In the present study, within the same wetland, we further demonstrate that the speciation of U at a location not impacted by the clay-rich layer is a different noncrystalline U(IV) species, consisting of U(IV) bound to organic matter in soil. We also show that the clay-poor location includes an abundant sulfate supply and active microbial sulfate reduction that induce substantial pyrite (FeS2) precipitation. As a result, Fe(II) concentrations in the porewater are much lower than those at clay-impacted zones. U porewater concentrations (0.02-0.26 μM) are also considerably lower than those at the clay-impacted locations (0.21-3.4 μM) resulting in minimal U mobility. In both cases, soil-associated U represents more than 99% of U in the wetland. We conclude that the low U mobility reported at clay-poor locations is due to the limited association of Fe(II) with organic matter colloids in porewater and/or higher stability of the noncrystalline U(IV) species in soil at those locations.

Glass Fiber Reinforced Polypropylene Mechanical Properties Enhancement by Adhesion Improvement

PubMed Central

Etcheverry, Mariana; Barbosa, Silvia E.

2012-01-01

Glass fibers (GF) are the reinforcement agent most used in polypropylene (PP) based composites, as they have good balance between properties and costs. However, their final properties are mainly determined by the strength and stability of the polymer-fiber interphase. Fibers do not act as an effective reinforcing material when the adhesion is weak. Also, the adhesion between phases can be easily degraded in aggressive environmental conditions such as high temperatures and/or elevated moisture, and by the stress fields to which the material may be exposed. Many efforts have been done to improve polymer-glass fiber adhesion by compatibility enhancement. The most used techniques include modifications in glass surface, polymer matrix and/or both. However, the results obtained do not show a good costs/properties improvement relationship. The aim of this work is to perform an accurate analysis regarding methods for GF/PP adhesion improvement and to propose a new route based on PP in-situ polymerization onto fibers. This route involves the modification of fibers with an aluminum alkyl and hydroxy-α-olefin and from there to enable the growth of the PP chains using direct metallocenic copolymerization. The adhesion improvements were further proved by fragmentation test, as well as by mechanical properties measurements. The strength and toughness increases three times and the interfacial strength duplicates in PP/GF composites prepared with in-situ polymerized fibers. PMID:28817025

Spectroscopic, structural and computational analysis of [Re(CO)3(dippM)Br](n+) (dippM = 1,1'-bis(diiso-propylphosphino)metallocene, M = Fe, n = 0 or 1; M = Co, n = 1).

PubMed

Furneaux, Aliza G; Piro, Nicholas A; Hernández Sánchez, Raúl; Gramigna, Kathryn M; Fey, Natalie; Robinson, Michael J; Kassel, W Scott; Nataro, Chip

2016-03-21

While the redox active backbone of bis(phosphino)ferrocene ligands is often cited as an important feature of these ligands in catalytic studies, the structural parameters of oxidized bis(phosphino)ferrocene ligands have not been thoroughly studied. The reaction of [Re(CO)3(dippf)Br] (dippf = 1,1'-bis(diiso-propylphosphino)ferrocene) and [NO][BF4] in methylene chloride yields the oxidized compound, [Re(CO)3(dippf)Br][BF4]. The oxidized species, [Re(CO)3(dippf)Br][BF4], and the neutral species, [Re(CO)3(dippf)Br], are compared using X-ray crystallography, cyclic voltammetry, visible spectroscopy, IR spectroscopy and zero-field (57)Fe Mössbauer spectroscopy. In addition, the magnetic moment of the paramagnetic [Re(CO)3(dippf)Br][BF4] was measured in the solid state using SQUID magnetometry and in solution by the Evans method. The electron transfer reaction of [Re(CO)3(dippf)Br][BF4] with acetylferrocene was also examined. For additional comparison, the cationic compound, [Re(CO)3(dippc)Br][PF6] (dippc = 1,1'-bis(diiso-propylphosphino)cobaltocenium), was prepared and characterized by cyclic voltammetry, X-ray crystallography, and NMR, IR and visible spectroscopies. Finally, DFT was employed to examine the oxidized dippf ligand and the oxidized rhenium complex, [Re(CO)3(dippf)Br](+).

Anionic Hosts for the Incorporation of Cationic Guests

PubMed Central

Peresypkina, Eugenia; Heindl, Claudia; Virovets, Alexander; Brake, Helena; Mädl, Eric

2018-01-01

Abstract Pentaphosphaferrocene [Cp*Fe(η5‐P5)] (1 a) represents an excellent building block for the template‐directed synthesis of spherical supramolecules. Here, the self‐assembly of 1 a with CuI and CuII halides in the presence of the template complexes [FeCp2][PF6], [CoCp2][PF6] and [CoCp2] is reported, testifying to the redox behavior of the formed supramolecules. The oxidation or reduction capacity of these reactive complexes does not inhibit their template impact and, for the first time, the cationic metallocene [CoCp2]+ is enclosed in unprecedented anionic organometallic hosts. Furthermore, the large variety of structural motifs, as icosahedral, trigonal antiprismatic, cuboidal and tetragonal antiprismatic arrangements of 1 a units are realized in the supramolecules [FeCp2]@[{1 a}12(CuBr)17.3] (3), [CoCp2]+ 3{[CoCp2]+@[{1 a}8Cu24.25Br28.25(CH3CN)6]4−} (4), {[Cp2Co]+@[{1 a}8(CuI)28 (CH3CN)9.8]}{[Cp2Co]+@[{1 a)}8Cu24.4I26.4(CH3CN)8]2−} (5), and [{1 a}3{(1 a)2NH}3Cu16I10(CH3CN)7] (6), respectively. PMID:29236336

Redox-Active vs Redox-Innocent: A Comparison of Uranium Complexes Containing Diamine Ligands.

PubMed

Pattenaude, Scott A; Mullane, Kimberly C; Schelter, Eric J; Ferrier, Maryline G; Stein, Benjamin W; Bone, Sharon E; Lezama Pacheco, Juan S; Kozimor, Stosh A; Fanwick, Phillip E; Zeller, Matthias; Bart, Suzanne C

2018-05-11

Uranium complexes ( Mes DAE) 2 U(THF) (1-DAE) and Cp 2 U( Mes DAE) (2-DAE) ( Mes DAE = [ArN-CH 2 CH 2 -NAr]; Ar = 2,4,6-trimethylphenyl (Mes)), bearing redox-innocent diamide ligands, have been synthesized and characterized for a full comparison with previously published, redox-active diimine complexes, ( Mes DAB Me ) 2 U(THF) (1-DAB) and Cp 2 U( Mes DAB Me ) (2-DAB) ( Mes DAB Me = [ArN═C(Me)C(Me)═NAr]; Ar = Mes). These redox-innocent analogues maintain an analogous steric environment to their redox-active ligand counterparts to facilitate a study aimed at determining the differing electronic behavior around the uranium center. Structural analysis by X-ray crystallography showed 1-DAE and 2-DAE have a structural environment very similar to 1-DAB and 2-DAB, respectively. The main difference occurs with coordination of the ene-backbone to the uranium center in the latter species. Electronic absorption spectroscopy reveals these new DAE complexes are nearly identical to each other. X-ray absorption spectroscopy suggests all four species contain +4 uranium ions. The data also indicates that there is an electronic difference between the bis(diamide)-THF uranium complexes as opposed to those that only contain one diamide and two cyclopentadienyl rings. Finally, magnetic measurements reveal that all complexes display temperature-dependent behavior consistent with uranium(IV) ions that do not include ligand radicals. Overall, this study determines that there is no significant bonding difference between the redox-innocent and redox-active ligand frameworks on uranium. Furthermore, there are no data to suggest covalent bonding character using the latter ligand framework on uranium, despite what is known for transition metals.

Fundamental relation between molecular geometry and real-space topology. Combined AIM, ELI-D, and ASF analysis of hapticities and intramolecular hydrogen-hydrogen bonds in zincocene-related compounds.

PubMed

Mebs, Stefan; Chilleck, Maren Annika; Meindl, Kathrin; Hübschle, Christian Bertram

2014-06-19

Despite numerous advanced and widely distributed bonding theories such as MO, VB, NBO, AIM, and ELF/ELI-D, complex modes of bonding such as M-Cp*((R)) interactions (hapticities) in asymmetrical metallocenes or weak intramolecular interactions (e.g., hydrogen-hydrogen (H···H) bonds) still remain a challenge for these theories in terms of defining whether or not an atom-atom interaction line (a "chemical bond") should be drawn. In this work the intramolecular Zn-C(Cp*(R)) (R = Me, -(CH2)2NMe2, and -(CH2)3NMe2) and H···H connectivity of a systematic set of 12 zincocene-related compounds is analyzed in terms of AIM and ELI-D topology combined with the recently introduced aspherical stockholder fragment (ASF) surfaces. This computational analysis unravels a distinct dependency of the AIM and ELI-D topology against the molecular geometry for both types of interactions, which confirms and extends earlier findings on smaller sets of compounds. According to these results the complete real-space topology including strong, medium, and weak interactions of very large compounds such as proteins may be reliably predicted by sole inspection of accurately determined molecular geometries, which would on the one hand afford new applications (e.g., accurate estimation of numbers, types, and strengths of intra- and intermolecular interactions) and on the other hand have deep implications on the significance of the method.

Dipolar Second-Order Nonlinear Optical Chromophores Containing Ferrocene, Octamethylferrocene, and Ruthenocene Donors and Strong π-Acceptors: Crystal Structures and Comparison of π-Donor Strengths

PubMed Central

Kinnibrugh, Tiffany L.; Salman, Seyhan; Getmanenko, Yulia A.; Coropceanu, Veaceslav; Porter, William W.; Timofeeva, Tatiana V.; Matzger, Adam J.; Brédas, Jean-Luc; Marder, Seth R.; Barlow, Stephen

2009-01-01

Crystal structures have been determined for six dipolar polyene chromophores with metallocenyl – ferrocenyl (Fc), octamethylferrocenyl (Fc″), or ruthenocenyl (Rc) – donors and strong heterocyclic acceptors based on 1,3-diethyl-2-thiobarbituric acid or 3-dicyanomethylidene-2,3-dihydrobenzothiophene-1,1-dioxide. In each case, crystals were found to belong to centrosymmetric space groups. For one example, polymer-induced heteronucleation revealed the existence of two additional polymorphs, which were inactive in second-harmonic generation, suggesting that they were also centrosymmetric. The bond-length alternations between the formally double and single bonds of the polyene bridges are reduced compared to simple polyenes, indicating significant contribution from charge-separated resonance structures, although the metallocenes are not significantly distorted towards the [(η6-fulvene)(η5-cyclopentadienyl)metal(II)]+ extreme. DFT geometries are in excellent agreement with those determined crystallographically; while the π-donor strengths of the three metallocenyl groups are insufficiently different to result in detectable differences in the crystallographic bond-length alternations, the DFT geometries, as well as DFT-calculations of partial charges for atoms, suggest that π-donor strength decreases in the order Fc″ ≫ Fc > Rc. NMR, IR and electrochemical evidence also suggests that octamethylferrocenyl is the stronger π-donor, exhibiting similar π-donor strength to a p-(dialkylamino)phenyl group, while ferrocenyl and ruthenocenyl show very similar π-donor strengths to one another in chromophores of this type. PMID:20047010

Chemical activation of molecules by metals: Experimental studies of electron distributions and bonding

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lichtenberger, D.L.

1991-10-01

The formal relationship between measured molecular ionization energies and thermodynamic bond dissociation energies has been developed into a single equation which unifies the treatment of covalent bonds, ionic bonds, and partially ionic bonds. This relationship has been used to clarify the fundamental thermodynamic information relating to metal-hydrogen, metal-alkyl, and metal-metal bond energies. We have been able to obtain a direct observation and measurement of the stabilization energy provided by the agostic interaction of the C-H bond with the metal. The ionization energies have also been used to correlate the rates of carbonyl substitution reactions of ({eta}{sup 5}-C{sub 5}H{sub 4}X)Rh(CO){sub 2}more » complexes, and to reveal the electronic factors that control the stability of the transition state. The extent that the electronic features of these bonding interactions transfer to other chemical systems is being investigated in terms of the principle of additivity of ligand electronic effects. Specific examples under study include metal- phosphines, metal-halides, and metallocenes. Especially interesting has been the recent application of these techniques to the characterization of the soccer-ball shaped C{sub 60} molecule, buckminsterfullerene, and its interaction with a metal surface. The high-resolution valence ionizations in the gas phase reveal the high symmetry of the molecule, and studies of thin films of C{sub 60} reveal weak intermolecular interactions. Scanning tunneling and atomic force microscopy reveal the arrangement of spherical molecules on gold substrates, with significant delocalization of charge from the metal surface. 21 refs.« less

Progress in understanding uranium(IV) speciation and dynamics in biologically reduced sediments: Research at molecular to centimeter scales by the SLAC SFA program

NASA Astrophysics Data System (ADS)

Bargar, J.; Williams, K. H.; Campbell, K. M.; Stubbs, J. E.; Suvorova, E.; Lezama-Pacheco, J. S.; Alessi, D.; Stylo, M.; Handley, K. M.; Bernier-Latmani, R.; Cerrato, J.; Davis, J. A.; Fox, P. M.; Giammar, D.; Long, P. E.

2011-12-01

The chemical and physical forms of U(IV) in reduced sediments, as well as the biogeochemical processes by which they form and transform, profoundly influence the stability of reduced U(IV) species and the behavior of uranium in biostimulated aquifers. Obtaining such information in field sediments is important because biogeochemical field conditions and their time dependence are difficult to replicate in the laboratory. The majority of contaminated aquifers in which bioremediation is of potential interest, including the Old Rifle, CO IFRC site, exhibit relatively low uranium sediment concentrations, i.e., < 10 ppm, presenting a formidable challenge to the use of spectroscopy and microscopy techniques that typically require 10-fold or higher uranium loadings. We have developed an in-situ column technique to study U(IV) species and evolving microbial communities in the Old Rifle aquifer and to correlate them with changes in trace and major ion groundwater composition during biostimulation treatments. Sediments were examined using x-ray and electron microscopy, x-ray absorption spectroscopy (XAS), and chemical extractions. XAS analysis showed that U(IV) occurred predominantly or exclusively as monomeric U(IV) complexes coordinated to oxo (or similar N/C) neighbors, and is associated with biomass or Fe sulfides. Even in the latter case, U(IV) was not coordinated directly to S neighbors. Sediment-hosted monomeric U(IV) complexes were found to partially transform into uraninite in the aquifer over a subsequent 12 month period. This work establishes the importance of monomeric U(IV) complexes in subsurface sediments at the Old Rifle site and provides a conceptual framework in which previously observed U(IV) reduction products can be related. These experiments also establish that U(IV) species are dynamic in aquifers and can undergo non-oxidative transformation reactions. These new results have important implications for uranium reactive transport models, long-term assessment of remediation technologies, and understanding natural uranium reduction in aquifers.

Thiocyanate complexes of uranium in multiple oxidation states: a combined structural, magnetic, spectroscopic, spectroelectrochemical, and theoretical study.

PubMed

Hashem, Emtithal; Platts, James A; Hartl, František; Lorusso, Giulia; Evangelisti, Marco; Schulzke, Carola; Baker, Robert J

2014-08-18

A comprehensive study of the complexes A4[U(NCS)8] (A = Cs, Et4N, (n)Bu4N) and A3[UO2(NCS)5] (A = Cs, Et4N) is described, with the crystal structures of [(n)Bu4N]4[U(NCS)8]·2MeCN and Cs3[UO2(NCS)5]·O0.5 reported. The magnetic properties of square antiprismatic Cs4[U(NCS)8] and cubic [Et4N]4[U(NCS)8] have been probed by SQUID magnetometry. The geometry has an important impact on the low-temperature magnetic moments: at 2 K, μeff = 1.21 μB and 0.53 μB, respectively. Electronic absorption and photoluminescence spectra of the uranium(IV) compounds have been measured. The redox chemistry of [Et4N]4[U(NCS)8] has been explored using IR and UV-vis spectroelectrochemical methods. Reversible 1-electron oxidation of one of the coordinated thiocyanate ligands occurs at +0.22 V vs Fc/Fc(+), followed by an irreversible oxidation to form dithiocyanogen (NCS)2 which upon back reduction regenerates thiocyanate anions coordinating to UO2(2+). NBO calculations agree with the experimental spectra, suggesting that the initial electron loss of [U(NCS)8](4-) is delocalized over all NCS(-) ligands. Reduction of the uranyl(VI) complex [Et4N]3[UO2(NCS)5] to uranyl(V) is accompanied by immediate disproportionation and has only been studied by DFT methods. The bonding in [An(NCS)8](4-) (An = Th, U) and [UO2(NCS)5](3-) has been explored by a combination of DFT and QTAIM analysis, and the U-N bonds are predominantly ionic, with the uranyl(V) species more ionic that the uranyl(VI) ion. Additionally, the U(IV)-NCS ion is more ionic than what was found for U(IV)-Cl complexes.

Adventures in main group chemistry: From molecules to materials

NASA Astrophysics Data System (ADS)

Findlater, Michael

Three synthetic methods have been explored for the preparation of several novel boron-substituted amidinates and guanidinates. The extension of heterocumulene insertion chemistries to boron-aryl, boron-metallocene and boron-transition metal moieties has also been achieved and the mechanism of such insertions is addressed via density functional theory modeling techniques. The reactivity of these complexes is also explored, mainly through halide abstraction methodologies to generate boron cations, which are potent Lewis Acids and may be useful in promoting organic transformations or in the polymerization of ethylene. The synthesis and characterization of the elusive monomeric low valent carbenoid boron(I), a compound with a formal lone pair located upon the boron center, has been lacking. The suitability of the guanidinate ligand system to support such a species is also discussed and a combined experimental and theoretical approach to this highly topical problem is also presented. Thirdly, the use of photovoltaics (devices which convert solar energy directly into electricity) as an alternative source of energy outwith fossil fuel technologies is a rapidly growing area of interest. Initial efforts to use a novel approach, which incorporates inorganic nanocrystals wired into a conducting polymer matrix, are also presented. Successful synthetic approaches to the gallium, aluminum and indium monomeric precursors suitable for electropolymerization were developed. These compounds proved to be effective starting points for the generation of conducting polymers with embedded III/VI (Ga2S 3) nanocrystals with further studies currently underway as to their III/V (InP, GaAs) compatriots. Finally, a retrospective of projects that may best be described in terms of the moniker "Loose Ends and Future Directions" will be presented. The aim of which will be to serve as a useful guidepost for further studies in the fields and topics discussed.

Activation of SO2 with [(η(5) -C5 Me5 )2 Ln(THF)2 ] (Ln=Eu, Yb) leading to dithionite and sulfinate complexes.

PubMed

Klementyeva, Svetlana V; Gamer, Michael T; Schmidt, Anna-Corina; Meyer, Karsten; Konchenko, Sergey N; Roesky, Peter W

2014-10-13

The reaction of decamethylytterbocene [(η(5) -C5 Me5 )2 Yb(THF)2 ] with SO2 at low temperature gave two new compounds, namely, the Yb(III) dithionite/sulfinate complex [{(η(5) -C5 Me5 )2 Yb(μ3 ,1κ(2) O(1,3) ,2κ(3) O(2,2',4) -S2 O4 )}2 {(η(5) -C5 Me5 )Yb(μ,1κO,2κO'-C5 Me5 SO2 )}2 ] (1) and the Yb(III) dithionite complex [{(η(5) -C5 Me5 )2 Yb}2 (μ,1κ(2) O(1,3) ,2κ(2) O(2,4) -S2 O4 )] (2). After extraction of 1, the mixture was heated to give the dinuclear tetrasulfinate complex [{(η(5) -C5 Me5 )Yb}2 (μ,κO,κO'-C5 Me5 SO2 )4 ] (3 a). In contrast, from the reaction of [(η(5) -C5 Me5 )2 Eu(THF)2 ] with SO2 only the tetrasulfinate complex [{(η(5) -C5 Me5 )Eu}2 (μ,κO,κO'-C5 Me5 SO2 )4 ] (3 b) was isolated. Two major reaction pathways were observed: 1) reductive coupling of two SO2 molecules to form the dithionite anion S2 O4 (2-) ; and 2) nucleophilic attack of one metallocene C5 Me5 ligand on the sulfur atom of SO2 . The compounds presented are the first dithionite and sulfinate complexes of the f-elements. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fulvene to cyclopentadienyl conversion with homoleptic complexes of zirconium and hafnium

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rogers, J.S.; Lachicotte, R.J.; Bazan, G.C.

1999-09-27

The reaction of 6,6-dimethylfulvene with M(CH{sub 2}Ph){sub 4} (M = Zr, Hf) in benzene gives [{eta}{sup 5}-C{sub 5}H{sub 4}(CMe{sub 2}CH{sub 2}Ph)]M(CH{sub 2}Ph){sub 3} (1, M = Zr; 2, M = Hf) without any observable byproducts. A similar reaction for M = Ti is not observed. The single-crystal X-ray study of 1 shows a three-legged piano-stool geometry with an {eta}{sup 2}-bound benzyl ligand. A second equivalent of 6,6-dimethylfulvene does not react with either 1 or 2. The bulkier 6,6-diphenyfulvene only reacts cleanly with the more Lewis acidic Hf(CH{sub 2}Ph){sub 4} to give [{eta}{sup 5}-C{sub 5}H{sub 4}(CPh{sub 2}CH{sub 2}Ph)]Hf(CH{sub 2}Ph){sub 3} (3).more » Using the tetraamido complexes M(NMe{sub 2}Ph){sub 4} and 6,6-dimethylfulvene, one obtains dimethylamine and [{eta}{sup 5}-C{sub 5}H{sub 4}(CMeCH{sub 2})]M(NMe{sub 2}){sub 3} (4 for M = Zr) in good yield. These products are formally derived from the deprotonation of a fulvene methyl group and subsequent coordination of the resulting 2-propenylcyclopentadienyl fragment. Reaction of 4 and 6,6-dimethylfulvene affords the bent metallocene [{eta}{sup 5}-C{sub 5}H{sub 4}(CMeCH{sub 2})]{sub 2}Zr(NMe{sub 2}){sub 2} (5). Excess 8,8-dimethylbenzofulvene and M(NMe{sub 2}){sub 4} provides exclusively the product with only one coordinated indene.« less

Microwave-assisted fibrous decoration of mPE surface utilizing Aloe vera extract for tissue engineering applications

PubMed Central

Balaji, Arunpandian; Jaganathan, Saravana Kumar; Supriyanto, Eko; Muhamad, Ida Idayu; Khudzari, Ahmad Zahran Md

2015-01-01

Developing multifaceted, biocompatible, artificial implants for tissue engineering is a growing field of research. In recent times, several works have been reported about the utilization of biomolecules in combination with synthetic materials to achieve this process. Accordingly, in this study, the ability of an extract obtained from Aloe vera, a commonly used medicinal plant in influencing the biocompatibility of artificial material, is scrutinized using metallocene polyethylene (mPE). The process of coating dense fibrous Aloe vera extract on the surface of mPE was carried out using microwaves. Then, several physicochemical and blood compatibility characterization experiments were performed to disclose the effects of corresponding surface modification. The Fourier transform infrared spectrum showed characteristic vibrations of several active constituents available in Aloe vera and exhibited peak shifts at far infrared regions due to aloe-based mineral deposition. Meanwhile, the contact angle analysis demonstrated a drastic increase in wettability of coated samples, which confirmed the presence of active components on glazed mPE surface. Moreover, the bio-mimic structure of Aloe vera fibers and the influence of microwaves in enhancing the coating characteristics were also meticulously displayed through scanning electron microscopy micrographs and Hirox 3D images. The existence of nanoscale roughness was interpreted through high-resolution profiles obtained from atomic force microscopy. And the extent of variations in irregularities was delineated by measuring average roughness. Aloe vera-induced enrichment in the hemocompatible properties of mPE was established by carrying out in vitro tests such as activated partial thromboplastin time, prothrombin time, platelet adhesion, and hemolysis assay. In conclusion, the Aloe vera-glazed mPE substrate was inferred to attain desirable properties required for multifaceted biomedical implants. PMID:26425089

Infrared Multiple Photon Dissociation Spectroscopy of a Gas-Phase Oxo-Molybdenum Complex with 1,2-Dithiolene Ligands

PubMed Central

2015-01-01

Electrospray ionization (ESI) in the negative ion mode was used to create anionic, gas-phase oxo-molybdenum complexes with dithiolene ligands. By varying ESI and ion transfer conditions, both doubly and singly charged forms of the complex, with identical formulas, could be observed. Collision-induced dissociation (CID) of the dianion generated exclusively the monoanion, while fragmentation of the monoanion involved decomposition of the dithiolene ligands. The intrinsic structure of the monoanion and the dianion were determined by using wavelength-selective infrared multiple-photon dissociation (IRMPD) spectroscopy and density functional theory calculations. The IRMPD spectrum for the dianion exhibits absorptions that can be assigned to (ligand) C=C, C–S, C—C≡N, and Mo=O stretches. Comparison of the IRMPD spectrum to spectra predicted for various possible conformations allows assignment of a pseudo square pyramidal structure with C2v symmetry, equatorial coordination of MoO2+ by the S atoms of the dithiolene ligands, and a singlet spin state. A single absorption was observed for the oxidized complex. When the same scaling factor employed for the dianion is used for the oxidized version, theoretical spectra suggest that the absorption is the Mo=O stretch for a distorted square pyramidal structure and doublet spin state. A predicted change in conformation upon oxidation of the dianion is consistent with a proposed bonding scheme for the bent-metallocene dithiolene compounds [Lauher, J. W.; Hoffmann, R. J. Am. Chem. Soc.1976, 98, 1729−1742], where a large folding of the dithiolene moiety along the S···S vector is dependent on the occupancy of the in-plane metal d-orbital. PMID:24988369

Microwave-assisted fibrous decoration of mPE surface utilizing Aloe vera extract for tissue engineering applications.

PubMed

Balaji, Arunpandian; Jaganathan, Saravana Kumar; Supriyanto, Eko; Muhamad, Ida Idayu; Khudzari, Ahmad Zahran Md

2015-01-01

Developing multifaceted, biocompatible, artificial implants for tissue engineering is a growing field of research. In recent times, several works have been reported about the utilization of biomolecules in combination with synthetic materials to achieve this process. Accordingly, in this study, the ability of an extract obtained from Aloe vera, a commonly used medicinal plant in influencing the biocompatibility of artificial material, is scrutinized using metallocene polyethylene (mPE). The process of coating dense fibrous Aloe vera extract on the surface of mPE was carried out using microwaves. Then, several physicochemical and blood compatibility characterization experiments were performed to disclose the effects of corresponding surface modification. The Fourier transform infrared spectrum showed characteristic vibrations of several active constituents available in Aloe vera and exhibited peak shifts at far infrared regions due to aloe-based mineral deposition. Meanwhile, the contact angle analysis demonstrated a drastic increase in wettability of coated samples, which confirmed the presence of active components on glazed mPE surface. Moreover, the bio-mimic structure of Aloe vera fibers and the influence of microwaves in enhancing the coating characteristics were also meticulously displayed through scanning electron microscopy micrographs and Hirox 3D images. The existence of nanoscale roughness was interpreted through high-resolution profiles obtained from atomic force microscopy. And the extent of variations in irregularities was delineated by measuring average roughness. Aloe vera-induced enrichment in the hemocompatible properties of mPE was established by carrying out in vitro tests such as activated partial thromboplastin time, prothrombin time, platelet adhesion, and hemolysis assay. In conclusion, the Aloe vera-glazed mPE substrate was inferred to attain desirable properties required for multifaceted biomedical implants.

DOE Office of Scientific and Technical Information (OSTI.GOV)

de Hatten, Xavier; Cournia, Zoe; Huc, Ivan

The increasing importance of hydrogenase enzymes in the new energy research field has led us to examine the structure and dynamics of potential hydrogenase mimics, based on a ferrocene-peptide scaffold, using molecular dynamics (MD) simulations. To enable this MD study, a molecular mechanics force field for ferrocene-bearing peptides was developed and implemented in the CHARMM simulation package, thus extending the usefulness of the package into peptide-bioorganometallic chemistry. Using the automated frequency-matching method (AFMM), optimized intramolecular force-field parameters were generated through quantum chemical reference normal modes. The partial charges for ferrocene were derived by fitting point charges to quantum-chemically computed electrostaticmore » potentials. The force field was tested against experimental X-ray crystal structures of dipeptide derivatives of ferrocene-1,1'-dicarboxylic acid. The calculations reproduce accurately the molecular geometries, including the characteristic C{sub 2}-symmetrical intramolecular hydrogen-bonding pattern, that were stable over 0.1 {micro}s MD simulations. The crystal packing properties of ferrocene-1-(D)alanine-(D)proline-1'-(D)alanine-(D)proline were also accurately reproduced. The lattice parameters of this crystal were conserved during a 0.1 {micro}s MD simulation and match the experimental values almost exactly. Simulations of the peptides in dichloromethane are also in good agreement with experimental NMR and circular dichroism (CD) data in solution. The developed force field was used to perform MD simulations on novel, as yet unsynthesized peptide fragments that surround the active site of [Ni-Fe] hydrogenase. The results of this simulation lead us to propose an improved design for synthetic peptide-based hydrogenase models. The presented MD simulation results of metallocenes thereby provide a convincing validation of our proposal to use ferrocene-peptides as minimal enzyme mimics.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

De Hatten, Xavier; Cournia, Zoe; Smith, Jeremy C

The increasing importance of hydrogenase enzymes in the new energy research field has led us to examine the structure and dynamics of potential hydrogenase mimics, based on a ferrocene-peptide scaffold, using molecular dynamics (MD) simulations. To enable this MD study, a molecular mechanics force field for ferrocene-bearing peptides was developed and implemented in the CHARMM simulation package, thus extending the usefulness of the package into peptide-bioorganometallic chemistry. Using the automated frequency-matching method (AFMM), optimized intramolecular force-field parameters were generated through quantum chemical reference normal modes. The partial charges for ferrocene were derived by fitting point charges to quantum-chemically computed electrostaticmore » potentials. The force field was tested against experimental X-ray crystal structures of dipeptide derivatives of ferrocene-1,1{prime}-dicarboxylic acid. The calculations reproduce accurately the molecular geometries, including the characteristic C2-symmetrical intramolecular hydrogen-bonding pattern, that were stable over 0.1{micro}s MD simulations. The crystal packing properties of ferrocene-1-(D)alanine-(D)proline{prime}-1-(D)alanine-(D)proline were also accurately reproduced. The lattice parameters of this crystal were conserved during a 0.1 s MD simulation and match the experimental values almost exactly. Simulations of the peptides in dichloromethane are also in good agreement with experimental NMR and circular dichroism (CD) data in solution. The developed force field was used to perform MD simulations on novel, as yet unsynthesized peptide fragments that surround the active site of [Ni-Fe] hydrogenase. The results of this simulation lead us to propose an improved design for synthetic peptide-based hydrogenase models. The presented MD simulation results of metallocenes thereby provide a convincing validation of our proposal to use ferrocene-peptides as minimal enzyme mimics.« less

U(SMes*)n, (n = 3, 4) and Ln(SMes*)3 (Ln = La, Ce, Pr, Nd): lanthanide(III)/actinide(III) differentiation in agostic interactions and an unprecedented eta3 ligation mode of the arylthiolate ligand, from X-ray diffraction and DFT analysis.

PubMed

Roger, Mathieu; Barros, Noémi; Arliguie, Thérèse; Thuéry, Pierre; Maron, Laurent; Ephritikhine, Michel

2006-07-12

Reaction of U(NEt(2))(4) with HS-2,4,6-(t)Bu(3)C(6)H(2) (HSMes) gave U(SMes)(3)(NEt(2))(py) (1), whereas similar treatment of U[N(SiMe(3))SiMe(2)CH(2)][N(SiMe(3))(2)](2) afforded U(SMes)[N(SiMe(3))(2)](3) (2) and U(SMes)(3)[N(SiMe(3))(2)]. The first neutral homoleptic uranium(IV) thiolate to have been crystallographically characterized, U(SMes)(4) (4), was isolated from the reaction of U(BH(4))(4) and KSMes. The first homoleptic thiolate complex of uranium(III), U(SMes)(3) (5), was synthesized by protonolysis of U[N(SiMe(3))(2)](3) with HSMes in cyclohexane. The crystal structure of 5 exhibits the novel eta(3) ligation mode for the arylthiolate ligand. Comparison of the crystal structure of 5 with those of the isomorphous lanthanide congeners Ln(SMes)(3) (Ln = La, Ce, Pr, and Nd) indicates that the U-S, U-C(ipso)(), and U-C(ortho)() bond lengths are shorter than the corresponding ones in the 4f-element analogues, when taking into account the variation in the ionic radii of the metals. The distance between the uranium and the carbon atoms involved in the U...H-C epsilon agostic interaction of each thiolate ligand is shorter, by approximately 0.05 A, than that expected from a purely ionic bonding model. The lanthanide(III)/actinide(III) differentiation was analyzed by density functional theory (DFT). The nature of the M-S bond is shown to be ionic strongly polarized at the sulfur for M = U and iono-covalent (i.e. strongly ionic with low orbital interaction), for M = Ln. The strength of the U...H-C epsilon agostic interaction is proposed to be controlled by the maximization of the interaction between U(+) and S(-) under steric constraints. The eta(3) ligation mode of the arylthiolate ligand is also obtained from DFT.

Biopolymers Containing Unnatural Amino Acids

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schultz, Peter

Although the main chain structure of polymers has a profound effect on their materials properties, the side groups can also have dramatic effects on their properties including conductivity, liquid crystallinity, hydrophobicity, elasticity and biodegradability. Unfortunately control over the side chain structure of polymers remains a challenge – it is difficult to control the sequence of chain elongation when mixtures of monomers are polymerized, and postpolymerization side chain modification is made difficult by polymer effects on side chain reactivity. In contrast, the mRNA templated synthesis of polypeptides on the ribosome affords absolute control over the primary sequence of the twenty aminomore » acid monomers. Moreover, the length of the biopolymer is precisely controlled as are sites of crosslinking. However, whereas synthetic polymers can be synthesized from monomers with a wide range of chemically defined structures, ribosomal biosynthesis is largely limited to the 20 canonical amino acids. For many applications in material sciences, additional building blocks would be desirable, for example, amino acids containing metallocene, photoactive, and halogenated side chains. To overcome this natural constraint we have developed a method that allows unnatural amino acids, beyond the common twenty, to be genetically encoded in response to nonsense or frameshift codons in bacteria, yeast and mammalian cells with high fidelity and good yields. Here we have developed methods that allow identical or distinct noncanonical amino acids to be incorporated at multiple sites in a polypeptide chain, potentially leading to a new class of templated biopolymers. We have also developed improved methods for genetically encoding unnatural amino acids. In addition, we have genetically encoded new amino acids with novel physical and chemical properties that allow selective modification of proteins with synthetic agents. Finally, we have evolved new metal-ion binding sites in proteins using a novel metal-ion binding amino acid, which may facilitate our ability to generate new protein based sensors and catalysts.« less

Expanding the Chemistry of Actinide Metallocene Bromides. Synthesis, Properties and Molecular Structures of the Tetravalent and Trivalent Uranium Bromide Complexes: (C 5Me 4R) 2UBr 2, (C 5Me 4R) 2U(O-2,6- iPr 2C 6H 3)(Br), and [K(THF)][(C 5Me 4R) 2UBr 2] (R = Me, Et)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lichtscheidl, Alejandro Gaston; Pagano, Justin K.; Scott, Brian Lindley

The organometallic uranium species (C 5Me 4R) 2UBr 2 (R = Me, Et) were obtained by treating their chloride analogues (C 5Me 4R) 2UCl 2 (R = Me, Et) with Me 3SiBr. Treatment of (C 5Me 4R) 2UCl 2 and (C 5Me 4R) 2UBr 2 (R = Me, Et) with K(O-2,6- iPr 2C 6H 3) afforded the halide aryloxide mixed-ligand complexes (C 5Me 4R) 2U(O-2,6- iPr 2C 6H 3)(X) (R = Me, Et; X = Cl, Br). Complexes (C 5Me 4R) 2U(O-2,6- iPr 2C 6H 3)(Br) (R = Me, Et) can also be synthesized by treating (C 5Me 4R) 2U(O-2,6-more » iPr 2C 6H 3)(Cl) (R = Me, Et) with Me 3SiBr, respectively. Reduction of (C 5Me 4R) 2UCl 2 and (C 5Me 4R) 2UBr 2 (R = Me, Et) with KC 8 led to isolation of uranium(III) “ate” species [K(THF)][(C 5Me 5) 2UX 2] (X = Cl, Br) and [K(THF) 0.5][(C 5Me 4Et) 2UX 2] (X = Cl, Br), which can be converted to the neutral complexes (C 5Me 4R) 2U[N(SiMe 3) 2] (R = Me, Et). Analyses by nuclear magnetic resonance spectroscopy, X-ray crystallography, and elemental analysis are also presented.« less

A series of energetic metal pentazolate hydrates.

PubMed

Xu, Yuangang; Wang, Qian; Shen, Cheng; Lin, Qiuhan; Wang, Pengcheng; Lu, Ming

2017-09-07

Singly or doubly bonded polynitrogen compounds can decompose to dinitrogen (N 2 ) with an extremely large energy release. This makes them attractive as potential explosives or propellants, but also challenging to produce in a stable form. Polynitrogen materials containing nitrogen as the only element exist in the form of high-pressure polymeric phases, but under ambient conditions even metastability is realized only in the presence of other elements that provide stabilization. An early example is the molecule phenylpentazole, with a five-membered all-nitrogen ring, which was first reported in the 1900s and characterized in the 1950s. Salts containing the azide anion (N 3 - ) or pentazenium cation (N 5 + ) are also known, with compounds containing the pentazole anion, cyclo-N 5 - , a more recent addition. Very recently, a bulk material containing this species was reported and then used to prepare the first example of a solid-state metal-N 5 complex. Here we report the synthesis and characterization of five metal pentazolate hydrate complexes [Na(H 2 O)(N 5 )]·2H 2 O, [M(H 2 O) 4 (N 5 ) 2 ]·4H 2 O (M = Mn, Fe and Co) and [Mg(H 2 O) 6 (N 5 ) 2 ]·4H 2 O that, with the exception of the Co complex, exhibit good thermal stability with onset decomposition temperatures greater than 100 °C. For this series we find that the N 5 - ion can coordinate to the metal cation through either ionic or covalent interactions, and is stabilized through hydrogen-bonding interactions with water. Given their energetic properties and stability, pentazole-metal complexes might potentially serve as a new class of high-energy density materials or enable the development of such materials containing only nitrogen. We also anticipate that the adaptability of the N 5 - ion in terms of its bonding interactions will enable the exploration of inorganic nitrogen analogues of metallocenes and other unusual polynitrogen complexes.

A series of energetic metal pentazolate hydrates

NASA Astrophysics Data System (ADS)

Xu, Yuangang; Wang, Qian; Shen, Cheng; Lin, Qiuhan; Wang, Pengcheng; Lu, Ming

2017-09-01

Singly or doubly bonded polynitrogen compounds can decompose to dinitrogen (N2) with an extremely large energy release. This makes them attractive as potential explosives or propellants, but also challenging to produce in a stable form. Polynitrogen materials containing nitrogen as the only element exist in the form of high-pressure polymeric phases, but under ambient conditions even metastability is realized only in the presence of other elements that provide stabilization. An early example is the molecule phenylpentazole, with a five-membered all-nitrogen ring, which was first reported in the 1900s and characterized in the 1950s. Salts containing the azide anion (N3-) or pentazenium cation (N5+) are also known, with compounds containing the pentazole anion, cyclo-N5-, a more recent addition. Very recently, a bulk material containing this species was reported and then used to prepare the first example of a solid-state metal-N5 complex. Here we report the synthesis and characterization of five metal pentazolate hydrate complexes [Na(H2O)(N5)]·2H2O, [M(H2O)4(N5)2]·4H2O (M = Mn, Fe and Co) and [Mg(H2O)6(N5)2]·4H2O that, with the exception of the Co complex, exhibit good thermal stability with onset decomposition temperatures greater than 100 °C. For this series we find that the N5- ion can coordinate to the metal cation through either ionic or covalent interactions, and is stabilized through hydrogen-bonding interactions with water. Given their energetic properties and stability, pentazole-metal complexes might potentially serve as a new class of high-energy density materials or enable the development of such materials containing only nitrogen. We also anticipate that the adaptability of the N5- ion in terms of its bonding interactions will enable the exploration of inorganic nitrogen analogues of metallocenes and other unusual polynitrogen complexes.

Biopolymers Containing Unnatural Building Blocks

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schultz, Peter G.

2013-06-30

Although the main chain structure of polymers has a profound effect on their materials properties, the side groups can also have dramatic effects on their properties including conductivity, liquid crystallinity, hydrophobicity, elasticity and biodegradability. Unfortunately control over the side chain structure of polymers remains a challenge – it is difficult to control the sequence of chain elongation when mixtures of monomers are polymerized, and postpolymerization side chain modification is made difficult by polymer effects on side chain reactivity. In contrast, the mRNA templated synthesis of polypeptides on the ribosome affords absolute control over the primary sequence of the twenty aminomore » acid monomers. Moreover, the length of the biopolymer is precisely controlled as are sites of crosslinking. However, whereas synthetic polymers can be synthesized from monomers with a wide range of chemically defined structures, ribosomal biosynthesis is largely limited to the 20 canonical amino acids. For many applications in material sciences, additional building blocks would be desirable, for example, amino acids containing metallocene, photoactive, and halogenated side chains. To overcome this natural constraint we have developed a method that allows unnatural amino acids, beyond the common twenty, to be genetically encoded in response to nonsense or frameshift codons in bacteria, yeast and mammalian cells with high fidelity and good yields. Here we have developed methods that allow identical or distinct noncanonical amino acids to be incorporated at multiple sites in a polypeptide chain, potentially leading to a new class of templated biopolymers. We have also developed improved methods for genetically encoding unnatural amino acids. In addition, we have genetically encoded new amino acids with novel physical and chemical properties that allow selective modification of proteins with synthetic agents. Finally, we have evolved new metal-ion binding sites in proteins using a novel metal-ion binding amino acid, which may facilitate our ability to generate new protein based sensors and catalysts.« less

Gold(I) Complexes of Ferrocenyl Polyphosphines: Aurophilic Gold Chloride Formation and Phosphine-Concerted Shuttling of a Dinuclear [ClAu···AuCl] Fragment.

PubMed

Rampazzi, Vincent; Roger, Julien; Amardeil, Régine; Penouilh, Marie-José; Richard, Philippe; Fleurat-Lessard, Paul; Hierso, Jean-Cyrille

2016-11-07

A smart steric control of the metallocene backbone in bis- and poly(phosphino)ferrocene ligands favors intramolecular aurophilic interactions between [AuCl] fragments in polynuclear gold(I) complexes. We synthesized and characterized by multinuclear NMR and X-ray diffraction analysis mono-, di-, and polynuclear gold complexes of constrained ferrocenyl diphosphines, which bear either bulky tert-butyl groups or more flexible siloxane substituents at the cyclopentadienyl rings. The complexes meso-1,1'-bis(diphenylphosphino)-3,3'-di-tert-butylferrocene (4-m), rac-1,1'-bis[bis(5-methyl-2-furyl)phosphino]-3,3'-di-tert-butylferrocene (5-r), and rac-1,1'-bis(diphenylphosphino)-3,3'-bis[(tri-iso-propylsilyl)oxy]ferrocene (6-r) were used to form dinuclear gold complexes. Coordination of tert-butylated ferrocenyl phosphines generated aurophilic interactions in the corresponding dinuclear gold complexes, contrary to gold(I) complexes reported with 1,1'-bis(diphenylphosphino)ferrocene. The structurally related tetraphosphine 1,1',2,2'-tetrakis(diphenylphosphino)-4,4'-di-tert-butylferrocene (11) also gave access to mononuclear, dinuclear, and the original trinuclear gold chloride aurophilic complexes in which 14e - to 16e - gold centers coexist. In such complexes, nonbonded ("through-space") 31 P- 31 P' nuclear spin couplings were evidenced by high-resolution NMR. In these interactions nuclear spin information is transferred between the lone-pair electron of an uncoordinated phosphorus P and a phosphorus P' that is involved in a σ covalent bond Au-P'. The dinuclear aurophilic complex displayed a concerted shuttling of its [ClAu···AuCl] fragment between the four phosphorus donors of the tetraphosphine ligand. Thus, an aurophilic Au···Au bond, which is assumed to be a weak energy interaction, can be conserved within a dynamic shuttling process at high temperature involving an intramolecular coordination-decoordination process of digold(I) at phosphorus atoms.

Synthesis and Mossbauer spectroscopic studies of chemically oxidized ferrocenyl(phenyl)phosphines.

PubMed

Durfey, D A; Kirss, R U; Frommen, C; Feighery, W

The electrochemical potentials of Fc3-xPPhx, (1-3, x = 0-2) and (FcPPh)n (4) indicate that iodine should oxidize ferrocenyl(phenyl)phosphines. The molar conductivity of solutions of 1-3 increases sharply when the solutions are titrated with iodine, leveling off after the addition of > 2 equiv of oxidant, consistent with formation of 1:1 electrolytes. Diamagnetic salts 6-9 are observed upon addition of a benzene solution of iodine to a benzene solution of 1-4 at ambient temperature in ratios of I2/metallocene ranging from 1:1 to 2:1. Well-resolved 1H and 31P NMR spectra are obtained for 6-8. Absorptions assigned to the I3- anion dominate the UV-vis spectrum of 6-8, whereas characteristic absorptions for [Fc][I3] are absent. Mossbauer spectra of 7-9 reveal isomer shifts consistent with low-spin iron(II) in ferrocene derivatives rather than those in ferricenium ions. Small amounts of low-spin FeIII appear to be present in 6. Taken together, the results suggest that 6-9 are iodophosphonium salts and not ferricenium salts. Diferrocenyl(phenyl)phosphine oxide (5) reacts with iodine to produce a diamagnetic, dark solid 10. Low-spin FeII is observed at 77 and 293 K in the Mossbauer spectra of 10 with no evidence for oxidation of FeII to FeIII. Compound 10 is proposed to be a neutral complex between 5 and I2. Reactions between 5 and 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) yield [Fc2P(=O)][DDQ]2 (11). Mossbauer spectroscopy of 11 indicates the presence of a mixture of low-spin FeII and low-spin FeIII at 77 K, suggesting that some electron transfer occurs from 5 to DDQ. The fraction of low-spin FeIII increases at room temperature.

Expanding the Chemistry of Actinide Metallocene Bromides. Synthesis, Properties and Molecular Structures of the Tetravalent and Trivalent Uranium Bromide Complexes: (C 5Me 4R) 2UBr 2, (C 5Me 4R) 2U(O-2,6- iPr 2C 6H 3)(Br), and [K(THF)][(C 5Me 4R) 2UBr 2] (R = Me, Et)

DOE PAGES

Lichtscheidl, Alejandro Gaston; Pagano, Justin K.; Scott, Brian Lindley; ...

2016-01-06

The organometallic uranium species (C 5Me 4R) 2UBr 2 (R = Me, Et) were obtained by treating their chloride analogues (C 5Me 4R) 2UCl 2 (R = Me, Et) with Me 3SiBr. Treatment of (C 5Me 4R) 2UCl 2 and (C 5Me 4R) 2UBr 2 (R = Me, Et) with K(O-2,6- iPr 2C 6H 3) afforded the halide aryloxide mixed-ligand complexes (C 5Me 4R) 2U(O-2,6- iPr 2C 6H 3)(X) (R = Me, Et; X = Cl, Br). Complexes (C 5Me 4R) 2U(O-2,6- iPr 2C 6H 3)(Br) (R = Me, Et) can also be synthesized by treating (C 5Me 4R) 2U(O-2,6-more » iPr 2C 6H 3)(Cl) (R = Me, Et) with Me 3SiBr, respectively. Reduction of (C 5Me 4R) 2UCl 2 and (C 5Me 4R) 2UBr 2 (R = Me, Et) with KC 8 led to isolation of uranium(III) “ate” species [K(THF)][(C 5Me 5) 2UX 2] (X = Cl, Br) and [K(THF) 0.5][(C 5Me 4Et) 2UX 2] (X = Cl, Br), which can be converted to the neutral complexes (C 5Me 4R) 2U[N(SiMe 3) 2] (R = Me, Et). Analyses by nuclear magnetic resonance spectroscopy, X-ray crystallography, and elemental analysis are also presented.« less

The Lewis superacid Al[N(C6F5)2]3 and its higher homolog Ga[N(C6F5)2]3 – structural features, theoretical investigation and reactions of a metal amide with higher fluoride ion affinity than SbF5† †Electronic supplementary information (ESI) available. CCDC 1557072–1557076. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c7sc03988c

PubMed Central

Kögel, J. F.; Sorokin, D. A.; Khvorost, A.; Scott, M.; Harms, K.; Himmel, D.; Krossing, I.

2017-01-01

Herein we present the synthesis of the two Lewis acids Al[N(C6F5)2]3 (ALTA) and Ga[N(C6F5)2]3 (GATA) via salt elimination reactions. The metal complexes were characterized by NMR-spectroscopic methods and X-ray diffraction analysis revealing the stabilization of the highly Lewis acidic metal centers by secondary metal–fluorine contacts. The Lewis acidic properties of Al[N(C6F5)2]3 and Ga[N(C6F5)2]3 are demonstrated by reactions with Lewis bases resulting in the formation of metallates accompanied by crucial structural changes. The two metallates [Cs(Tol)3]+[FAl(N(C6F5)2)3]– and [AsPh4]+[ClGa(N(C6F5)2)3]– contain interesting weakly coordinating anions. The reaction of Al[N(C6F5)2]3 with trityl fluoride yielded [CPh3]+[FAl(N(C6F5)2)3]– which could find application in the activation of metallocene polymerization catalysts. The qualitative Lewis acidity of Al[N(C6F5)2]3 and Ga[N(C6F5)2]3 was investigated by means of competition experiments for chloride ions in solution. DFT calculations yielded fluoride ion affinities in the gas phase (FIA) of 555 kJ mol–1 for Al[N(C6F5)2]3 and 472 kJ mol–1 for Ga[N(C6F5)2]3. Thus, Al[N(C6F5)2]3 can be considered a Lewis superacid with a fluoride affinity higher than SbF5 (493 kJ mol–1) whereas the FIA of the corresponding gallium complex is slightly below the threshold to Lewis superacidity. PMID:29629094

Stereospecific olefin polymerization catalysts

DOEpatents

Bercaw, John E.; Herzog, Timothy A.

1998-01-01

A metallocene catalyst system for the polymerization of .alpha.-olefins to yield stereospecific polymers including syndiotactic, and isotactic polymers. The catalyst system includes a metal and a ligand of the formula ##STR1## wherein: R.sup.1, R.sup.2, and R.sup.3 are independently selected from the group consisting of hydrogen, C.sub.1 to C.sub.10 alkyl, 5 to 7 membered cycloalkyl, which in turn may have from 1 to 3 C.sub.1 to C.sub.10 alkyls as a substituent, C.sub.6 to C.sub.15 aryl or arylalkyl in which two adjacent radicals may together stand for cyclic groups having 4 to 15 carbon atoms which in turn may be substituted, or Si(R.sup.8).sub.3 where R.sup.8 is selected from the group consisting of C.sub.1 to C.sub.10 alkyl, C.sub.6 to C.sub.15 aryl or C.sub.3 to C.sub.10 cycloalkyl; R.sup.4 and R.sup.6 are substituents both having van der Waals radii larger than the van der Waals radii of groups R.sup.1 and R.sup.3 ; R.sup.5 is a substituent having a van der Waals radius less than about the van der Waals radius of a methyl group; E.sup.1, E.sup.2 are independently selected from the group consisting of Si(R.sup.9).sub.2, Si(R.sup.9).sub.2 --Si(R.sup.9).sub.2, Ge(R.sup.9).sub.2, Sn(R.sup.9).sub.2, C(R.sup.9).sub.2, C(R.sup.9).sub.2 --C(R.sup.9).sub.2, where R.sup.9 is C.sub.1 to C.sub.10 alkyl, C.sub.6 to C.sub.15 aryl or C.sub.3 to C.sub.10 cycloalkyl; and the ligand may have C.sub.S or C.sub.1 -symmetry. Preferred metals are selected from the group consisting of group III, group IV, group V or lanthanide group elements. The catalysts are used to prepare stereoregular polymers including polypropylene from .alpha.-olefin monomers.

Experimental and DFT computational study of β-Me and β-H elimination coupled with proton transfer: From amides to enamides in Cp* 2MX (M = La, Ce)

DOE PAGES

Rozenel, Sergio S.; Perrin, Lionel; Eisenstein, Odile; ...

2016-10-26

The thermal rearrangement of the f-block metallocene amides Cp* 2MNR 1R 2, where R 1 is CHMe 2, R 2 is either CHMe 2 or CMe 3, and M is either La or Ce, to the corresponding enamides Cp* 2MNR 1[C(Me)=CH 2] and H 2 or CH 4, respectively, occurs when the solid amides are heated in sealed evacuated ampules at 160–180 °C for 1–2 weeks. The net reaction is a β-H or β-Me elimination followed by a γ-abstraction of a proton at the group from which the β-elimination occurs. When R 1 is either SiMe 3 or SiMe 2CMemore » 3 and R 2 is CMe 3, the enamide Cp* 2MNR 1[C(Me)=CH 2] is isolated, the result of β-Me elimination, but when R 2 is CHMe 2, the enamides Cp* 2MNR 1[C(Me)=CH 2] and Cp* 2NR 1[C(H)=CH 2] are isolated, the result of β-H and β-Me elimination. In the latter cases, both enamides are formed in similar amounts and the rates of the β-H and β-Me elimination steps must be similar. A two-step mechanism is developed from DFT calculations. The first step is migration of a hydride or a methyl anion to the Cp* 2M fragment, forming M–H or M–Me bonds as the N=C bond in the intermediate imine forms. Furthermore, the enamide evolves from the metal-coordinated imine by abstraction of a proton from the γ-carbon of the intermediate imine. The two elementary steps involve significant geometrical changes within the N αC βC γ set of atoms during the two-step elimination process that are in large part responsible for the relatively high activation barriers for the net reaction, which may be classified as a proton-coupled hydride or methyl anion transfer reaction.« less

Experimental and DFT computational study of β-Me and β-H elimination coupled with proton transfer: From amides to enamides in Cp* 2MX (M = La, Ce)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rozenel, Sergio S.; Perrin, Lionel; Eisenstein, Odile

The thermal rearrangement of the f-block metallocene amides Cp* 2MNR 1R 2, where R 1 is CHMe 2, R 2 is either CHMe 2 or CMe 3, and M is either La or Ce, to the corresponding enamides Cp* 2MNR 1[C(Me)=CH 2] and H 2 or CH 4, respectively, occurs when the solid amides are heated in sealed evacuated ampules at 160–180 °C for 1–2 weeks. The net reaction is a β-H or β-Me elimination followed by a γ-abstraction of a proton at the group from which the β-elimination occurs. When R 1 is either SiMe 3 or SiMe 2CMemore » 3 and R 2 is CMe 3, the enamide Cp* 2MNR 1[C(Me)=CH 2] is isolated, the result of β-Me elimination, but when R 2 is CHMe 2, the enamides Cp* 2MNR 1[C(Me)=CH 2] and Cp* 2NR 1[C(H)=CH 2] are isolated, the result of β-H and β-Me elimination. In the latter cases, both enamides are formed in similar amounts and the rates of the β-H and β-Me elimination steps must be similar. A two-step mechanism is developed from DFT calculations. The first step is migration of a hydride or a methyl anion to the Cp* 2M fragment, forming M–H or M–Me bonds as the N=C bond in the intermediate imine forms. Furthermore, the enamide evolves from the metal-coordinated imine by abstraction of a proton from the γ-carbon of the intermediate imine. The two elementary steps involve significant geometrical changes within the N αC βC γ set of atoms during the two-step elimination process that are in large part responsible for the relatively high activation barriers for the net reaction, which may be classified as a proton-coupled hydride or methyl anion transfer reaction.« less

Stereospecific olefin polymerization catalysts

DOEpatents

Bercaw, J.E.; Herzog, T.A.

1998-01-13

A metallocene catalyst system is described for the polymerization of {alpha}-olefins to yield stereospecific polymers including syndiotactic, and isotactic polymers. The catalyst system includes a metal and a ligand of the formula shown wherein: R{sup 1}, R{sup 2}, and R{sup 3} are independently selected from the group consisting of hydrogen, C{sub 1} to C{sub 10} alkyl, 5 to 7 membered cycloalkyl, which in turn may have from 1 to 3 C{sub 1} to C{sub 10} alkyls as a substituent, C{sub 6} to C{sub 15} aryl or arylalkyl in which two adjacent radicals may together stand for cyclic groups having 4 to 15 carbon atoms which in turn may be substituted, or Si(R{sup 8}){sub 3} where R{sup 8} is selected from the group consisting of C{sub 1} to C{sub 10} alkyl, C{sub 6} to C{sub 15} aryl or C{sub 3} to C{sub 10} cycloalkyl; R{sup 4} and R{sup 6} are substituents both having van der Waals radii larger than the van der Waals radii of groups R{sup 1} and R{sup 3}; R{sup 5} is a substituent having a van der Waals radius less than about the van der Waals radius of a methyl group; E{sup 1}, E{sup 2} are independently selected from the group consisting of Si(R{sup 9}){sub 2}, Si(R{sup 9}){sub 2}--Si(R{sup 9}){sub 2}, Ge(R{sup 9}){sub 2}, Sn(R{sup 9}){sub 2}, C(R{sup 9}){sub 2}, C(R{sup 9}){sub 2}--C(R{sup 9}){sub 2}, where R{sup 9} is C{sub 1} to C{sub 10} alkyl, C{sub 6} to C{sub 15} aryl or C{sub 3} to C{sub 10} cycloalkyl; and the ligand may have C{sub S} or C{sub 1}-symmetry. Preferred metals are selected from the group consisting of group III, group IV, group V or lanthanide group elements. The catalysts are used to prepare stereoregular polymers including polypropylene from {alpha}-olefin monomers.

Monochloro non-bridged half-metallocene-type zirconium complexes containing phosphine oxide-(thio)phenolate chelating ligands as efficient ethylene polymerization catalysts.

PubMed

Tang, Xiao-Yan; Wang, Yong-Xia; Liu, San-Rong; Liu, Jing-Yu; Li, Yue-Sheng

2013-01-14

A series of novel monochloro half-zirconocene complexes containing phosphine oxide-(thio)phenolate chelating ligands of the type, ClCp'Zr[X-2-R(1)-4-R(2)-6-(Ph(2)P=O)C(6)H(2)](2) (Cp' = C(5)H(5), 2a: X = O, R(1) = Ph, R(2) = H; 2b: X = O, R(1) = F, R(2) = H; 2c: X = O, R(1) = (t)Bu, R(2) = H; 2d: X = O, R(1) = R(2) = (t)Bu; 2e: X = O, R(1) = SiMe(3), R(2) = H; 2f: X = S, R(1) = SiMe(3), R(2) = H; Cp' = C(5)Me(5), 2g: X = O, R(1) = SiMe(3), R(2) = H), have been synthesized in high yields. These complexes were identified by (1)H {(13)C} NMR and elemental analyses. Structures for 2b, 2c and 2f were further confirmed by X-ray crystallography. Structural characterization of these complexes reveals crowded environments around the zirconium. Complexes 2b and 2c adopt six-coordinate, distorted octahedral geometry around the zirconium center, in which the equatorial positions are occupied by three oxygen atoms of two chelating phosphine oxide-bridged phenolate ligands and a chlorine atom. The cyclopentadienyl ring and one oxygen atom of the ligand are coordinated on the axial position. Complex 2f also folds a six-coordinate, distorted octahedral geometry around the Zr center, consisting of a Cp-Zr-O (in P=O) axis [177.16°] and a distorted plane of two sulfur atoms and one oxygen atom of two chelating phosphine oxide-bridged thiophenolate ligands as well as a chlorine atom. When activated by modified methylaluminoxane (MMAO), all the complexes exhibited high activities towards ethylene polymerization at high temperature (75 °C), giving high molecular weight polymers with unimodal molecular weight distribution. The formation of 14-electron, cationic metal alkyl species might come from the Zr-O (in phenol ring) bond cleavage based on the DFT calculations study.

Mediated water electrolysis in biphasic systems.

PubMed

Scanlon, Micheál D; Peljo, Pekka; Rivier, Lucie; Vrubel, Heron; Girault, Hubert H

2017-08-30

The concept of efficient electrolysis by linking photoelectrochemical biphasic H 2 evolution and water oxidation processes in the cathodic and anodic compartments of an H-cell, respectively, is introduced. Overpotentials at the cathode and anode are minimised by incorporating light-driven elements into both biphasic reactions. The concepts viability is demonstrated by electrochemical H 2 production from water splitting utilising a polarised water-organic interface in the cathodic compartment of a prototype H-cell. At the cathode the reduction of decamethylferrocenium cations ([Cp 2 *Fe (III) ] + ) to neutral decamethylferrocene (Cp 2 *Fe (II) ) in 1,2-dichloroethane (DCE) solvent takes place at the solid electrode/oil interface. This electron transfer process induces the ion transfer of a proton across the immiscible water/oil interface to maintain electroneutrality in the oil phase. The oil-solubilised proton immediately reacts with Cp 2 *Fe (II) to form the corresponding hydride species, [Cp 2 *Fe (IV) (H)] + . Subsequently, [Cp 2 *Fe (IV) (H)] + spontaneously undergoes a chemical reaction in the oil phase to evolve hydrogen gas (H 2 ) and regenerate [Cp 2 *Fe (III) ] + , whereupon this catalytic Electrochemical, Chemical, Chemical (ECC') cycle is repeated. During biphasic electrolysis, the stability and recyclability of the [Cp 2 *Fe (III) ] + /Cp 2 *Fe (II) redox couple were confirmed by chronoamperometric measurements and, furthermore, the steady-state concentration of [Cp 2 *Fe (III) ] + monitored in situ by UV/vis spectroscopy. Post-biphasic electrolysis, the presence of H 2 in the headspace of the cathodic compartment was established by sampling with gas chromatography. The rate of the biphasic hydrogen evolution reaction (HER) was enhanced by redox electrocatalysis in the presence of floating catalytic molybdenum carbide (Mo 2 C) microparticles at the immiscible water/oil interface. The use of a superhydrophobic organic electrolyte salt was critical to ensure proton transfer from water to oil, and not anion transfer from oil to water, in order to maintain electroneutrality after electron transfer. The design, testing and successful optimisation of the operation of the biphasic electrolysis cell under dark conditions with Cp 2 *Fe (II) lays the foundation for the achievement of photo-induced biphasic water electrolysis at low overpotentials using another metallocene, decamethylrutheneocene (Cp 2 *Ru (II) ). Critically, Cp 2 *Ru (II) may be recycled at a potential more positive than that of proton reduction in DCE.

Congested ferrocenyl polyphosphanes bearing electron-donating or electron-withdrawing phosphanyl groups: assessment of metallocene conformation from NMR spin couplings and use in palladium-catalyzed chloroarenes activation.

PubMed

Mom, Sophal; Beaupérin, Matthieu; Roy, David; Royer, Sylviane; Amardeil, Régine; Cattey, Hélène; Doucet, Henri; Hierso, J-C

2011-11-21

The synthesis of novel substituted cyclopentadienyl salts that incorporate both a congested branched alkyl group (tert-butyl, (triphenyl)methyl, or tri(4-tert-butyl)phenylmethyl) and a phosphanyl group is reported. The introduction of either electron-withdrawing or electron-donating substituents (furyl, i-propyl, cyclohexyl, tert-butyl) on P atoms was generally achieved in high yield. The modular synthesis of ferrocenyl polyphosphanes from an assembly of these cyclopentadienyl salts was investigated, leading to the formation of new triphosphanes (denoted as 9-12) and diphosphanes (denoted as 14-16). The resulting phosphanes are not sensitive to air or moisture, even when electron-rich substituents are present. This set of polyphosphanes displays varied conformational features, which are discussed in the light of their multinuclear NMR characterization in solution and of the X-ray solid state structure of the representative triphosphane 1,2-bis(diphenylphosphanyl)-1'-(diisopropylphosphanyl)-3'-(triphenyl)methyl-4-tert-butyl ferrocene, 11. In particular, the existence of a range of significantly different nonbonded ("through-space", TS) spin-spin coupling constants between heteroannular P atoms, for the triphosphanes of this class, allowed their preferred conformation in solution to be appraised. The study evidences an unanticipated flexibility of the ferrocene platform, despite the presence of very congested tert-butyl and trityl groups. Herein, we show that, contrary to our first belief, the preferred conformation for the backbone of ferrocenyl polyphosphanes can not only depend on the hindrance of the groups decorating the cyclopentadienyl rings but is also a function of the substituents of the phosphanyl groups. The interest of these robust phosphanes as ligands was illustrated in palladium catalysis for the arylation of n-butyl furan with chloroarenes, using direct C-H activation of the heteroaromatic in the presence of low metal/ligand loadings (0.5-1.0 mol %). Thus, 4-chlorobenzonitrile, 4-chloronitrobenzene, 4-chloropropiophenone, and 4-(trifluoromethyl)chlorobenzene were efficiently coupled to n-butyl furan, using Pd(OAc)(2) associated to the new diphosphane ligands 1,1'-bis(diisopropylphosphanyl)-3,3'-di(triphenyl)methyl ferrocene (15) or 1,1'-bis(dicyclohexylphosphanyl)-3,3'-di(triphenyl)methylferrocene (16), which respectively hold the electron-rich -Pi-Pr(2) and -PCy(2) groups.

Concurrent synergism and inhibition in bimetallic catalysis: catalytic binuclear elimination, solute-solute interactions and a hetero-bimetallic hydrogen-bonded complex in rh-mo hydroformylations.

PubMed

Li, Chuanzhao; Cheng, Shuying; Tjahjono, Martin; Schreyer, Martin; Garland, Marc

2010-04-07

Hydroformylations of cyclopentene and 3,3-dimethylbut-1-ene were performed using both Rh(4)(CO)(12) and (eta(5)-C(5)H(5))Mo(CO)(3)H as precursors in n-hexane at 298 K. Both stoichiometric and catalytic hydroformylations were conducted as well as isotopic labeling experiments. Six organometallic pure component spectra were recovered from the high-pressure FTIR experiments, namely the known species Rh(4)(CO)(12), (eta(5)-C(5)H(5))Mo(CO)(3)H, RCORh(CO)(4), and the new heterobimetallic complexes RhMo(CO)(7)(eta(5)-C(5)H(5)), a weak hydrogen bonded species (eta(5)-C(5)H(5))Mo(CO)(3)H-C(5)H(9)CORh(CO)(4), and a substituted RhMo(CO)(7-y)(eta(5)-C(5)H(5))L(y), where y = 1 or 2 and L = (pi-C(5)H(8)). The main findings were (1) catalytic binuclear elimination (CBER) occurs between (eta(5)-C(5)H(5))Mo(CO)(3)H and RCORh(CO)(4) resulting in aldehyde and RhMo(CO)(7)(eta(5)-C(5)H(5)), and this mechanism is responsible for ca. 10% of the product formation; (2) molecular hydrogen is readily activated by the new heterobimetallic complex(es); (3) FTIR and DFT spectroscopic evidence suggests that the weak hydrogen bonded species (eta(5)-C(5)H(5))Mo(CO)(3)H-C(5)H(9)CORh(CO)(4) has an interaction of the type eta(5)-C(5)H(4)-H...O=C; and (4) independent physicochemical experiments for volumes of interaction confirm that significant solute-solute interactions are present. With respect to the efficiency of the catalytic cycle, the formation of a weak (eta(5)-C(5)H(5))Mo(CO)(3)H-C(5)H(9)CORh(CO)(4) complex results in a significant decrease in the measured turnover frequency (TOF) and is the primary reason for the inhibition observed in the bimetallic catalytic hydroformylation. Such hydrogen bonding through the eta(5)-C(5)H(5) ring might have relevance to inhibition observed in other catalytic metallocene systems. The present catalytic system is an example of concurrent synergism and inhibition in bimetallic homogeneous catalysis.

Self-Consistency of the Lauritzen-Hoffman and Strobl Models of Polymer Crystallization Evaluated for Poly(epsilon-caprolactone) Fractions and Effect of Composition on the Phenomenon of Concurrent Crystallization in Polyethylene Blends

NASA Astrophysics Data System (ADS)

Sheth, Swapnil Suhas

Narrow molecular weight fractions of poly(epsilon-caprolactone) were successfully obtained using the successive precipitation fractionation technique with toluene/n-heptane as a solvent/nonsolvent pair. Calorimetric studies of the melting behavior of fractions that were crystallized either isothermally or under constant cooling rate conditions suggested that the isothermal crystallization of the samples should be used for a proper evaluation of the molecular weight dependence of the observed melting temperature and degree of crystallinity in PCL. The molecular weight and temperature dependence of the spherulitic growth rate of fractions was studied in the context of the Lauritzen-Hoffman two-phase model and the Strobl three-phase model of polymer crystallization. The zero-growth rate temperatures, determined from spherulitic growth rates using four different methods, are consistent with each other and increase with chain length. The concomitant increase in the apparent secondary nucleation constant was attributed to two factors. First, for longer chains there is an increase in the probability that crystalline stems belong to loose chain-folds, hence, an increase in fold surface free energy. It is speculated that the increase in loose folding and resulting decrease in crystallinity with increasing chain length are associated with the ester group registration requirement in PCL crystals. The second contribution to the apparent nucleation constant arises from chain friction associated with segmental transport across the melt/crystal interface. These factors were responsible for the much stronger chain length dependence of spherulitic growth rates at fixed undercooling observed here with PCL than previously reported for PE and PEO. In the case of PCL, the scaling exponent associated with the chain length dependence of spherulitic growth rates exceeds the upper theoretical bound of 2 predicted from the Brochard- DeGennes chain pullout model. Observation that zero-growth and equilibrium melting temperature values are identical with each other within the uncertainty of their determinations casts serious doubt on the validity of Strobl three-phase model. A novel method is proposed to determine the Porod constant necessary to extrapolate the small angle X-ray scattering intensity data to large scattering vectors. The one-dimensional correlation function determined using this Porod constant yielded the values of lamellar crystal thickness, which were similar to these estimated using the Hosemann-Bagchi Paracrystalline Lattice model. The temperature dependence of the lamellar crystal thickness was consistent with both LH and the Strobl model of polymer crystallization. However, in contrast to the predictions of Strobl's model, the value of the mesomorph-to-crystal equilibrium transition temperature was very close to the zero-growth temperature. Moreover, the lateral block sizes (obtained using wide angle X-ray diffraction) and the lamellar thicknesses were not found to be controlled by the mesomorph-to-crystal equilibrium transition temperature. Hence, we concluded that the crystallization of PCL is not mediated by a mesophase. Metallocene-catalyzed linear low-density (m-LLDPE with 3.4 mol% 1-octene) and conventional low-density (LDPE) polyethylene blends of different compositions were investigated for their melt-state miscibility and concurrent crystallization tendency. Differential scanning calorimetric studies and morphological studies using atomic force microscopy confirm that these blends are miscible in the melt-state for all compositions. LDPE chains are found to crystallize concurrently with m-LLDPE chains during cooling in the m-LLDPE crystallization temperature range. While the extent of concurrent crystallization was found to be optimal in .. .. iv blends with highest m-LLDPE content studied, strong evidence was uncovered for the existence of a saturation effect in the concurrent crystallization behavior. This observation leads us to suggest that co-crystallization, rather than mere concurrent crystallization, of LDPE with m- LLDPE can indeed take place. Matching of the respective sequence length distributions in LDPE and m-LLDPE is suggested to control the extent of co-crystallization.

PROGRESS REPORT ON RAW MATERIALS FOR MAY 1957. Chemical Technology Div.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Brown, K.B.; Coleman, C.F.; Crouse, D.J.

1957-09-27

Systematic Studies. A mixed n-octyl-n-decyl tertiary amine, commercially available in development quantities, appeared promising for process use. Its U extraction power was similar to that of tri-n-octylamine, and loss by distribution to a sulfate liquor was lower. A corresponding secondary amine was similar in extraction behavior to di-n-decylamine, but loss by distribution was higher. Screening tests of U extraction power from diluteacid test solutions are summarized for various organophosphoras compounds, with principal attention to dialkylphosphinic acids, monoalkylphosphonic acids, and some polymeric compounds. Unusually high U extraction power was shown by in alpha -hydroxy phosphinic acid, phenyl(1hydroxy-2-ethylhexyl)phosphinic acid. Uranium(IV) was extractedmore » strongly from dilute icidic sulfate solution by a primary and s secondaryamine, but not bya tertiary amine. It was extracted more strongly than U/sup 6+/ from hydrochloric acid solutions by di(2-ethylhexyl)phosphoric acid (D2EHPA). In contrast to U/sup 6+/, U/sup 4+/ extraction by D2EHPA was enhanced little if any by the presence of TBP. Process Development. In tests with tri-iso-octylamine, a number of diluent additives were tested for ability to prevent separation of amine heteropolymolybdate precipitates from the usual kerosene-alcohol diluent during the chloride stripping cycle. Addition of nitrobenzeneat 100 g/liter was effective for this purpose. In other tests, several of the Mo precipitates were separated and analyzed for amine, Mo, phosphate,and V content. The amount of Mo reporting to U products from the Dapex process varied with the method and conditions by which uranium was precipitated from the sodium carbonate strip solution. Direct caustic precipitation of the U gave products essentially free of Mo although filtration characteristics of the precipitate were poor. When the U was recovered by first acidifying with H/sub 2/SO/sub 4/ and then precipitating with NH/sub 3/, most of the Mo remained in the product even when an excess of ammonia was used. Recovery by acidification and precipitation with caustic resulted in better Mo decontamination, particularly when an appreciable excess of caustic was added. Engineering Studies. The rate of U extraction from a synthetic H/sub 2/SO/sub 4/ leach liquor by a Dapex-tyne organic was proportional to the cube root of power input and was slightly faster in a 12-in. than in a 6- in. mixer at the same power input per unit volume. At a given power input the rate increased with decreased turbine diameter. Location of the turbine at one diameter from the bottom of the mixer tank provided only slightly faster extraction than at a center location. (For preceding period see ORNL-2346.) (auth)« less

Tabulation of comet observations.

NASA Astrophysics Data System (ADS)

2000-04-01

Concerning comets: C/1995 O1 (Hale-Bopp), C/1997 BA6 (Spacewatch), C/1998 K2 (LINEAR), C/1998 M5 (LINEAR), C/1998 P1 (Williams), C/1998 T1 (LINEAR), C/1998 U5 (LINEAR), C/1999 A1 (Tilbrook), C/1999 E1 (Li), C/1999 F1 (Catalina), C/1999 F2 (Dalcanton), C/1999 H1 (Lee), C/1999 H3 (LINEAR), C/1999 J2 (Skiff), C/1999 J3 (LINEAR), C/1999 K1 (SOHO), C/1999 K2 (Ferris), C/1999 K3 (LINEAR), C/1999 K5 (LINEAR), C/1999 K6 (LINEAR), C/1999 K8 (LINEAR), C/1999 L3 (LINEAR), C/1999 N2 (Lynn), C/1999 N4 (LINEAR), C/1999 S2 (McNaught-Watson), C/1999 S3 (LINEAR), C/1999 S4 (LINEAR), C/1999 T1 (McNaught-Hartley), C/1999 T2 (LINEAR), C/1999 T3 (LINEAR), C/1999 U1 (Ferris), C/1999 U4 (Catalina-Skiff), C/1999 XS87 (LINEAR), C/1999 Y1 (LINEAR), C/2000 A1 (Montani), C/2000 B2 (LINEAR), C/2000 B4 (LINEAR), C/2000 CT54 (LINEAR), C/2000 D2 (LINEAR), 4P/Faye, 9P/Tempel 1, 10P/Tempel 2, 21P/Giacobini-Zinner, 29P/Schwassmann-Wachmann 1, 37P/Forbes, 50P/Arend, 52P/Harrington-Abell, 59P/Kearns-Kwee, 60P/Tsuchinshan 2, 63P/Wild 1, 71P/Clark, 73P/Schwassmann-Wachmann 3, 74P/Smirnova-Chernykh, 84P/Giclas, 93P/Lovas 1, 95P/Chiron, 105P/Singer Brewster, 106P/Schuster, 114P/Wisemann-Skiff, 140P/Bowell-Skiff, 141P/Machholz 2, 142P/Ge-Wang, 143P/Kowal-Mrkos, P/1998 S1 (LINEAR-Mueller), P/1998 U3 (Jäger), P/1998 W1 (Spahr), P/1998 Y2 (Li), P/1999 RO28 (LONEOS), P/1999 U3 (LINEAR), P/1999 V1 (Catalina), P/1999 WJ7 (Korlević), P/1999 X1 (Hug-Bell), P/1999 XB69 (LINEAR), P/1999 XN120 (Catalina), P/2000 B3 (LINEAR), P/2000 C1 (Hergenrother), P/2000 G1 (LINEAR).

Multigrid approaches to non-linear diffusion problems on unstructured meshes

NASA Technical Reports Server (NTRS)

Mavriplis, Dimitri J.; Bushnell, Dennis M. (Technical Monitor)

2001-01-01

The efficiency of three multigrid methods for solving highly non-linear diffusion problems on two-dimensional unstructured meshes is examined. The three multigrid methods differ mainly in the manner in which the nonlinearities of the governing equations are handled. These comprise a non-linear full approximation storage (FAS) multigrid method which is used to solve the non-linear equations directly, a linear multigrid method which is used to solve the linear system arising from a Newton linearization of the non-linear system, and a hybrid scheme which is based on a non-linear FAS multigrid scheme, but employs a linear solver on each level as a smoother. Results indicate that all methods are equally effective at converging the non-linear residual in a given number of grid sweeps, but that the linear solver is more efficient in cpu time due to the lower cost of linear versus non-linear grid sweeps.

Tabulation of comet observations.

NASA Astrophysics Data System (ADS)

1999-10-01

Concerning comets: C/1995 O1 (Hale-Bopp), C/1997 BA6 (Spacewatch), C/1997 J2 (Meunier-Dupouy), C/1998 K5 (LINEAR), C/1998 M2 (LINEAR), C/1998 M5 (LINEAR), C/1998 P1 (Williams), C/1998 Q1 (LINEAR), C/1998 T1 (LINEAR), C/1998 U5 (LINEAR), C/1999 F2 (Dalcanton), C/1999 H1 (Lee), C/1999 H3 (LINEAR), C/1999 J2 (Skiff), C/1999 J3 (LINEAR), C/1999 K2 (Ferris), C/1999 K3 (LINEAR), C/1999 K5 (LINEAR), C/1999 K6 (LINEAR), C/1999 K8 (LINEAR), C/1999 L2 (LINEAR), C/1999 N2 (Lynn), C/1999 N4 (LINEAR), C/1999 S3 (LINEAR), C/1999 S4 (LINEAR), C/1999 T1 (McNaught-Hartley), C/1999 T2 (LINEAR), C/1999 T3 (LINEAR), C/1999 U1 (Ferris), 2P/Encke, 4P/Faye, 10P/Tempel 2, 21P/Giacobini-Zinner, 29P/Schwassmann-Wachmann 1, 37P/Forbes, 46P/Wirtanen, 50P/Arend, 52P/Harrington-Abell, 59P/Kearns-Kwee, 74P/Smirnova-Chernykh, 84P/Giclas, 88P/Howell, 93P/Lovas 1, 106P/Schuster, 114P/Wiseman-Skiff, 136P/Mueller 3, 137P/Shoemaker-Levy 2, 141P/Machholz 2, 142P/Ge-Wang, P/1998 G1 (LINEAR), P/1998 QP54 (LONEOS-Tucker), P/1998 S1 (LINEAR-Mueller), P/1998 U2 (Mueller), P/1998 U3 (Jäger), P/1998 W1 (Spahr), P/1998 Y1 (LINEAR), P/1999 RO2 (LONEOS).

I. Direct observation of zirconocene-catalyzed alkene polymerization via NMR and the role of an aluminum alkyl during polymerization. II. Design and evaluation of an online nanoscience course for teachers

NASA Astrophysics Data System (ADS)

Tomasik, Janice Hall

The plastics industry has been revolutionalized by development of group 4 metallocene polymerization catalysts. These catalysts have higher activities and stereoselectivities than traditional heterogeneous Ziegler-Natta polymerization catalysts, and produce polymers with narrower molecular weight distributions and with better control of the polymer stereochemistry. The reaction kinetics of catalytic alkene polymerizations are complicated and difficult to resolve macroscopically. To overcome these difficulties, research has used NMR spectroscopy to directly observe catalytic reaction intermediates; many advances in our understanding of the complex mechanisms behind these polymerization reactions have resulted. In this work, the direct observation of alkene insertion into zirconocene-polymeryls via NMR spectroscopy is presented. Alkenes studied are 3-methylpentene, styrene, and 1,4-pentadiene. Kinetic measurements are reported for the polymerization of 3-methylpentene by rac-(EBI)Zr(Me)(MeB(C6F 5)3) (EBI = C2H4(1-indenyl)2) and rac-(EBI)Zr(polyhexenyl)(MeB(C6F5) 3). Also presented are NMR spectroscopic characterizations of rac-(EBI)Zr(styrenyl)(MeB(C6F5)3) and rac-(EBI)Zr(1,4-pentadienyl)(MeB(C6F 5)3). In addition, NMR spectroscopy is used to directly monitor the behavior of an aluminum alkyl during the polymerization of 1-hexene by rac -(EBI)2Zr(Me)(MeB(C6F5)3). The rates of polymerization are not inhibited by Al(iBu) 2(BHT), Al(Me)(BHT)2, or Al(iBu)3 (BHT = 2,6-di- tert-butyl-4-methylphenyl). Detailed measurement of polymerization rate and catalyst speciation demonstrate that BHT modified aluminum alkyls protect active sites from decomposition in the presence of protic impurities such as methanol. Also presented in this work is the design and evaluation of an online course for teachers about nanoscience. Nanotechnology is an important emerging field that is estimated to need about 2 million workers worldwide by 2015. Therefore the educational system is being encouraged to incorporate major nanoscience concepts into curricula. In order to facilitate the integration of nanoscience, an online professional development course for teachers has been developed and offered at the University of Wisconsin-Madison. Evaluation results from the first three versions of the course indicate the online learning environment was very close to ideal. Comparisons of pre-instruction to post-instruction quiz responses indicate significant learning gains by participants. Importantly, survey results show the online course helped teachers to successfully incorporate nanoscience into their curricula.

High impact strength polymers having novel nano-structures produced via reactive extrusion

NASA Astrophysics Data System (ADS)

Tortorella, Nathan Fraser

A major focus of scientists and engineers over the last century has been to increase the impact strength and therefore reduce the brittleness of materials. By altering and adding energy absorption mechanisms, brittle failure can be averted. Isotactic polypropylene (PP) is the focus of this dissertation because it is an extremely low cost, high volume, versatile plastic but behaves in a brittle manner at or below room temperature or in a notched state. Early work on impact modification of polypropylene focused on blending energy-absorbing low density elastomers and rubbers. These binary blends all had a common problem---an increase in impact strength was paralleled by a significant decrease in both elastic modulus and yield stress. Reactive extrusion processing has allowed the in-situ compatibilization of isotactic polypropylene and metallocene-catalyzed ethylene-octene copolymers (EOCs). This process involves combining both the comonomer and vector fluid approaches to grafting polyolefins. Styrene monomer and a multifunctional acrylate monomer undergo peroxide-induced copolymerization and grafting in the presence of both PP and EOC. This results in a phase separated alloy with an impact strength over 13 times that of pure polypropylene and double that of the physical blend. There is also a significant improvement in stress-strain performance when comparing the alloys to physical blend counterparts. Many researchers have categorized the necessary components to toughening polypropylene as pertaining to the amorphous phase. The alloys described in this dissertation meet the criteria put forth by these researchers, namely low density, crystallinity, and modulus of the elastomer phase, sub-micron particle diameter, close inter-particle distance, and a high degree of entanglements of both the PP matrix phase and EOC minor phase. But many people neglect to study the crystalline state of impact modified PP in conjunction with the amorphous phase. This work shows that the typical 10-100 mum diameter spherulitic structures found in pure PP are not present in the alloys. In fact, the spherulites are less than a micron in diameter, are uniformly distributed throughout the sample, and crystallize at much higher temperatures. SEM images, when coupled with DSC and XRD, reveal the presence of a high number of small lamellar crystals composed of a unique highly dense cross-hatched structure. Thus, impact strength and stiffness can be simultaneously improved by controlling the size and cross-hatch density of the lamellar crystals and applying phase transformation toughening concepts.

Tabulation of comet observations.

NASA Astrophysics Data System (ADS)

2000-01-01

Concerning comets: C/1995 O1 (Hale-Bopp), C/1997 BA6 (Spacewatch), C/1998 K2 (LINEAR), C/1998 M1 (LINEAR), C/1998 M5 (LINEAR), C/1998 P1 (Williams), C/1998 T1 (LINEAR), C/1998 W3 (LINEAR), C/1999 E1 (Li), C/1999 F2 (Dalcanton), C/1999 H1 (Lee), C/1999 H3 (LINEAR), C/1999 J2 (Skiff), C/1999 J3 (LINEAR), C/1999 K2 (Ferris), C/1999 K5 (LINEAR), C/1999 K6 (LINEAR), C/1999 K8 (LINEAR), C/1999 L2 (LINEAR), C/1999 L3 (LINEAR), C/1999 N2 (Lynn), C/1999 S3 (LINEAR), C/1999 S4 (LINEAR), C/1999 T1 (McNaught-Hartley), C/1999 T2 (LINEAR), C/1999 T3 (LINEAR), C/1999 U1 (Ferris), C/1999 U4 (Catalina-Skiff), C/1999 Y1 (LINEAR), 4P/Faye, 10P/Tempel 2, 29P/Schwassmann-Wachmann 1, 37P/Forbes, 50P/Arend, 59P/Kearns-Kwee, 63P/Wild 1, 65P/Gunn, 74P/Smirnova-Chernykh, 84P/Giclas, 106P/Schuster, 108P/Ciffréo, 114P/Wisemann-Skiff, 117P/Helin-Roman-Alu 1, 136P/Mueller 3, 137P/Shoemaker-Levy 2, 141P/Machholz 2, P/1998 U4 (Spahr), P/1999 RO28 (LEONOS), P/1999 U3 (LINEAR), P/1999 V1 (Catalina), P/1999 X1 (Hug-Bell).

Second-order kinetic model for the sorption of cadmium onto tree fern: a comparison of linear and non-linear methods.

PubMed

Ho, Yuh-Shan

2006-01-01

A comparison was made of the linear least-squares method and a trial-and-error non-linear method of the widely used pseudo-second-order kinetic model for the sorption of cadmium onto ground-up tree fern. Four pseudo-second-order kinetic linear equations are discussed. Kinetic parameters obtained from the four kinetic linear equations using the linear method differed but they were the same when using the non-linear method. A type 1 pseudo-second-order linear kinetic model has the highest coefficient of determination. Results show that the non-linear method may be a better way to obtain the desired parameters.

Population response to climate change: linear vs. non-linear modeling approaches.

PubMed

Ellis, Alicia M; Post, Eric

2004-03-31

Research on the ecological consequences of global climate change has elicited a growing interest in the use of time series analysis to investigate population dynamics in a changing climate. Here, we compare linear and non-linear models describing the contribution of climate to the density fluctuations of the population of wolves on Isle Royale, Michigan from 1959 to 1999. The non-linear self excitatory threshold autoregressive (SETAR) model revealed that, due to differences in the strength and nature of density dependence, relatively small and large populations may be differentially affected by future changes in climate. Both linear and non-linear models predict a decrease in the population of wolves with predicted changes in climate. Because specific predictions differed between linear and non-linear models, our study highlights the importance of using non-linear methods that allow the detection of non-linearity in the strength and nature of density dependence. Failure to adopt a non-linear approach to modelling population response to climate change, either exclusively or in addition to linear approaches, may compromise efforts to quantify ecological consequences of future warming.

Effects of calcium and phosphate on uranium(IV) oxidation: Comparison between nanoparticulate uraninite and amorphous UIV-phosphate

NASA Astrophysics Data System (ADS)

Latta, Drew E.; Kemner, Kenneth M.; Mishra, Bhoopesh; Boyanov, Maxim I.

2016-02-01

The mobility of uranium in subsurface environments depends strongly on its redox state, with UIV phases being significantly less soluble than UVI minerals. This study compares the oxidation kinetics and mechanisms of two potential products of UVI reduction in natural systems, a nanoparticulate UO2 phase and an amorphous UIV-Ca-PO4 analog to ningyoite (CaUIV(PO4)2·1-2H2O). The valence of U was tracked by X-ray absorption near-edge spectroscopy (XANES), showing similar oxidation rate constants for UIVO2 and UIV-phosphate in solutions equilibrated with atmospheric O2 and CO2 at pH 7.0 (kobs,UO2 = 0.17 ± 0.075 h-1 vs. kobs,UIVPO4 = 0.30 ± 0.25 h-1). Addition of up to 400 μM Ca and PO4 decreased the oxidation rate constant by an order of magnitude for both UO2 and UIV-phosphate. The intermediates and products of oxidation were tracked by electron microscopy, powder X-ray diffraction (pXRD), and extended X-ray absorption fine-structure spectroscopy (EXAFS). In the absence of Ca or PO4, the product of UO2 oxidation is Na-uranyl oxyhydroxide (under environmentally relevant concentrations of sodium, 15 mM NaClO4 and low carbonate concentration), resulting in low concentrations of dissolved UVI (<2.5 × 10-7 M). Oxidation of UIV-phosphate produced a Na-autunite phase (Na2(UO2)PO4·xH2O), resulting in similarly low dissolved U concentrations (<7.3 × 10-8 M). When Ca and PO4 are present in the solution, the EXAFS data and the solubility of the UVI phase resulting from oxidation of UO2 and UIV-phosphate are consistent with the precipitation of Na-autunite. Bicarbonate extractions and Ca K-edge X-ray absorption spectroscopy of oxidized solids indicate the formation of a Ca-UVI-PO4 layer on the UO2 surface and suggest a passivation layer mechanism for the decreased rate of UO2 oxidation in the presence of Ca and PO4. Interestingly, the extractions were unable to remove all of the oxidized U from partially oxidized UO2 solids, suggesting that oxidized U is distributed between the interior of the UO2 nanoparticles and the labile surface layer. Accounting for the entire pool of oxidized U by XANES is the likely reason for the higher UO2 oxidation rate constants determined here relative to prior studies. Our results suggest that the natural presence or addition of Ca and PO4 in groundwater could slow the rates of UIV oxidation, but that the rates are still fast enough to cause complete oxidation of UIV within days under fully oxygenated conditions.

Exploratory Solid-State Synthesis of Uranium Chalcogenides and Mixed Anion Uranium Chalcogenides

NASA Astrophysics Data System (ADS)

Ward, Matthew David

Several uranium chalcogenides and mixed anion uranium chalcogenides have been synthesized by solid-state synthetic methods. Structural determinations were carried out via single-crystal X-ray diffraction. Some of these compounds have been further characterized by magnetic measurements, optical properties measurements, Raman spectroscopy, resistivity measurements, XANES and XPS. Eight compounds of the composition MU8Q17 were synthesized and characterized by single-crystal X-ray diffraction. All of these compounds crystallize in the CrU8S17 structure type. XANES measurements indicate that ScU8S17 contains Sc3+ and must be charge balanced with some amount of U 3+. Two compounds of the composition ATiU3Te9 crystallize as black rectangular plates. From single-crystal magnetic measurements, CsTiU 3Te9 is consistent with antiferromagnetic coupling between magnetic U atoms. The uranium chalcogenide compounds NiUS3 and Cr4US 8 were synthesized from reaction of the elements in various fluxes. NiUS3 crystallizes in the GdFeO3 structure type. Cr 4US8 crystallizes in the orthorhombic space group D - Pnma and its structure is related to that of Li4UF 8. The compounds Rh2U6S15, Cs 2Ti2U6Se15, and Cs2Cr 2U6Se15 crystallize as black prisms in the cubic space group O-Im3m. Magnetic measurements on Cs 2Cr2U6Se15 give a value for the Weiss temperature, θWeiss, of 57.59 K, indicative of ferromagnetic coupling. Black plates of CsScU(Se2)Se3 were synthesized from the reaction of the elements in a CsCl flux. CsScU(Se2)Se 3 crystallizes in the orthorhombic space group D- Cmcm . Magnetic susceptibility measurements on CsScU(Se2)Se 3 indicate three regions of magnetic response. The uranium double salt Cs5[U2(μ-S 2)2Cl8]I crystallizes as red plates. Cs 5[U2(μ-S2)2Cl 8]I displays optical anisotropy with band gap energies of 1.99 eV and 2.08 eV along the [001] and [100] polarizations. The uranium oxychalcogenides U7O2Se12 and Na2Ba2(UO2)S4 were synthesized by intentional oxygen contamination. The structure of U7O 2Se12 is related to the previously reported U7Q 12. Na2Ba2(UO2)S4 contains isolated uranyl polyhedra in which each uranium atom may be assigned an oxidation state of +6. The four uranium(IV) chlorophosphates, UCl4(POCl3), [U2Cl9][PCl4], UCl3(PO2Cl 2), and U2Cl8(POCl3) were synthesized in an effort to synthesize new novel uranyl sulfides. All are unstable, but UCl4(POCl3) is the thermodynamically favorable phase.

Effects of calcium and phosphate on uranium(IV) oxidation: Comparison between nanoparticulate uraninite and amorphous U IV–phosphate

DOE PAGES

Latta, Drew E.; Kemner, Kenneth M.; Mishra, Bhoopesh; ...

2015-11-17

The mobility of uranium in subsurface environments depends strongly on its redox state, with U IV phases being significantly less soluble than U VI minerals. This study compares the oxidation kinetics and mechanisms of two potential products of U VI reduction in natural systems, a nanoparticulate UO 2 phase and an amorphous U IV–Ca–PO 4 analog to ningyoite (CaU IV(PO 4) 2·1–2H 2O). The valence of U was tracked by X-ray absorption near-edge spectroscopy (XANES), showing similar oxidation rate constants for U IVO 2 and U IV–phosphate in solutions equilibrated with atmospheric O 2 and CO 2 at pH 7.0more » (k obs,UO2 = 0.17 ± 0.075 h -1 vs. k obs,U IV PO4 = 0.30 ± 0.25 h -1). Addition of up to 400 μM Ca and PO 4 decreased the oxidation rate constant by an order of magnitude for both UO 2 and U IV–phosphate. The intermediates and products of oxidation were tracked by electron microscopy, powder X-ray diffraction (pXRD), and extended X-ray absorption fine-structure spectroscopy (EXAFS). In the absence of Ca or PO 4, the product of UO 2 oxidation is Na–uranyl oxyhydroxide (under environmentally relevant concentrations of sodium, 15 mM NaClO 4 and low carbonate concentration), resulting in low concentrations of dissolved U VI (<2.5 × 10 -7 M). Oxidation of U IV–phosphate produced a Na-autunite phase (Na 2(UO 2)PO 4·xH 2O), resulting in similarly low dissolved U concentrations (<7.3 × 10 -8 M). When Ca and PO 4 are present in the solution, the EXAFS data and the solubility of the UVI phase resulting from oxidation of UO 2 and UIV–phosphate are consistent with the precipitation of Na-autunite. Bicarbonate extractions and Ca K-edge X-ray absorption spectroscopy of oxidized solids indicate the formation of a Ca–UVI–PO 4 layer on the UO 2 surface and suggest a passivation layer mechanism for the decreased rate of UO 2 oxidation in the presence of Ca and PO 4. Interestingly, the extractions were unable to remove all of the oxidized U from partially oxidized UO 2 solids, suggesting that oxidized U is distributed between the interior of the UO 2 nanoparticles and the labile surface layer. Accounting for the entire pool of oxidized U by XANES is the likely reason for the higher UO 2 oxidation rate constants determined here relative to prior studies. In conclusion, our results suggest that the natural presence or addition of Ca and PO 4 in groundwater could slow the rates of U IV oxidation, but that the rates are still fast enough to cause complete oxidation of U IV within days under fully oxygenated conditions.« less

New evidence and impact of electron transport non-linearities based on new perturbative inter-modulation analysis

NASA Astrophysics Data System (ADS)

van Berkel, M.; Kobayashi, T.; Igami, H.; Vandersteen, G.; Hogeweij, G. M. D.; Tanaka, K.; Tamura, N.; Zwart, H. J.; Kubo, S.; Ito, S.; Tsuchiya, H.; de Baar, M. R.; LHD Experiment Group

2017-12-01

A new methodology to analyze non-linear components in perturbative transport experiments is introduced. The methodology has been experimentally validated in the Large Helical Device for the electron heat transport channel. Electron cyclotron resonance heating with different modulation frequencies by two gyrotrons has been used to directly quantify the amplitude of the non-linear component at the inter-modulation frequencies. The measurements show significant quadratic non-linear contributions and also the absence of cubic and higher order components. The non-linear component is analyzed using the Volterra series, which is the non-linear generalization of transfer functions. This allows us to study the radial distribution of the non-linearity of the plasma and to reconstruct linear profiles where the measurements were not distorted by non-linearities. The reconstructed linear profiles are significantly different from the measured profiles, demonstrating the significant impact that non-linearity can have.

Monte Carlo simulation of star/linear and star/star blends with chemically identical monomers

NASA Astrophysics Data System (ADS)

Theodorakis, P. E.; Avgeropoulos, A.; Freire, J. J.; Kosmas, M.; Vlahos, C.

2007-11-01

The effects of chain size and architectural asymmetry on the miscibility of blends with chemically identical monomers, differing only in their molecular weight and architecture, are studied via Monte Carlo simulation by using the bond fluctuation model. Namely, we consider blends composed of linear/linear, star/linear and star/star chains. We found that linear/linear blends are more miscible than the corresponding star/star mixtures. In star/linear blends, the increase in the volume fraction of the star chains increases the miscibility. For both star/linear and star/star blends, the miscibility decreases with the increase in star functionality. When we increase the molecular weight of linear chains of star/linear mixtures the miscibility decreases. Our findings are compared with recent analytical and experimental results.

On the linear programming bound for linear Lee codes.

PubMed

Astola, Helena; Tabus, Ioan

2016-01-01

Based on an invariance-type property of the Lee-compositions of a linear Lee code, additional equality constraints can be introduced to the linear programming problem of linear Lee codes. In this paper, we formulate this property in terms of an action of the multiplicative group of the field [Formula: see text] on the set of Lee-compositions. We show some useful properties of certain sums of Lee-numbers, which are the eigenvalues of the Lee association scheme, appearing in the linear programming problem of linear Lee codes. Using the additional equality constraints, we formulate the linear programming problem of linear Lee codes in a very compact form, leading to a fast execution, which allows to efficiently compute the bounds for large parameter values of the linear codes.

Linearization of digital derived rate algorithm for use in linear stability analysis

NASA Technical Reports Server (NTRS)

Graham, R. E.; Porada, T. W.

1985-01-01

The digital derived rate (DDR) algorithm is used to calculate the rate of rotation of the Centaur upper-stage rocket. The DDR is highly nonlinear algorithm, and classical linear stability analysis of the spacecraft cannot be performed without linearization. The performance of this rate algorithm is characterized by a gain and phase curve that drop off at the same frequency. This characteristic is desirable for many applications. A linearization technique for the DDR algorithm is investigated. The linearization method is described. Examples of the results of the linearization technique are illustrated, and the effects of linearization are described. A linear digital filter may be used as a substitute for performing classical linear stability analyses, while the DDR itself may be used in time response analysis.

LINEAR - DERIVATION AND DEFINITION OF A LINEAR AIRCRAFT MODEL

NASA Technical Reports Server (NTRS)

Duke, E. L.

1994-01-01

The Derivation and Definition of a Linear Model program, LINEAR, provides the user with a powerful and flexible tool for the linearization of aircraft aerodynamic models. LINEAR was developed to provide a standard, documented, and verified tool to derive linear models for aircraft stability analysis and control law design. Linear system models define the aircraft system in the neighborhood of an analysis point and are determined by the linearization of the nonlinear equations defining vehicle dynamics and sensors. LINEAR numerically determines a linear system model using nonlinear equations of motion and a user supplied linear or nonlinear aerodynamic model. The nonlinear equations of motion used are six-degree-of-freedom equations with stationary atmosphere and flat, nonrotating earth assumptions. LINEAR is capable of extracting both linearized engine effects, such as net thrust, torque, and gyroscopic effects and including these effects in the linear system model. The point at which this linear model is defined is determined either by completely specifying the state and control variables, or by specifying an analysis point on a trajectory and directing the program to determine the control variables and the remaining state variables. The system model determined by LINEAR consists of matrices for both the state and observation equations. The program has been designed to provide easy selection of state, control, and observation variables to be used in a particular model. Thus, the order of the system model is completely under user control. Further, the program provides the flexibility of allowing alternate formulations of both the state and observation equations. Data describing the aircraft and the test case is input to the program through a terminal or formatted data files. All data can be modified interactively from case to case. The aerodynamic model can be defined in two ways: a set of nondimensional stability and control derivatives for the flight point of interest, or a full non-linear aerodynamic model as used in simulations. LINEAR is written in FORTRAN and has been implemented on a DEC VAX computer operating under VMS with a virtual memory requirement of approximately 296K of 8 bit bytes. Both an interactive and batch version are included. LINEAR was developed in 1988.

Can Linear Superiorization Be Useful for Linear Optimization Problems?

PubMed Central

Censor, Yair

2017-01-01

Linear superiorization considers linear programming problems but instead of attempting to solve them with linear optimization methods it employs perturbation resilient feasibility-seeking algorithms and steers them toward reduced (not necessarily minimal) target function values. The two questions that we set out to explore experimentally are (i) Does linear superiorization provide a feasible point whose linear target function value is lower than that obtained by running the same feasibility-seeking algorithm without superiorization under identical conditions? and (ii) How does linear superiorization fare in comparison with the Simplex method for solving linear programming problems? Based on our computational experiments presented here, the answers to these two questions are: “yes” and “very well”, respectively. PMID:29335660

Linear versus non-linear measures of temporal variability in finger tapping and their relation to performance on open- versus closed-loop motor tasks: comparing standard deviations to Lyapunov exponents.

PubMed

Christman, Stephen D; Weaver, Ryan

2008-05-01

The nature of temporal variability during speeded finger tapping was examined using linear (standard deviation) and non-linear (Lyapunov exponent) measures. Experiment 1 found that right hand tapping was characterised by lower amounts of both linear and non-linear measures of variability than left hand tapping, and that linear and non-linear measures of variability were often negatively correlated with one another. Experiment 2 found that increased non-linear variability was associated with relatively enhanced performance on a closed-loop motor task (mirror tracing) and relatively impaired performance on an open-loop motor task (pointing in a dark room), especially for left hand performance. The potential uses and significance of measures of non-linear variability are discussed.

Estimation of suspended-sediment rating curves and mean suspended-sediment loads

USGS Publications Warehouse

Crawford, Charles G.

1991-01-01

A simulation study was done to evaluate: (1) the accuracy and precision of parameter estimates for the bias-corrected, transformed-linear and non-linear models obtained by the method of least squares; (2) the accuracy of mean suspended-sediment loads calculated by the flow-duration, rating-curve method using model parameters obtained by the alternative methods. Parameter estimates obtained by least squares for the bias-corrected, transformed-linear model were considerably more precise than those obtained for the non-linear or weighted non-linear model. The accuracy of parameter estimates obtained for the biascorrected, transformed-linear and weighted non-linear model was similar and was much greater than the accuracy obtained by non-linear least squares. The improved parameter estimates obtained by the biascorrected, transformed-linear or weighted non-linear model yield estimates of mean suspended-sediment load calculated by the flow-duration, rating-curve method that are more accurate and precise than those obtained for the non-linear model.

Tabulation of comet observations.

NASA Astrophysics Data System (ADS)

1999-07-01

Concerning comets: C/1995 O1 (Hale-Bopp), C/1996 J1 (Evans-Drinkwater), C/1997 BA6 (Spacewatch), C/1997 D1 (Mueller), C/1997 H2 (SOHO), C/1997 J1 (Mueller), C/1997 J2 (Meunier-Dupouy), C/1997 N1 (Tabur), C/1997 O1 (Tilbrook), C/1997 T1 (Utsunomiya), C/1998 H1 (Stonehouse), C/1998 J1 (SOHO), C/1998 K1 (Mueller), C/1998 K2 (LINEAR), C/1998 K5 (LINEAR), C/1998 M1 (LINEAR), C/1998 M2 (LINEAR), C/1998 M3 (Larsen), C/1998 M4 (LINEAR), C/1998 M5 (LINEAR), C/1998 P1 (Williams), C/1998 T1 (LINEAR), C/1998 U5 (LINEAR), C/1999 F1 (Catalina), C/1999 F2 (Dalcanton), C/1999 H1 (Lee), C/1999 H3 (LINEAR), C/1999 J2 (Skiff), C/1999 J3 (LINEAR), C/1999 J4 (LINEAR), C/1999 K2 (Ferris), C/1999 K3 (LINEAR), C/1999 K5 (LINEAR), C/1999 K6 (LINEAR), C/1999 K7 (LINEAR), C/1999 K8 (LINEAR), C/1999 L2 (LINEAR), C/1999 N2 (Lynn), 2P/Encke, 9P/Tempel 1, 10P/Tempel 2, 21P/Giacobini-Zinner, 29P/Schwassmann-Wachmann 1, 37P/Forbes, 43P/Wolf-Harrington, 46P/Wirtanen, 48P/Johnson, 49P/Arend-Rigaux, 52P/Harrington-Abell, 55P/Tempel-Tuttle, 62P/Tsuchinshan 1, 65P/Gunn, 69P/Taylor, 78P/Gehrels 2, 81P/Wild 2, 88P/Howell, 92P/Lovas 1, 94P/Russell 4, 95P/Chiron, 100P/Hartley 1, 103P/Hartley 2, 104P/Kowal 2, 105P/Singer Brewster, 118P/Shoemaker-Levy 4, 121P/Shoemaker-Holt 2, 128P/Shoemaker-Holt 1, 132P/Helin-Roman-Alu 2, 134P/Kowal-Vávrová, 135P/Shoemaker-Levy 8, 137P/Shoemaker-Levy 2, 140P/Bowell-Skiff, P/1998 U3 (Jäger), P/1998 W1 (Spahr), P/1999 DN3 (Korlević-Jurić), P/1999 E1 (Li), P/1999 G1 (LINEAR), P/1999 J5 (LINEAR).

Stress Induced in Periodontal Ligament under Orthodontic Loading (Part II): A Comparison of Linear Versus Non-Linear Fem Study.

PubMed

Hemanth, M; Deoli, Shilpi; Raghuveer, H P; Rani, M S; Hegde, Chatura; Vedavathi, B

2015-09-01

Simulation of periodontal ligament (PDL) using non-linear finite element method (FEM) analysis gives better insight into understanding of the biology of tooth movement. The stresses in the PDL were evaluated for intrusion and lingual root torque using non-linear properties. A three-dimensional (3D) FEM model of the maxillary incisors was generated using Solidworks modeling software. Stresses in the PDL were evaluated for intrusive and lingual root torque movements by 3D FEM using ANSYS software. These stresses were compared with linear and non-linear analyses. For intrusive and lingual root torque movements, distribution of stress over the PDL was within the range of optimal stress value as proposed by Lee, but was exceeding the force system given by Proffit as optimum forces for orthodontic tooth movement with linear properties. When same force load was applied in non-linear analysis, stresses were more compared to linear analysis and were beyond the optimal stress range as proposed by Lee for both intrusive and lingual root torque. To get the same stress as linear analysis, iterations were done using non-linear properties and the force level was reduced. This shows that the force level required for non-linear analysis is lesser than that of linear analysis.

The Overgeneralization of Linear Models among University Students' Mathematical Productions: A Long-Term Study

ERIC Educational Resources Information Center

Esteley, Cristina B.; Villarreal, Monica E.; Alagia, Humberto R.

2010-01-01

Over the past several years, we have been exploring and researching a phenomenon that occurs among undergraduate students that we called extension of linear models to non-linear contexts or overgeneralization of linear models. This phenomenon appears when some students use linear representations in situations that are non-linear. In a first phase,…

The Effects of Linear and Modified Linear Programed Materials on the Achievement of Slow Learners in Tenth Grade BSCS Special Materials Biology.

ERIC Educational Resources Information Center

Moody, John Charles

Assessed were the effects of linear and modified linear programed materials on the achievement of slow learners in tenth grade Biological Sciences Curriculum Study (BSCS) Special Materials biology. Two hundred and six students were randomly placed into four programed materials formats: linear programed materials, modified linear program with…

Comparative analysis of linear and non-linear method of estimating the sorption isotherm parameters for malachite green onto activated carbon.

PubMed

Kumar, K Vasanth

2006-08-21

The experimental equilibrium data of malachite green onto activated carbon were fitted to the Freundlich, Langmuir and Redlich-Peterson isotherms by linear and non-linear method. A comparison between linear and non-linear of estimating the isotherm parameters was discussed. The four different linearized form of Langmuir isotherm were also discussed. The results confirmed that the non-linear method as a better way to obtain isotherm parameters. The best fitting isotherm was Langmuir and Redlich-Peterson isotherm. Redlich-Peterson is a special case of Langmuir when the Redlich-Peterson isotherm constant g was unity.

Genomic prediction based on data from three layer lines using non-linear regression models.

PubMed

Huang, Heyun; Windig, Jack J; Vereijken, Addie; Calus, Mario P L

2014-11-06

Most studies on genomic prediction with reference populations that include multiple lines or breeds have used linear models. Data heterogeneity due to using multiple populations may conflict with model assumptions used in linear regression methods. In an attempt to alleviate potential discrepancies between assumptions of linear models and multi-population data, two types of alternative models were used: (1) a multi-trait genomic best linear unbiased prediction (GBLUP) model that modelled trait by line combinations as separate but correlated traits and (2) non-linear models based on kernel learning. These models were compared to conventional linear models for genomic prediction for two lines of brown layer hens (B1 and B2) and one line of white hens (W1). The three lines each had 1004 to 1023 training and 238 to 240 validation animals. Prediction accuracy was evaluated by estimating the correlation between observed phenotypes and predicted breeding values. When the training dataset included only data from the evaluated line, non-linear models yielded at best a similar accuracy as linear models. In some cases, when adding a distantly related line, the linear models showed a slight decrease in performance, while non-linear models generally showed no change in accuracy. When only information from a closely related line was used for training, linear models and non-linear radial basis function (RBF) kernel models performed similarly. The multi-trait GBLUP model took advantage of the estimated genetic correlations between the lines. Combining linear and non-linear models improved the accuracy of multi-line genomic prediction. Linear models and non-linear RBF models performed very similarly for genomic prediction, despite the expectation that non-linear models could deal better with the heterogeneous multi-population data. This heterogeneity of the data can be overcome by modelling trait by line combinations as separate but correlated traits, which avoids the occasional occurrence of large negative accuracies when the evaluated line was not included in the training dataset. Furthermore, when using a multi-line training dataset, non-linear models provided information on the genotype data that was complementary to the linear models, which indicates that the underlying data distributions of the three studied lines were indeed heterogeneous.

A Characterization of a Unified Notion of Mathematical Function: The Case of High School Function and Linear Transformation

ERIC Educational Resources Information Center

Zandieh, Michelle; Ellis, Jessica; Rasmussen, Chris

2017-01-01

As part of a larger study of student understanding of concepts in linear algebra, we interviewed 10 university linear algebra students as to their conceptions of functions from high school algebra and linear transformation from their study of linear algebra. An overarching goal of this study was to examine how linear algebra students see linear…

Prediction of optimum sorption isotherm: comparison of linear and non-linear method.

PubMed

Kumar, K Vasanth; Sivanesan, S

2005-11-11

Equilibrium parameters for Bismarck brown onto rice husk were estimated by linear least square and a trial and error non-linear method using Freundlich, Langmuir and Redlich-Peterson isotherms. A comparison between linear and non-linear method of estimating the isotherm parameters was reported. The best fitting isotherm was Langmuir isotherm and Redlich-Peterson isotherm equation. The results show that non-linear method could be a better way to obtain the parameters. Redlich-Peterson isotherm is a special case of Langmuir isotherm when the Redlich-Peterson isotherm constant g was unity.

Cotton-type and joint invariants for linear elliptic systems.

PubMed

Aslam, A; Mahomed, F M

2013-01-01

Cotton-type invariants for a subclass of a system of two linear elliptic equations, obtainable from a complex base linear elliptic equation, are derived both by spliting of the corresponding complex Cotton invariants of the base complex equation and from the Laplace-type invariants of the system of linear hyperbolic equations equivalent to the system of linear elliptic equations via linear complex transformations of the independent variables. It is shown that Cotton-type invariants derived from these two approaches are identical. Furthermore, Cotton-type and joint invariants for a general system of two linear elliptic equations are also obtained from the Laplace-type and joint invariants for a system of two linear hyperbolic equations equivalent to the system of linear elliptic equations by complex changes of the independent variables. Examples are presented to illustrate the results.

Cotton-Type and Joint Invariants for Linear Elliptic Systems

PubMed Central

Aslam, A.; Mahomed, F. M.

2013-01-01

Cotton-type invariants for a subclass of a system of two linear elliptic equations, obtainable from a complex base linear elliptic equation, are derived both by spliting of the corresponding complex Cotton invariants of the base complex equation and from the Laplace-type invariants of the system of linear hyperbolic equations equivalent to the system of linear elliptic equations via linear complex transformations of the independent variables. It is shown that Cotton-type invariants derived from these two approaches are identical. Furthermore, Cotton-type and joint invariants for a general system of two linear elliptic equations are also obtained from the Laplace-type and joint invariants for a system of two linear hyperbolic equations equivalent to the system of linear elliptic equations by complex changes of the independent variables. Examples are presented to illustrate the results. PMID:24453871

Pseudo-second order models for the adsorption of safranin onto activated carbon: comparison of linear and non-linear regression methods.

PubMed

Kumar, K Vasanth

2007-04-02

Kinetic experiments were carried out for the sorption of safranin onto activated carbon particles. The kinetic data were fitted to pseudo-second order model of Ho, Sobkowsk and Czerwinski, Blanchard et al. and Ritchie by linear and non-linear regression methods. Non-linear method was found to be a better way of obtaining the parameters involved in the second order rate kinetic expressions. Both linear and non-linear regression showed that the Sobkowsk and Czerwinski and Ritchie's pseudo-second order models were the same. Non-linear regression analysis showed that both Blanchard et al. and Ho have similar ideas on the pseudo-second order model but with different assumptions. The best fit of experimental data in Ho's pseudo-second order expression by linear and non-linear regression method showed that Ho pseudo-second order model was a better kinetic expression when compared to other pseudo-second order kinetic expressions.

Asymptotic aspect of derivations in Banach algebras.

PubMed

Roh, Jaiok; Chang, Ick-Soon

2017-01-01

We prove that every approximate linear left derivation on a semisimple Banach algebra is continuous. Also, we consider linear derivations on Banach algebras and we first study the conditions for a linear derivation on a Banach algebra. Then we examine the functional inequalities related to a linear derivation and their stability. We finally take central linear derivations with radical ranges on semiprime Banach algebras and a continuous linear generalized left derivation on a semisimple Banach algebra.

Mössbauer spectra linearity improvement by sine velocity waveform followed by linearization process

NASA Astrophysics Data System (ADS)

Kohout, Pavel; Frank, Tomas; Pechousek, Jiri; Kouril, Lukas

2018-05-01

This note reports the development of a new method for linearizing the Mössbauer spectra recorded with a sine drive velocity signal. Mössbauer spectra linearity is a critical parameter to determine Mössbauer spectrometer accuracy. Measuring spectra with a sine velocity axis and consecutive linearization increases the linearity of spectra in a wider frequency range of a drive signal, as generally harmonic movement is natural for velocity transducers. The obtained data demonstrate that linearized sine spectra have lower nonlinearity and line width parameters in comparison with those measured using a traditional triangle velocity signal.

Computing Linear Mathematical Models Of Aircraft

NASA Technical Reports Server (NTRS)

Duke, Eugene L.; Antoniewicz, Robert F.; Krambeer, Keith D.

1991-01-01

Derivation and Definition of Linear Aircraft Model (LINEAR) computer program provides user with powerful, and flexible, standard, documented, and verified software tool for linearization of mathematical models of aerodynamics of aircraft. Intended for use in software tool to drive linear analysis of stability and design of control laws for aircraft. Capable of both extracting such linearized engine effects as net thrust, torque, and gyroscopic effects, and including these effects in linear model of system. Designed to provide easy selection of state, control, and observation variables used in particular model. Also provides flexibility of allowing alternate formulations of both state and observation equations. Written in FORTRAN.

Non-Linear Approach in Kinesiology Should Be Preferred to the Linear--A Case of Basketball.

PubMed

Trninić, Marko; Jeličić, Mario; Papić, Vladan

2015-07-01

In kinesiology, medicine, biology and psychology, in which research focus is on dynamical self-organized systems, complex connections exist between variables. Non-linear nature of complex systems has been discussed and explained by the example of non-linear anthropometric predictors of performance in basketball. Previous studies interpreted relations between anthropometric features and measures of effectiveness in basketball by (a) using linear correlation models, and by (b) including all basketball athletes in the same sample of participants regardless of their playing position. In this paper the significance and character of linear and non-linear relations between simple anthropometric predictors (AP) and performance criteria consisting of situation-related measures of effectiveness (SE) in basketball were determined and evaluated. The sample of participants consisted of top-level junior basketball players divided in three groups according to their playing time (8 minutes and more per game) and playing position: guards (N = 42), forwards (N = 26) and centers (N = 40). Linear (general model) and non-linear (general model) regression models were calculated simultaneously and separately for each group. The conclusion is viable: non-linear regressions are frequently superior to linear correlations when interpreting actual association logic among research variables.

FAST TRACK PAPER: Non-iterative multiple-attenuation methods: linear inverse solutions to non-linear inverse problems - II. BMG approximation

NASA Astrophysics Data System (ADS)

Ikelle, Luc T.; Osen, Are; Amundsen, Lasse; Shen, Yunqing

2004-12-01

The classical linear solutions to the problem of multiple attenuation, like predictive deconvolution, τ-p filtering, or F-K filtering, are generally fast, stable, and robust compared to non-linear solutions, which are generally either iterative or in the form of a series with an infinite number of terms. These qualities have made the linear solutions more attractive to seismic data-processing practitioners. However, most linear solutions, including predictive deconvolution or F-K filtering, contain severe assumptions about the model of the subsurface and the class of free-surface multiples they can attenuate. These assumptions limit their usefulness. In a recent paper, we described an exception to this assertion for OBS data. We showed in that paper that a linear and non-iterative solution to the problem of attenuating free-surface multiples which is as accurate as iterative non-linear solutions can be constructed for OBS data. We here present a similar linear and non-iterative solution for attenuating free-surface multiples in towed-streamer data. For most practical purposes, this linear solution is as accurate as the non-linear ones.

An extended harmonic balance method based on incremental nonlinear control parameters

NASA Astrophysics Data System (ADS)

Khodaparast, Hamed Haddad; Madinei, Hadi; Friswell, Michael I.; Adhikari, Sondipon; Coggon, Simon; Cooper, Jonathan E.

2017-02-01

A new formulation for calculating the steady-state responses of multiple-degree-of-freedom (MDOF) non-linear dynamic systems due to harmonic excitation is developed. This is aimed at solving multi-dimensional nonlinear systems using linear equations. Nonlinearity is parameterised by a set of 'non-linear control parameters' such that the dynamic system is effectively linear for zero values of these parameters and nonlinearity increases with increasing values of these parameters. Two sets of linear equations which are formed from a first-order truncated Taylor series expansion are developed. The first set of linear equations provides the summation of sensitivities of linear system responses with respect to non-linear control parameters and the second set are recursive equations that use the previous responses to update the sensitivities. The obtained sensitivities of steady-state responses are then used to calculate the steady state responses of non-linear dynamic systems in an iterative process. The application and verification of the method are illustrated using a non-linear Micro-Electro-Mechanical System (MEMS) subject to a base harmonic excitation. The non-linear control parameters in these examples are the DC voltages that are applied to the electrodes of the MEMS devices.

Application of linear logic to simulation

NASA Astrophysics Data System (ADS)

Clarke, Thomas L.

1998-08-01

Linear logic, since its introduction by Girard in 1987 has proven expressive and powerful. Linear logic has provided natural encodings of Turing machines, Petri nets and other computational models. Linear logic is also capable of naturally modeling resource dependent aspects of reasoning. The distinguishing characteristic of linear logic is that it accounts for resources; two instances of the same variable are considered differently from a single instance. Linear logic thus must obey a form of the linear superposition principle. A proportion can be reasoned with only once, unless a special operator is applied. Informally, linear logic distinguishes two kinds of conjunction, two kinds of disjunction, and also introduces a modal storage operator that explicitly indicates propositions that can be reused. This paper discuses the application of linear logic to simulation. A wide variety of logics have been developed; in addition to classical logic, there are fuzzy logics, affine logics, quantum logics, etc. All of these have found application in simulations of one sort or another. The special characteristics of linear logic and its benefits for simulation will be discussed. Of particular interest is a connection that can be made between linear logic and simulated dynamics by using the concept of Lie algebras and Lie groups. Lie groups provide the connection between the exponential modal storage operators of linear logic and the eigen functions of dynamic differential operators. Particularly suggestive are possible relations between complexity result for linear logic and non-computability results for dynamical systems.

Non-linear analysis of wave progagation using transform methods and plates and shells using integral equations

NASA Astrophysics Data System (ADS)

Pipkins, Daniel Scott

Two diverse topics of relevance in modern computational mechanics are treated. The first involves the modeling of linear and non-linear wave propagation in flexible, lattice structures. The technique used combines the Laplace Transform with the Finite Element Method (FEM). The procedure is to transform the governing differential equations and boundary conditions into the transform domain where the FEM formulation is carried out. For linear problems, the transformed differential equations can be solved exactly, hence the method is exact. As a result, each member of the lattice structure is modeled using only one element. In the non-linear problem, the method is no longer exact. The approximation introduced is a spatial discretization of the transformed non-linear terms. The non-linear terms are represented in the transform domain by making use of the complex convolution theorem. A weak formulation of the resulting transformed non-linear equations yields a set of element level matrix equations. The trial and test functions used in the weak formulation correspond to the exact solution of the linear part of the transformed governing differential equation. Numerical results are presented for both linear and non-linear systems. The linear systems modeled are longitudinal and torsional rods and Bernoulli-Euler and Timoshenko beams. For non-linear systems, a viscoelastic rod and Von Karman type beam are modeled. The second topic is the analysis of plates and shallow shells under-going finite deflections by the Field/Boundary Element Method. Numerical results are presented for two plate problems. The first is the bifurcation problem associated with a square plate having free boundaries which is loaded by four, self equilibrating corner forces. The results are compared to two existing numerical solutions of the problem which differ substantially.

Comparison of linear and non-linear models for the adsorption of fluoride onto geo-material: limonite.

PubMed

Sahin, Rubina; Tapadia, Kavita

2015-01-01

The three widely used isotherms Langmuir, Freundlich and Temkin were examined in an experiment using fluoride (F⁻) ion adsorption on a geo-material (limonite) at four different temperatures by linear and non-linear models. Comparison of linear and non-linear regression models were given in selecting the optimum isotherm for the experimental results. The coefficient of determination, r², was used to select the best theoretical isotherm. The four Langmuir linear equations (1, 2, 3, and 4) are discussed. Langmuir isotherm parameters obtained from the four Langmuir linear equations using the linear model differed but they were the same when using the nonlinear model. Langmuir-2 isotherm is one of the linear forms, and it had the highest coefficient of determination (r² = 0.99) compared to the other Langmuir linear equations (1, 3 and 4) in linear form, whereas, for non-linear, Langmuir-4 fitted best among all the isotherms because it had the highest coefficient of determination (r² = 0.99). The results showed that the non-linear model may be a better way to obtain the parameters. In the present work, the thermodynamic parameters show that the absorption of fluoride onto limonite is both spontaneous (ΔG < 0) and endothermic (ΔH > 0). Scanning electron microscope and X-ray diffraction images also confirm the adsorption of F⁻ ion onto limonite. The isotherm and kinetic study reveals that limonite can be used as an adsorbent for fluoride removal. In future we can develop new technology for fluoride removal in large scale by using limonite which is cost-effective, eco-friendly and is easily available in the study area.

Pseudo second order kinetics and pseudo isotherms for malachite green onto activated carbon: comparison of linear and non-linear regression methods.

PubMed

Kumar, K Vasanth; Sivanesan, S

2006-08-25

Pseudo second order kinetic expressions of Ho, Sobkowsk and Czerwinski, Blanachard et al. and Ritchie were fitted to the experimental kinetic data of malachite green onto activated carbon by non-linear and linear method. Non-linear method was found to be a better way of obtaining the parameters involved in the second order rate kinetic expressions. Both linear and non-linear regression showed that the Sobkowsk and Czerwinski and Ritchie's pseudo second order model were the same. Non-linear regression analysis showed that both Blanachard et al. and Ho have similar ideas on the pseudo second order model but with different assumptions. The best fit of experimental data in Ho's pseudo second order expression by linear and non-linear regression method showed that Ho pseudo second order model was a better kinetic expression when compared to other pseudo second order kinetic expressions. The amount of dye adsorbed at equilibrium, q(e), was predicted from Ho pseudo second order expression and were fitted to the Langmuir, Freundlich and Redlich Peterson expressions by both linear and non-linear method to obtain the pseudo isotherms. The best fitting pseudo isotherm was found to be the Langmuir and Redlich Peterson isotherm. Redlich Peterson is a special case of Langmuir when the constant g equals unity.

Next Linear Collider Home Page

Science.gov Websites

Welcome to the Next Linear Collider NLC Home Page If you would like to learn about linear colliders in general and about this next-generation linear collider project's mission, design ideas, and Linear Collider. line | NLC Home | NLC Technical | SLAC | mcdunn Tuesday, February 14, 2006 01:32:11 PM

Pupils' over-reliance on linearity: a scholastic effect?

PubMed

Van Dooren, Wim; De Bock, Dirk; Janssens, Dirk; Verschaffel, Lieven

2007-06-01

From upper elementary education on, children develop a tendency to over-use linearity. Particularly, it is found that many pupils assume that if a figure enlarges k times, the area enlarges k times too. However, most research was conducted with traditional, school-like word problems. This study examines whether pupils also over-use linearity if non-linear problems are embedded in meaningful, authentic performance tasks instead of traditional, school-like word problems, and whether this experience influences later behaviour. Ninety-three sixth graders from two primary schools in Flanders, Belgium. Pupils received a pre-test with traditional word problems. Those who made a linear error on the non-linear area problem were subjected to individual interviews. They received one new non-linear problem, in the S-condition (again a traditional, scholastic word problem), D-condition (the same word problem with a drawing) or P-condition (a meaningful performance-based task). Shortly afterwards, pupils received a post-test, containing again a non-linear word problem. Most pupils from the S-condition displayed linear reasoning during the interview. Offering drawings (D-condition) had a positive effect, but presenting the problem as a performance task (P-condition) was more beneficial. Linear reasoning was nearly absent in the P-condition. Remarkably, at the post-test, most pupils from all three groups again applied linear strategies. Pupils' over-reliance on linearity seems partly elicited by the school-like word problem format of test items. Pupils perform much better if non-linear problems are offered as performance tasks. However, a single experience does not change performances on a comparable word problem test afterwards.

User's manual for LINEAR, a FORTRAN program to derive linear aircraft models

NASA Technical Reports Server (NTRS)

Duke, Eugene L.; Patterson, Brian P.; Antoniewicz, Robert F.

1987-01-01

This report documents a FORTRAN program that provides a powerful and flexible tool for the linearization of aircraft models. The program LINEAR numerically determines a linear system model using nonlinear equations of motion and a user-supplied nonlinear aerodynamic model. The system model determined by LINEAR consists of matrices for both state and observation equations. The program has been designed to allow easy selection and definition of the state, control, and observation variables to be used in a particular model.

Investigating Students' Modes of Thinking in Linear Algebra: The Case of Linear Independence

ERIC Educational Resources Information Center

Çelik, Derya

2015-01-01

Linear algebra is one of the most challenging topics to learn and teach in many countries. To facilitate the teaching and learning of linear algebra, priority should be given to epistemologically analyze the concepts that the undergraduate students have difficulty in conceptualizing and to define their ways of reasoning in linear algebra. After…

The Next Linear Collider Program-News

Science.gov Websites

The Next Linear Collider at SLAC Navbar The Next Linear Collider In The Press The Secretary of Linear Collider is a high-priority goal of this plan. http://www.sc.doe.gov/Sub/Facilities_for_future/20 -term projects in conceputal stages (the Linear Collider is the highest priority project in this

Fast and local non-linear evolution of steep wave-groups on deep water: A comparison of approximate models to fully non-linear simulations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Adcock, T. A. A.; Taylor, P. H.

2016-01-15

The non-linear Schrödinger equation and its higher order extensions are routinely used for analysis of extreme ocean waves. This paper compares the evolution of individual wave-packets modelled using non-linear Schrödinger type equations with packets modelled using fully non-linear potential flow models. The modified non-linear Schrödinger Equation accurately models the relatively large scale non-linear changes to the shape of wave-groups, with a dramatic contraction of the group along the mean propagation direction and a corresponding extension of the width of the wave-crests. In addition, as extreme wave form, there is a local non-linear contraction of the wave-group around the crest whichmore » leads to a localised broadening of the wave spectrum which the bandwidth limited non-linear Schrödinger Equations struggle to capture. This limitation occurs for waves of moderate steepness and a narrow underlying spectrum.« less

Study on static and dynamic characteristics of moving magnet linear compressors

NASA Astrophysics Data System (ADS)

Chen, N.; Tang, Y. J.; Wu, Y. N.; Chen, X.; Xu, L.

2007-09-01

With the development of high-strength NdFeB magnetic material, moving magnet linear compressors have been gradually introduced in the fields of refrigeration and cryogenic engineering, especially in Stirling and pulse tube cryocoolers. This paper presents simulation and experimental investigations on the static and dynamic characteristics of a moving magnet linear motor and a moving magnet linear compressor. Both equivalent magnetic circuits and finite element approaches have been used to model the moving magnet linear motor. Subsequently, the force and equilibrium characteristics of the linear motor have been predicted and verified by detailed static experimental analyses. In combination with a harmonic analysis, experimental investigations were conducted on a prototype of a moving magnet linear compressor. A voltage-stroke relationship, the effect of charging pressure on the performance and dynamic frequency response characteristics are investigated. Finally, the method to identify optimal points of the linear compressor has been described, which is indispensable to the design and operation of moving magnet linear compressors.

Comparison Between Linear and Non-parametric Regression Models for Genome-Enabled Prediction in Wheat

PubMed Central

Pérez-Rodríguez, Paulino; Gianola, Daniel; González-Camacho, Juan Manuel; Crossa, José; Manès, Yann; Dreisigacker, Susanne

2012-01-01

In genome-enabled prediction, parametric, semi-parametric, and non-parametric regression models have been used. This study assessed the predictive ability of linear and non-linear models using dense molecular markers. The linear models were linear on marker effects and included the Bayesian LASSO, Bayesian ridge regression, Bayes A, and Bayes B. The non-linear models (this refers to non-linearity on markers) were reproducing kernel Hilbert space (RKHS) regression, Bayesian regularized neural networks (BRNN), and radial basis function neural networks (RBFNN). These statistical models were compared using 306 elite wheat lines from CIMMYT genotyped with 1717 diversity array technology (DArT) markers and two traits, days to heading (DTH) and grain yield (GY), measured in each of 12 environments. It was found that the three non-linear models had better overall prediction accuracy than the linear regression specification. Results showed a consistent superiority of RKHS and RBFNN over the Bayesian LASSO, Bayesian ridge regression, Bayes A, and Bayes B models. PMID:23275882

Comparison between linear and non-parametric regression models for genome-enabled prediction in wheat.

PubMed

Pérez-Rodríguez, Paulino; Gianola, Daniel; González-Camacho, Juan Manuel; Crossa, José; Manès, Yann; Dreisigacker, Susanne

2012-12-01

In genome-enabled prediction, parametric, semi-parametric, and non-parametric regression models have been used. This study assessed the predictive ability of linear and non-linear models using dense molecular markers. The linear models were linear on marker effects and included the Bayesian LASSO, Bayesian ridge regression, Bayes A, and Bayes B. The non-linear models (this refers to non-linearity on markers) were reproducing kernel Hilbert space (RKHS) regression, Bayesian regularized neural networks (BRNN), and radial basis function neural networks (RBFNN). These statistical models were compared using 306 elite wheat lines from CIMMYT genotyped with 1717 diversity array technology (DArT) markers and two traits, days to heading (DTH) and grain yield (GY), measured in each of 12 environments. It was found that the three non-linear models had better overall prediction accuracy than the linear regression specification. Results showed a consistent superiority of RKHS and RBFNN over the Bayesian LASSO, Bayesian ridge regression, Bayes A, and Bayes B models.

Comparison of linear and non-linear models for predicting energy expenditure from raw accelerometer data.

PubMed

Montoye, Alexander H K; Begum, Munni; Henning, Zachary; Pfeiffer, Karin A

2017-02-01

This study had three purposes, all related to evaluating energy expenditure (EE) prediction accuracy from body-worn accelerometers: (1) compare linear regression to linear mixed models, (2) compare linear models to artificial neural network models, and (3) compare accuracy of accelerometers placed on the hip, thigh, and wrists. Forty individuals performed 13 activities in a 90 min semi-structured, laboratory-based protocol. Participants wore accelerometers on the right hip, right thigh, and both wrists and a portable metabolic analyzer (EE criterion). Four EE prediction models were developed for each accelerometer: linear regression, linear mixed, and two ANN models. EE prediction accuracy was assessed using correlations, root mean square error (RMSE), and bias and was compared across models and accelerometers using repeated-measures analysis of variance. For all accelerometer placements, there were no significant differences for correlations or RMSE between linear regression and linear mixed models (correlations: r  =  0.71-0.88, RMSE: 1.11-1.61 METs; p  >  0.05). For the thigh-worn accelerometer, there were no differences in correlations or RMSE between linear and ANN models (ANN-correlations: r  =  0.89, RMSE: 1.07-1.08 METs. Linear models-correlations: r  =  0.88, RMSE: 1.10-1.11 METs; p  >  0.05). Conversely, one ANN had higher correlations and lower RMSE than both linear models for the hip (ANN-correlation: r  =  0.88, RMSE: 1.12 METs. Linear models-correlations: r  =  0.86, RMSE: 1.18-1.19 METs; p  <  0.05), and both ANNs had higher correlations and lower RMSE than both linear models for the wrist-worn accelerometers (ANN-correlations: r  =  0.82-0.84, RMSE: 1.26-1.32 METs. Linear models-correlations: r  =  0.71-0.73, RMSE: 1.55-1.61 METs; p  <  0.01). For studies using wrist-worn accelerometers, machine learning models offer a significant improvement in EE prediction accuracy over linear models. Conversely, linear models showed similar EE prediction accuracy to machine learning models for hip- and thigh-worn accelerometers and may be viable alternative modeling techniques for EE prediction for hip- or thigh-worn accelerometers.

The Growing Importance of Linear Algebra in Undergraduate Mathematics.

ERIC Educational Resources Information Center

Tucker, Alan

1993-01-01

Discusses the theoretical and practical importance of linear algebra. Presents a brief history of linear algebra and matrix theory and describes the place of linear algebra in the undergraduate curriculum. (MDH)

Conditions for Stabilizability of Linear Switched Systems

NASA Astrophysics Data System (ADS)

Minh, Vu Trieu

2011-06-01

This paper investigates some conditions that can provide stabilizability for linear switched systems with polytopic uncertainties via their closed loop linear quadratic state feedback regulator. The closed loop switched systems can stabilize unstable open loop systems or stable open loop systems but in which there is no solution for a common Lyapunov matrix. For continuous time switched linear systems, we show that if there exists solution in an associated Riccati equation for the closed loop systems sharing one common Lyapunov matrix, the switched linear systems are stable. For the discrete time switched systems, we derive a Linear Matrix Inequality (LMI) to calculate a common Lyapunov matrix and solution for the stable closed loop feedback systems. These closed loop linear quadratic state feedback regulators guarantee the global asymptotical stability for any switched linear systems with any switching signal sequence.

Linear and angular control of circular walking in healthy older adults and subjects with cerebellar ataxia.

PubMed

Goodworth, Adam D; Paquette, Caroline; Jones, Geoffrey Melvill; Block, Edward W; Fletcher, William A; Hu, Bin; Horak, Fay B

2012-05-01

Linear and angular control of trunk and leg motion during curvilinear navigation was investigated in subjects with cerebellar ataxia and age-matched control subjects. Subjects walked with eyes open around a 1.2-m circle. The relationship of linear to angular motion was quantified by determining the ratios of trunk linear velocity to trunk angular velocity and foot linear position to foot angular position. Errors in walking radius (the ratio of linear to angular motion) also were quantified continuously during the circular walk. Relative variability of linear and angular measures was compared using coefficients of variation (CoV). Patterns of variability were compared using power spectral analysis for the trunk and auto-covariance analysis for the feet. Errors in radius were significantly increased in patients with cerebellar damage as compared to controls. Cerebellar subjects had significantly larger CoV of feet and trunk in angular, but not linear, motion. Control subjects also showed larger CoV in angular compared to linear motion of the feet and trunk. Angular and linear components of stepping differed in that angular, but not linear, foot placement had a negative correlation from one stride to the next. Thus, walking in a circle was associated with more, and a different type of, variability in angular compared to linear motion. Results are consistent with increased difficulty of, and role of the cerebellum in, control of angular trunk and foot motion for curvilinear locomotion.

Unambiguous discrimination between linearly dependent equidistant states with multiple copies

NASA Astrophysics Data System (ADS)

Zhang, Wen-Hai; Ren, Gang

2018-07-01

Linearly independent quantum states can be unambiguously discriminated, but linearly dependent ones cannot. For linearly dependent quantum states, however, if C copies of the single states are available, then they may form linearly independent states, and can be unambiguously discriminated. We consider unambiguous discrimination among N = D + 1 linearly dependent states given that C copies are available and that the single copies span a D-dimensional space with equal inner products. The maximum unambiguous discrimination probability is derived for all C with equal a priori probabilities. For this classification of the linearly dependent equidistant states, our result shows that if C is even then adding a further copy fails to increase the maximum discrimination probability.

Can linear superiorization be useful for linear optimization problems?

NASA Astrophysics Data System (ADS)

Censor, Yair

2017-04-01

Linear superiorization (LinSup) considers linear programming problems but instead of attempting to solve them with linear optimization methods it employs perturbation resilient feasibility-seeking algorithms and steers them toward reduced (not necessarily minimal) target function values. The two questions that we set out to explore experimentally are: (i) does LinSup provide a feasible point whose linear target function value is lower than that obtained by running the same feasibility-seeking algorithm without superiorization under identical conditions? (ii) How does LinSup fare in comparison with the Simplex method for solving linear programming problems? Based on our computational experiments presented here, the answers to these two questions are: ‘yes’ and ‘very well’, respectively.

User's manual for interactive LINEAR: A FORTRAN program to derive linear aircraft models

NASA Technical Reports Server (NTRS)

Antoniewicz, Robert F.; Duke, Eugene L.; Patterson, Brian P.

1988-01-01

An interactive FORTRAN program that provides the user with a powerful and flexible tool for the linearization of aircraft aerodynamic models is documented in this report. The program LINEAR numerically determines a linear system model using nonlinear equations of motion and a user-supplied linear or nonlinear aerodynamic model. The nonlinear equations of motion used are six-degree-of-freedom equations with stationary atmosphere and flat, nonrotating earth assumptions. The system model determined by LINEAR consists of matrices for both the state and observation equations. The program has been designed to allow easy selection and definition of the state, control, and observation variables to be used in a particular model.

Using Example Generation to Explore Students' Understanding of the Concepts of Linear Dependence/Independence in Linear Algebra

ERIC Educational Resources Information Center

Aydin, Sinan

2014-01-01

Linear algebra is a basic mathematical subject taught in mathematics and science depar-tments of universities. The teaching and learning of this course has always been difficult. This study aims to contribute to the research in linear algebra education, focusing on linear dependence and independence concepts. This was done by introducing…

Semilinear programming: applications and implementation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mohan, S.

Semilinear programming is a method of solving optimization problems with linear constraints where the non-negativity restrictions on the variables are dropped and the objective function coefficients can take on different values depending on whether the variable is positive or negative. The simplex method for linear programming is modified in this thesis to solve general semilinear and piecewise linear programs efficiently without having to transform them into equivalent standard linear programs. Several models in widely different areas of optimization such as production smoothing, facility locations, goal programming and L/sub 1/ estimation are presented first to demonstrate the compact formulation that arisesmore » when such problems are formulated as semilinear programs. A code SLP is constructed using the semilinear programming techniques. Problems in aggregate planning and L/sub 1/ estimation are solved using SLP and equivalent linear programs using a linear programming simplex code. Comparisons of CPU times and number iterations indicate SLP to be far superior. The semilinear programming techniques are extended to piecewise linear programming in the implementation of the code PLP. Piecewise linear models in aggregate planning are solved using PLP and equivalent standard linear programs using a simple upper bounded linear programming code SUBLP.« less

[Detection of linear chromosomes and plasmids among 15 genera in the Actinomycetales].

PubMed

Ma, Ning; Ma, Wei; Jiang, Chenglin; Fang, Ping; Qin, Zhongjun

2003-10-01

Bacterial chromosomes and plasmids are commonly circular, however, linear chromosomes and plasmids were discovered among 5 genera of the Actinomycetales. Here, we use pulsed field gel electrophoresis to study the genomes of 19 species which belong to 15 genera in the Actinomycetales. All chromosomes of 19 species are linear DNA, and linear plasmids with different sizes and copy numbers are detected among 5 species. This work provide basis for investigating the possible novel functions of linear replicons beyond Streptomyces and also helps to develop Actinomycetales artificial linear chromosome.

Compensatory selection for roads over natural linear features by wolves in northern Ontario: Implications for caribou conservation

PubMed Central

Patterson, Brent R.; Anderson, Morgan L.; Rodgers, Arthur R.; Vander Vennen, Lucas M.; Fryxell, John M.

2017-01-01

Woodland caribou (Rangifer tarandus caribou) in Ontario are a threatened species that have experienced a substantial retraction of their historic range. Part of their decline has been attributed to increasing densities of anthropogenic linear features such as trails, roads, railways, and hydro lines. These features have been shown to increase the search efficiency and kill rate of wolves. However, it is unclear whether selection for anthropogenic linear features is additive or compensatory to selection for natural (water) linear features which may also be used for travel. We studied the selection of water and anthropogenic linear features by 52 resident wolves (Canis lupus x lycaon) over four years across three study areas in northern Ontario that varied in degrees of forestry activity and human disturbance. We used Euclidean distance-based resource selection functions (mixed-effects logistic regression) at the seasonal range scale with random coefficients for distance to water linear features, primary/secondary roads/railways, and hydro lines, and tertiary roads to estimate the strength of selection for each linear feature and for several habitat types, while accounting for availability of each feature. Next, we investigated the trade-off between selection for anthropogenic and water linear features. Wolves selected both anthropogenic and water linear features; selection for anthropogenic features was stronger than for water during the rendezvous season. Selection for anthropogenic linear features increased with increasing density of these features on the landscape, while selection for natural linear features declined, indicating compensatory selection of anthropogenic linear features. These results have implications for woodland caribou conservation. Prey encounter rates between wolves and caribou seem to be strongly influenced by increasing linear feature densities. This behavioral mechanism–a compensatory functional response to anthropogenic linear feature density resulting in decreased use of natural travel corridors–has negative consequences for the viability of woodland caribou. PMID:29117234

Compensatory selection for roads over natural linear features by wolves in northern Ontario: Implications for caribou conservation.

PubMed

Newton, Erica J; Patterson, Brent R; Anderson, Morgan L; Rodgers, Arthur R; Vander Vennen, Lucas M; Fryxell, John M

2017-01-01

Woodland caribou (Rangifer tarandus caribou) in Ontario are a threatened species that have experienced a substantial retraction of their historic range. Part of their decline has been attributed to increasing densities of anthropogenic linear features such as trails, roads, railways, and hydro lines. These features have been shown to increase the search efficiency and kill rate of wolves. However, it is unclear whether selection for anthropogenic linear features is additive or compensatory to selection for natural (water) linear features which may also be used for travel. We studied the selection of water and anthropogenic linear features by 52 resident wolves (Canis lupus x lycaon) over four years across three study areas in northern Ontario that varied in degrees of forestry activity and human disturbance. We used Euclidean distance-based resource selection functions (mixed-effects logistic regression) at the seasonal range scale with random coefficients for distance to water linear features, primary/secondary roads/railways, and hydro lines, and tertiary roads to estimate the strength of selection for each linear feature and for several habitat types, while accounting for availability of each feature. Next, we investigated the trade-off between selection for anthropogenic and water linear features. Wolves selected both anthropogenic and water linear features; selection for anthropogenic features was stronger than for water during the rendezvous season. Selection for anthropogenic linear features increased with increasing density of these features on the landscape, while selection for natural linear features declined, indicating compensatory selection of anthropogenic linear features. These results have implications for woodland caribou conservation. Prey encounter rates between wolves and caribou seem to be strongly influenced by increasing linear feature densities. This behavioral mechanism-a compensatory functional response to anthropogenic linear feature density resulting in decreased use of natural travel corridors-has negative consequences for the viability of woodland caribou.

Mechanism Underlying IκB Kinase Activation Mediated by the Linear Ubiquitin Chain Assembly Complex

PubMed Central

Fujita, Hiroaki; Akita, Mariko; Kato, Ryuichi; Sasaki, Yoshiteru; Wakatsuki, Soichi

2014-01-01

The linear ubiquitin chain assembly complex (LUBAC) ligase, consisting of HOIL-1L, HOIP, and SHARPIN, specifically generates linear polyubiquitin chains. LUBAC-mediated linear polyubiquitination has been implicated in NF-κB activation. NEMO, a component of the IκB kinase (IKK) complex, is a substrate of LUBAC, but the precise molecular mechanism underlying linear chain-mediated NF-κB activation has not been fully elucidated. Here, we demonstrate that linearly polyubiquitinated NEMO activates IKK more potently than unanchored linear chains. In mutational analyses based on the crystal structure of the complex between the HOIP NZF1 and NEMO CC2-LZ domains, which are involved in the HOIP-NEMO interaction, NEMO mutations that impaired linear ubiquitin recognition activity and prevented recognition by LUBAC synergistically suppressed signal-induced NF-κB activation. HOIP NZF1 bound to NEMO and ubiquitin simultaneously, and HOIP NZF1 mutants defective in interaction with either NEMO or ubiquitin could not restore signal-induced NF-κB activation. Furthermore, linear chain-mediated activation of IKK2 involved homotypic interaction of the IKK2 kinase domain. Collectively, these results demonstrate that linear polyubiquitination of NEMO plays crucial roles in IKK activation and that this modification involves the HOIP NZF1 domain and recognition of NEMO-conjugated linear ubiquitin chains by NEMO on another IKK complex. PMID:24469399

Mathematical Techniques for Nonlinear System Theory.

DTIC Science & Technology

1981-09-01

This report deals with research results obtained in the following areas: (1) Finite-dimensional linear system theory by algebraic methods--linear...Infinite-dimensional linear systems--realization theory of infinite-dimensional linear systems; (3) Nonlinear system theory --basic properties of

An Instructional Note on Linear Programming--A Pedagogically Sound Approach.

ERIC Educational Resources Information Center

Mitchell, Richard

1998-01-01

Discusses the place of linear programming in college curricula and the advantages of using linear-programming software. Lists important characteristics of computer software used in linear programming for more effective teaching and learning. (ASK)

Parameter estimation of Monod model by the Least-Squares method for microalgae Botryococcus Braunii sp

NASA Astrophysics Data System (ADS)

See, J. J.; Jamaian, S. S.; Salleh, R. M.; Nor, M. E.; Aman, F.

2018-04-01

This research aims to estimate the parameters of Monod model of microalgae Botryococcus Braunii sp growth by the Least-Squares method. Monod equation is a non-linear equation which can be transformed into a linear equation form and it is solved by implementing the Least-Squares linear regression method. Meanwhile, Gauss-Newton method is an alternative method to solve the non-linear Least-Squares problem with the aim to obtain the parameters value of Monod model by minimizing the sum of square error ( SSE). As the result, the parameters of the Monod model for microalgae Botryococcus Braunii sp can be estimated by the Least-Squares method. However, the estimated parameters value obtained by the non-linear Least-Squares method are more accurate compared to the linear Least-Squares method since the SSE of the non-linear Least-Squares method is less than the linear Least-Squares method.

Linear relationship between water wetting behavior and microscopic interactions of super-hydrophilic surfaces.

PubMed

Liu, Jian; Wang, Chunlei; Guo, Pan; Shi, Guosheng; Fang, Haiping

2013-12-21

Using molecular dynamics simulations, we show a fine linear relationship between surface energies and microscopic Lennard-Jones parameters of super-hydrophilic surfaces. The linear slope of the super-hydrophilic surfaces is consistent with the linear slope of the super-hydrophobic, hydrophobic, and hydrophilic surfaces where stable water droplets can stand, indicating that there is a universal linear behavior of the surface energies with the water-surface van der Waals interaction that extends from the super-hydrophobic to super-hydrophilic surfaces. Moreover, we find that the linear relationship exists for various substrate types, and the linear slopes of these different types of substrates are dependent on the surface atom density, i.e., higher surface atom densities correspond to larger linear slopes. These results enrich our understanding of water behavior on solid surfaces, especially the water wetting behaviors on uncharged super-hydrophilic metal surfaces.

Linear Cowden nevus: a new distinct epidermal nevus.

PubMed

Happle, Rudolf

2007-01-01

Within the group of epidermal nevi, a so far nameless disorder is described under the term "linear Cowden nevus". This non-organoid epidermal nevus is caused by loss of heterozygosity, occurring at an early developmental stage in an embryo with a germline PTEN mutation, giving rise to Cowden disease. Hence, linear Cowden nevus can be categorized as a characteristic feature of type 2 segmental Cowden disease. Until now, several authors had mistaken this epidermal nevus as a manifestation of Proteus syndrome. The concept of linear Cowden nevus implies that Proteus syndrome is by no means caused by PTEN mutations. As a clinical difference, linear Cowden nevus is markedly papillomatous and thick, whereas linear Proteus nevus tends to be rather flat. Moreover, the spectrum of possibly associated cutaneous or extracutaneous anomalies differs in the two types of nevi. In conclusion, linear Cowden nevus, that may also be called "linear PTEN nevus", represents a distinct clinicogenetic entity.

SNDR enhancement in noisy sinusoidal signals by non-linear processing elements

NASA Astrophysics Data System (ADS)

Martorell, Ferran; McDonnell, Mark D.; Abbott, Derek; Rubio, Antonio

2007-06-01

We investigate the possibility of building linear amplifiers capable of enhancing the Signal-to-Noise and Distortion Ratio (SNDR) of sinusoidal input signals using simple non-linear elements. Other works have proven that it is possible to enhance the Signal-to-Noise Ratio (SNR) by using limiters. In this work we study a soft limiter non-linear element with and without hysteresis. We show that the SNDR of sinusoidal signals can be enhanced by 0.94 dB using a wideband soft limiter and up to 9.68 dB using a wideband soft limiter with hysteresis. These results indicate that linear amplifiers could be constructed using non-linear circuits with hysteresis. This paper presents mathematical descriptions for the non-linear elements using statistical parameters. Using these models, the input-output SNDR enhancement is obtained by optimizing the non-linear transfer function parameters to maximize the output SNDR.

A sequential linear optimization approach for controller design

NASA Technical Reports Server (NTRS)

Horta, L. G.; Juang, J.-N.; Junkins, J. L.

1985-01-01

A linear optimization approach with a simple real arithmetic algorithm is presented for reliable controller design and vibration suppression of flexible structures. Using first order sensitivity of the system eigenvalues with respect to the design parameters in conjunction with a continuation procedure, the method converts a nonlinear optimization problem into a maximization problem with linear inequality constraints. The method of linear programming is then applied to solve the converted linear optimization problem. The general efficiency of the linear programming approach allows the method to handle structural optimization problems with a large number of inequality constraints on the design vector. The method is demonstrated using a truss beam finite element model for the optimal sizing and placement of active/passive-structural members for damping augmentation. Results using both the sequential linear optimization approach and nonlinear optimization are presented and compared. The insensitivity to initial conditions of the linear optimization approach is also demonstrated.

Efficient Craig Interpolation for Linear Diophantine (Dis)Equations and Linear Modular Equations

DTIC Science & Technology

2008-02-01

Craig interpolants has enabled the development of powerful hardware and software model checking techniques. Efficient algorithms are known for computing...interpolants in rational and real linear arithmetic. We focus on subsets of integer linear arithmetic. Our main results are polynomial time algorithms ...congruences), and linear diophantine disequations. We show the utility of the proposed interpolation algorithms for discovering modular/divisibility predicates

Testing the dose-response specification in epidemiology: public health and policy consequences for lead.

PubMed

Rothenberg, Stephen J; Rothenberg, Jesse C

2005-09-01

Statistical evaluation of the dose-response function in lead epidemiology is rarely attempted. Economic evaluation of health benefits of lead reduction usually assumes a linear dose-response function, regardless of the outcome measure used. We reanalyzed a previously published study, an international pooled data set combining data from seven prospective lead studies examining contemporaneous blood lead effect on IQ (intelligence quotient) of 7-year-old children (n = 1,333). We constructed alternative linear multiple regression models with linear blood lead terms (linear-linear dose response) and natural-log-transformed blood lead terms (log-linear dose response). We tested the two lead specifications for nonlinearity in the models, compared the two lead specifications for significantly better fit to the data, and examined the effects of possible residual confounding on the functional form of the dose-response relationship. We found that a log-linear lead-IQ relationship was a significantly better fit than was a linear-linear relationship for IQ (p = 0.009), with little evidence of residual confounding of included model variables. We substituted the log-linear lead-IQ effect in a previously published health benefits model and found that the economic savings due to U.S. population lead decrease between 1976 and 1999 (from 17.1 microg/dL to 2.0 microg/dL) was 2.2 times (319 billion dollars) that calculated using a linear-linear dose-response function (149 billion dollars). The Centers for Disease Control and Prevention action limit of 10 microg/dL for children fails to protect against most damage and economic cost attributable to lead exposure.

Discriminative analysis of non-linear brain connectivity for leukoaraiosis with resting-state fMRI

NASA Astrophysics Data System (ADS)

Lai, Youzhi; Xu, Lele; Yao, Li; Wu, Xia

2015-03-01

Leukoaraiosis (LA) describes diffuse white matter abnormalities on CT or MR brain scans, often seen in the normal elderly and in association with vascular risk factors such as hypertension, or in the context of cognitive impairment. The mechanism of cognitive dysfunction is still unclear. The recent clinical studies have revealed that the severity of LA was not corresponding to the cognitive level, and functional connectivity analysis is an appropriate method to detect the relation between LA and cognitive decline. However, existing functional connectivity analyses of LA have been mostly limited to linear associations. In this investigation, a novel measure utilizing the extended maximal information coefficient (eMIC) was applied to construct non-linear functional connectivity in 44 LA subjects (9 dementia, 25 mild cognitive impairment (MCI) and 10 cognitively normal (CN)). The strength of non-linear functional connections for the first 1% of discriminative power increased in MCI compared with CN and dementia, which was opposed to its linear counterpart. Further functional network analysis revealed that the changes of the non-linear and linear connectivity have similar but not completely the same spatial distribution in human brain. In the multivariate pattern analysis with multiple classifiers, the non-linear functional connectivity mostly identified dementia, MCI and CN from LA with a relatively higher accuracy rate than the linear measure. Our findings revealed the non-linear functional connectivity provided useful discriminative power in classification of LA, and the spatial distributed changes between the non-linear and linear measure may indicate the underlying mechanism of cognitive dysfunction in LA.

Parallels between control PDE's (Partial Differential Equations) and systems of ODE's (Ordinary Differential Equations)

NASA Technical Reports Server (NTRS)

Hunt, L. R.; Villarreal, Ramiro

1987-01-01

System theorists understand that the same mathematical objects which determine controllability for nonlinear control systems of ordinary differential equations (ODEs) also determine hypoellipticity for linear partial differentail equations (PDEs). Moreover, almost any study of ODE systems begins with linear systems. It is remarkable that Hormander's paper on hypoellipticity of second order linear p.d.e.'s starts with equations due to Kolmogorov, which are shown to be analogous to the linear PDEs. Eigenvalue placement by state feedback for a controllable linear system can be paralleled for a Kolmogorov equation if an appropriate type of feedback is introduced. Results concerning transformations of nonlinear systems to linear systems are similar to results for transforming a linear PDE to a Kolmogorov equation.

Simplified large African carnivore density estimators from track indices.

PubMed

Winterbach, Christiaan W; Ferreira, Sam M; Funston, Paul J; Somers, Michael J

2016-01-01

The range, population size and trend of large carnivores are important parameters to assess their status globally and to plan conservation strategies. One can use linear models to assess population size and trends of large carnivores from track-based surveys on suitable substrates. The conventional approach of a linear model with intercept may not intercept at zero, but may fit the data better than linear model through the origin. We assess whether a linear regression through the origin is more appropriate than a linear regression with intercept to model large African carnivore densities and track indices. We did simple linear regression with intercept analysis and simple linear regression through the origin and used the confidence interval for ß in the linear model y  =  αx  + ß, Standard Error of Estimate, Mean Squares Residual and Akaike Information Criteria to evaluate the models. The Lion on Clay and Low Density on Sand models with intercept were not significant ( P  > 0.05). The other four models with intercept and the six models thorough origin were all significant ( P  < 0.05). The models using linear regression with intercept all included zero in the confidence interval for ß and the null hypothesis that ß = 0 could not be rejected. All models showed that the linear model through the origin provided a better fit than the linear model with intercept, as indicated by the Standard Error of Estimate and Mean Square Residuals. Akaike Information Criteria showed that linear models through the origin were better and that none of the linear models with intercept had substantial support. Our results showed that linear regression through the origin is justified over the more typical linear regression with intercept for all models we tested. A general model can be used to estimate large carnivore densities from track densities across species and study areas. The formula observed track density = 3.26 × carnivore density can be used to estimate densities of large African carnivores using track counts on sandy substrates in areas where carnivore densities are 0.27 carnivores/100 km 2 or higher. To improve the current models, we need independent data to validate the models and data to test for non-linear relationship between track indices and true density at low densities.

Reconstruction of real-space linear matter power spectrum from multipoles of BOSS DR12 results

NASA Astrophysics Data System (ADS)

Lee, Seokcheon

2018-02-01

Recently, the power spectrum (PS) multipoles using the Baryon Oscillation Spectroscopic Survey (BOSS) Data Release 12 (DR12) sample are analyzed [1]. The based model for the analysis is the so-called TNS quasi-linear model and the analysis provides the multipoles up to the hexadecapole [2]. Thus, one might be able to recover the real-space linear matter PS by using the combinations of multipoles to investigate the cosmology [3]. We provide the analytic form of the ratio of quadrupole (hexadecapole) to monopole moments of the quasi-linear PS including the Fingers-of-God (FoG) effect to recover the real-space PS in the linear regime. One expects that observed values of the ratios of multipoles should be consistent with those of the linear theory at large scales. Thus, we compare the ratios of multipoles of the linear theory, including the FoG effect with the measured values. From these, we recover the linear matter power spectra in real-space. These recovered power spectra are consistent with the linear matter power spectra.

Metallocenyl dendrimers and their applications in molecular electronics, sensing, and catalysis.

PubMed

Astruc, Didier; Ornelas, Cátia; Ruiz, Jaime

2008-07-01

We have investigated the movement of electrons around the peripheries of dendrimers and between their redox termini and electrodes through studies of the electrochemistry of dendrimers presenting metallocenes (and other transition metal sandwich complexes) as terminal groups. Because these compounds can be stabilized in both their oxidized and their reduced forms, their electrochemical and chemical redox processes proceed without decomposition (chemical reversibility). Most interestingly, electrochemical studies reveal that electron transfer within the dendrimers and between the dendrimers and electrodes are both very fast processes when the branches are flexible (electrochemical reversibility). When the dendrimer branches are sufficiently long, the redox events at the many termini of the metallodendrimer are independent, appearing as a single wave in the cyclic voltammogram, because of very weak electrostatic effects. As a result, these metallodendrimers have applications in the molecular recognition, sensing, and titration of anions (e.g., ATP(2-)) and cations (e.g., transition metal complexes). When the recognition properties are coupled with catalysis, the metallodendrimers function in an enzyme-like manner. For example, Pd(II) can be recognized and titrated using the dendrimer's terminal redox centers and internal coordinate ligands. Redox control over the number of Pd(II) species located within a dendrimer allows us to predetermine the number of metal atoms that end up in the form of a dendrimer-encapsulated Pd nanoparticle (PdNP). For hydrogenation of olefins, the efficiency (turnover frequency, TOF) and stability (turnover number, TON) depend on the size of the dendrimer-encapsulated PdNP catalysts, similar to the behavior of polymer-supported PdNP catalysts, suggesting a classic mechanism in which all of the steps proceed on the PdNP surface. On the other hand, Miyaura-Suzuki carbon-carbon bond-forming reactions catalyzed by dendrimer-encapsulated PdNPs proceed with TOFs and TONs that do not depend on the size of the PdNPs. Moreover these catalysts are more efficient when employed in lower (down to "homeopathic") amounts, presumably because of a leaching mechanism whereby Pd atoms escape from the PdNP surface subsequent to oxidative addition of the aryl halide. Under these conditions, the "mother" PdNPs have greater difficulty quenching the extremely active leached Pd atoms because of their low concentration. Although dendrimers presenting catalysts at their branch termini can be recovered and reused readily, their inner-sphere components can lead to steric inhibition of substrate approach. In contrast, star-shaped catalysts do not suffer from such steric problems, as has been demonstrated for water-soluble dendrimers bearing cationic iron-sandwich termini, which are redox catalysts of cathodic nitrate and nitrite reduction in water.

Electronic Structure Properties and a Bonding Model of Thermoelectric Half-Heusler and Boride Phases

NASA Astrophysics Data System (ADS)

Simonson, Jack William

Half-Heusler alloys MNiSn and MCoSb (M = Ti, Zr, Hf) and layered boride intermetallics with structure types YCrB4 and Er 3CrB7 were designed, synthesized, and characterized. The thermoelectric properties of these two classes of alloys were measured from room temperature to 1100 K with the intent of indirectly studying their electronic structure properties and gauging not only their suitability but that of related alloys for high temperature thermoelectric power generation. In the case of the half-Heusler alloys, transition metals were substituted to both the M and Ni/Co sites to study the resultant modifications of the d-orbital-rich portion of the electronic structure near the Fermi energy. This modification and subsequent pinning of the Fermi energy within the gap is discussed herein in terms of first principles electronic structure calculations from the literature. In the half-Heusler alloys, it was found that substitution of transition metals invariably led to a decrease in the thermopower, while the resistivity typically maintained its semiconducting trend. On the other hand, Sn doping in MCoSb type alloys -- a dopant that has been known for some time to be efficient -- was shown to result in high ZT at temperatures in excess of 1000 K. Moreover, the band gaps of the transition metal-doped alloys measured in this work offer insight into the discrepancy between the predicted and measured band gaps in the undoped parent compositions. In the case of the layered boride alloys, on the other hand, few electronic calculations have been published, thus prompting the generalization of a well-known electron counting rule -- which is typically used to study molecular organometallics, boranes, and metallocenes -- to predict the trends in the densities of states of crystalline solids that possess the requisite deltahedral bonding geometry. In accordance with these generalized electronic counting rules, alloys of the form RMB4 (R = Y, Gd, Ho; M = Cr, Mo, W) were measured to be n-type semiconductors with band gaps ranging from 0.15 eV to 0.25 eV. These alloys exhibited thermoelectric power factors comparable with those of other potential boride thermoelectric materials reported in the literature. Furthermore, as a result of the procedure developed for precision synthesis of boron-rich intermetallics and the improved understanding of bonding trends, layered borides of several previously overlooked structure-types were synthesized and screened for superconductivity. Consequently, alloys of the MoB4 phase were discovered to be superconducting when doped with Nb or Ti. Electrical resistivity measurements of superconducting transitions between 6 and 8 K in these materials were confirmed via magnetic susceptibility measurements and x-ray diffraction. Structural measurements indicated opposite trends in lattice modification than those reported for the superconducting transition metal diborides.

Structural Dynamic Analyses And Test Predictions For Spacecraft Structures With Non-Linearities

NASA Astrophysics Data System (ADS)

Vergniaud, Jean-Baptiste; Soula, Laurent; Newerla, Alfred

2012-07-01

The overall objective of the mechanical development and verification process is to ensure that the spacecraft structure is able to sustain the mechanical environments encountered during launch. In general the spacecraft structures are a-priori assumed to behave linear, i.e. the responses to a static load or dynamic excitation, respectively, will increase or decrease proportionally to the amplitude of the load or excitation induced. However, past experiences have shown that various non-linearities might exist in spacecraft structures and the consequences of their dynamic effects can significantly affect the development and verification process. Current processes are mainly adapted to linear spacecraft structure behaviour. No clear rules exist for dealing with major structure non-linearities. They are handled outside the process by individual analysis and margin policy, and analyses after tests to justify the CLA coverage. Non-linearities can primarily affect the current spacecraft development and verification process on two aspects. Prediction of flights loads by launcher/satellite coupled loads analyses (CLA): only linear satellite models are delivered for performing CLA and no well-established rules exist how to properly linearize a model when non- linearities are present. The potential impact of the linearization on the results of the CLA has not yet been properly analyzed. There are thus difficulties to assess that CLA results will cover actual flight levels. Management of satellite verification tests: the CLA results generated with a linear satellite FEM are assumed flight representative. If the internal non- linearities are present in the tested satellite then there might be difficulties to determine which input level must be passed to cover satellite internal loads. The non-linear behaviour can also disturb the shaker control, putting the satellite at risk by potentially imposing too high levels. This paper presents the results of a test campaign performed in the frame of an ESA TRP study [1]. A bread-board including typical non-linearities has been designed, manufactured and tested through a typical spacecraft dynamic test campaign. The study has demonstrate the capabilities to perform non-linear dynamic test predictions on a flight representative spacecraft, the good correlation of test results with respect to Finite Elements Model (FEM) prediction and the possibility to identify modal behaviour and to characterize non-linearities characteristics from test results. As a synthesis for this study, overall guidelines have been derived on the mechanical verification process to improve level of expertise on tests involving spacecraft including non-linearity.

Linear shaped charge

DOEpatents

Peterson, David; Stofleth, Jerome H.; Saul, Venner W.

2017-07-11

Linear shaped charges are described herein. In a general embodiment, the linear shaped charge has an explosive with an elongated arrowhead-shaped profile. The linear shaped charge also has and an elongated v-shaped liner that is inset into a recess of the explosive. Another linear shaped charge includes an explosive that is shaped as a star-shaped prism. Liners are inset into crevices of the explosive, where the explosive acts as a tamper.

Extending Linear Models to Non-Linear Contexts: An In-Depth Study about Two University Students' Mathematical Productions

ERIC Educational Resources Information Center

Esteley, Cristina; Villarreal, Monica; Alagia, Humberto

2004-01-01

This research report presents a study of the work of agronomy majors in which an extension of linear models to non-linear contexts can be observed. By linear models we mean the model y=a.x+b, some particular representations of direct proportionality and the diagram for the rule of three. Its presence and persistence in different types of problems…

Short Round Sub-Linear Zero-Knowledge Argument for Linear Algebraic Relations

NASA Astrophysics Data System (ADS)

Seo, Jae Hong

Zero-knowledge arguments allows one party to prove that a statement is true, without leaking any other information than the truth of the statement. In many applications such as verifiable shuffle (as a practical application) and circuit satisfiability (as a theoretical application), zero-knowledge arguments for mathematical statements related to linear algebra are essentially used. Groth proposed (at CRYPTO 2009) an elegant methodology for zero-knowledge arguments for linear algebraic relations over finite fields. He obtained zero-knowledge arguments of the sub-linear size for linear algebra using reductions from linear algebraic relations to equations of the form z = x *' y, where x, y ∈ Fnp are committed vectors, z ∈ Fp is a committed element, and *' : Fnp × Fnp → Fp is a bilinear map. These reductions impose additional rounds on zero-knowledge arguments of the sub-linear size. The round complexity of interactive zero-knowledge arguments is an important measure along with communication and computational complexities. We focus on minimizing the round complexity of sub-linear zero-knowledge arguments for linear algebra. To reduce round complexity, we propose a general transformation from a t-round zero-knowledge argument, satisfying mild conditions, to a (t - 2)-round zero-knowledge argument; this transformation is of independent interest.

Linear indices of the "molecular pseudograph's atom adjacency matrix": definition, significance-interpretation, and application to QSAR analysis of flavone derivatives as HIV-1 integrase inhibitors.

PubMed

Marrero-Ponce, Yovani

2004-01-01

This report describes a new set of molecular descriptors of relevance to QSAR/QSPR studies and drug design, atom linear indices fk(xi). These atomic level chemical descriptors are based on the calculation of linear maps on Rn[fk(xi): Rn--> Rn] in canonical basis. In this context, the kth power of the molecular pseudograph's atom adjacency matrix [Mk(G)] denotes the matrix of fk(xi) with respect to the canonical basis. In addition, a local-fragment (atom-type) formalism was developed. The kth atom-type linear indices are calculated by summing the kth atom linear indices of all atoms of the same atom type in the molecules. Moreover, total (whole-molecule) linear indices are also proposed. This descriptor is a linear functional (linear form) on Rn. That is, the kth total linear indices is a linear map from Rn to the scalar R[ fk(x): Rn --> R]. Thus, the kth total linear indices are calculated by summing the atom linear indices of all atoms in the molecule. The features of the kth total and local linear indices are illustrated by examples of various types of molecular structures, including chain-lengthening, branching, heteroatoms-content, and multiple bonds. Additionally, the linear independence of the local linear indices to other 0D, 1D, 2D, and 3D molecular descriptors is demonstrated by using principal component analysis for 42 very heterogeneous molecules. Much redundancy and overlapping was found among total linear indices and most of the other structural indices presently in use in the QSPR/QSAR practice. On the contrary, the information carried by atom-type linear indices was strikingly different from that codified in most of the 229 0D-3D molecular descriptors used in this study. It is concluded that the local linear indices are an independent indices containing important structural information to be used in QSPR/QSAR and drug design studies. In this sense, atom, atom-type, and total linear indices were used for the prediction of pIC50 values for the cleavage process of a set of flavone derivatives inhibitors of HIV-1 integrase. Quantitative models found are significant from a statistical point of view (R of 0.965, 0.902, and 0.927, respectively) and permit a clear interpretation of the studied properties in terms of the structural features of molecules. A LOO cross-validation procedure revealed that the regression models had a fairly good predictability (q2 of 0.679, 0.543, and 0.721, respectively). The comparison with other approaches reveals good behavior of the method proposed. The approach described in this paper appears to be an excellent alternative or guides for discovery and optimization of new lead compounds.

Linear summation of outputs in a balanced network model of motor cortex.

PubMed

Capaday, Charles; van Vreeswijk, Carl

2015-01-01

Given the non-linearities of the neural circuitry's elements, we would expect cortical circuits to respond non-linearly when activated. Surprisingly, when two points in the motor cortex are activated simultaneously, the EMG responses are the linear sum of the responses evoked by each of the points activated separately. Additionally, the corticospinal transfer function is close to linear, implying that the synaptic interactions in motor cortex must be effectively linear. To account for this, here we develop a model of motor cortex composed of multiple interconnected points, each comprised of reciprocally connected excitatory and inhibitory neurons. We show how non-linearities in neuronal transfer functions are eschewed by strong synaptic interactions within each point. Consequently, the simultaneous activation of multiple points results in a linear summation of their respective outputs. We also consider the effects of reduction of inhibition at a cortical point when one or more surrounding points are active. The network response in this condition is linear over an approximately two- to three-fold decrease of inhibitory feedback strength. This result supports the idea that focal disinhibition allows linear coupling of motor cortical points to generate movement related muscle activation patterns; albeit with a limitation on gain control. The model also explains why neural activity does not spread as far out as the axonal connectivity allows, whilst also explaining why distant cortical points can be, nonetheless, functionally coupled by focal disinhibition. Finally, we discuss the advantages that linear interactions at the cortical level afford to motor command synthesis.

Analysis and comparison of end effects in linear switched reluctance and hybrid motors

NASA Astrophysics Data System (ADS)

Barhoumi, El Manaa; Abo-Khalil, Ahmed Galal; Berrouche, Youcef; Wurtz, Frederic

2017-03-01

This paper presents and discusses the longitudinal and transversal end effects which affects the propulsive force of linear motors. Generally, the modeling of linear machine considers the forces distortion due to the specific geometry of linear actuators. The insertion of permanent magnets on the stator allows improving the propulsive force produced by switched reluctance linear motors. Also, the inserted permanent magnets in the hybrid structure allow reducing considerably the ends effects observed in linear motors. The analysis was conducted using 2D and 3D finite elements method. The permanent magnet reinforces the flux produced by the winding and reorients it which allows modifying the impact of end effects. Presented simulations and discussions show the importance of this study to characterize the end effects in two different linear motors.

Multispectral linear array visible and shortwave infrared sensors

NASA Astrophysics Data System (ADS)

Tower, J. R.; Warren, F. B.; Pellon, L. E.; Strong, R.; Elabd, H.; Cope, A. D.; Hoffmann, D. M.; Kramer, W. M.; Longsderff, R. W.

1984-08-01

All-solid state pushbroom sensors for multispectral linear array (MLA) instruments to replace mechanical scanners used on LANDSAT satellites are introduced. A buttable, four-spectral-band, linear-format charge coupled device (CCD) and a buttable, two-spectral-band, linear-format, shortwave infrared CCD are described. These silicon integrated circuits may be butted end to end to provide multispectral focal planes with thousands of contiguous, in-line photosites. The visible CCD integrated circuit is organized as four linear arrays of 1024 pixels each. Each array views the scene in a different spectral window, resulting in a four-band sensor. The shortwave infrared (SWIR) sensor is organized as 2 linear arrays of 512 detectors each. Each linear array is optimized for performance at a different wavelength in the SWIR band.

Advanced analysis technique for the evaluation of linear alternators and linear motors

NASA Technical Reports Server (NTRS)

Holliday, Jeffrey C.

1995-01-01

A method for the mathematical analysis of linear alternator and linear motor devices and designs is described, and an example of its use is included. The technique seeks to surpass other methods of analysis by including more rigorous treatment of phenomena normally omitted or coarsely approximated such as eddy braking, non-linear material properties, and power losses generated within structures surrounding the device. The technique is broadly applicable to linear alternators and linear motors involving iron yoke structures and moving permanent magnets. The technique involves the application of Amperian current equivalents to the modeling of the moving permanent magnet components within a finite element formulation. The resulting steady state and transient mode field solutions can simultaneously account for the moving and static field sources within and around the device.

Advanced statistics: linear regression, part I: simple linear regression.

PubMed

Marill, Keith A

2004-01-01

Simple linear regression is a mathematical technique used to model the relationship between a single independent predictor variable and a single dependent outcome variable. In this, the first of a two-part series exploring concepts in linear regression analysis, the four fundamental assumptions and the mechanics of simple linear regression are reviewed. The most common technique used to derive the regression line, the method of least squares, is described. The reader will be acquainted with other important concepts in simple linear regression, including: variable transformations, dummy variables, relationship to inference testing, and leverage. Simplified clinical examples with small datasets and graphic models are used to illustrate the points. This will provide a foundation for the second article in this series: a discussion of multiple linear regression, in which there are multiple predictor variables.

Modelling female fertility traits in beef cattle using linear and non-linear models.

PubMed

Naya, H; Peñagaricano, F; Urioste, J I

2017-06-01

Female fertility traits are key components of the profitability of beef cattle production. However, these traits are difficult and expensive to measure, particularly under extensive pastoral conditions, and consequently, fertility records are in general scarce and somehow incomplete. Moreover, fertility traits are usually dominated by the effects of herd-year environment, and it is generally assumed that relatively small margins are kept for genetic improvement. New ways of modelling genetic variation in these traits are needed. Inspired in the methodological developments made by Prof. Daniel Gianola and co-workers, we assayed linear (Gaussian), Poisson, probit (threshold), censored Poisson and censored Gaussian models to three different kinds of endpoints, namely calving success (CS), number of days from first calving (CD) and number of failed oestrus (FE). For models involving FE and CS, non-linear models overperformed their linear counterparts. For models derived from CD, linear versions displayed better adjustment than the non-linear counterparts. Non-linear models showed consistently higher estimates of heritability and repeatability in all cases (h 2  < 0.08 and r < 0.13, for linear models; h 2  > 0.23 and r > 0.24, for non-linear models). While additive and permanent environment effects showed highly favourable correlations between all models (>0.789), consistency in selecting the 10% best sires showed important differences, mainly amongst the considered endpoints (FE, CS and CD). In consequence, endpoints should be considered as modelling different underlying genetic effects, with linear models more appropriate to describe CD and non-linear models better for FE and CS. © 2017 Blackwell Verlag GmbH.

Design of Linear-Quadratic-Regulator for a CSTR process

NASA Astrophysics Data System (ADS)

Meghna, P. R.; Saranya, V.; Jaganatha Pandian, B.

2017-11-01

This paper aims at creating a Linear Quadratic Regulator (LQR) for a Continuous Stirred Tank Reactor (CSTR). A CSTR is a common process used in chemical industries. It is a highly non-linear system. Therefore, in order to create the gain feedback controller, the model is linearized. The controller is designed for the linearized model and the concentration and volume of the liquid in the reactor are kept at a constant value as required.

Feedback linearization for control of air breathing engines

NASA Technical Reports Server (NTRS)

Phillips, Stephen; Mattern, Duane

1991-01-01

The method of feedback linearization for control of the nonlinear nozzle and compressor components of an air breathing engine is presented. This method overcomes the need for a large number of scheduling variables and operating points to accurately model highly nonlinear plants. Feedback linearization also results in linear closed loop system performance simplifying subsequent control design. Feedback linearization is used for the nonlinear partial engine model and performance is verified through simulation.

Menu-Driven Solver Of Linear-Programming Problems

NASA Technical Reports Server (NTRS)

Viterna, L. A.; Ferencz, D.

1992-01-01

Program assists inexperienced user in formulating linear-programming problems. A Linear Program Solver (ALPS) computer program is full-featured LP analysis program. Solves plain linear-programming problems as well as more-complicated mixed-integer and pure-integer programs. Also contains efficient technique for solution of purely binary linear-programming problems. Written entirely in IBM's APL2/PC software, Version 1.01. Packed program contains licensed material, property of IBM (copyright 1988, all rights reserved).

Investigation on Constrained Matrix Factorization for Hyperspectral Image Analysis

DTIC Science & Technology

2005-07-25

analysis. Keywords: matrix factorization; nonnegative matrix factorization; linear mixture model ; unsupervised linear unmixing; hyperspectral imagery...spatial resolution permits different materials present in the area covered by a single pixel. The linear mixture model says that a pixel reflectance in...in r. In the linear mixture model , r is considered as the linear mixture of m1, m2, …, mP as nMαr += (1) where n is included to account for

The response of multidegree-of-freedom systems with quadratic non-linearities to a harmonic parametric resonance

NASA Astrophysics Data System (ADS)

Nayfeh, A. H.

1983-09-01

An analysis is presented of the response of multidegree-of-freedom systems with quadratic non-linearities to a harmonic parametric excitation in the presence of an internal resonance of the combination type ω3 ≈ ω2 + ω1, where the ωn are the linear natural frequencies of the systems. In the case of a fundamental resonance of the third mode (i.e., Ω ≈ω 3, where Ω is the frequency of the excitation), one can identify two critical values ζ 1 and ζ 2, where ζ 2 ⩾ ζ 1, of the amplitude F of the excitation. The value F = ζ2 corresponds to the transition from stable to unstable solutions. When F < ζ1, the motion decays to zero according to both linear and non-linear theories. When F > ζ2, the motion grows exponentially with time according to the linear theory but the non-linearity limits the motion to a finite amplitude steady state. The amplitude of the third mode, which is directly excited, is independent of F, whereas the amplitudes of the first and second modes, which are indirectly excited through the internal resonance, are functions of F. When ζ1 ⩽ F ⩽ ζ2, the motion decays or achieves a finite amplitude steady state depending on the initial conditions according to the non-linear theory, whereas it decays to zero according to the linear theory. This is an example of subcritical instability. In the case of a fundamental resonance of either the first or second mode, the trivial response is the only possible steady state. When F ⩽ ζ2, the motion decays to zero according to both linear and non-linear theories. When F > ζ2, the motion grows exponentially with time according to the linear theory but it is aperiodic according to the non-linear theory. Experiments are being planned to check these theoretical results.

Comparison of all atom, continuum, and linear fitting empirical models for charge screening effect of aqueous medium surrounding a protein molecule

NASA Astrophysics Data System (ADS)

Takahashi, Takuya; Sugiura, Junnnosuke; Nagayama, Kuniaki

2002-05-01

To investigate the role hydration plays in the electrostatic interactions of proteins, the time-averaged electrostatic potential of the B1 domain of protein G in an aqueous solution was calculated with full atomic molecular dynamics simulations that explicitly considers every atom (i.e., an all atom model). This all atom calculated potential was compared with the potential obtained from an electrostatic continuum model calculation. In both cases, the charge-screening effect was fairly well formulated with an effective relative dielectric constant which increased linearly with increasing charge-charge distance. This simulated linear dependence agrees with the experimentally determined linear relation proposed by Pickersgill. Cut-off approximations for Coulomb interactions failed to reproduce this linear relation. Correlation between the all atom model and the continuum models was found to be better than the respective correlation calculated for linear fitting to the two models. This confirms that the continuum model is better at treating the complicated shapes of protein conformations than the simple linear fitting empirical model. We have tried a sigmoid fitting empirical model in addition to the linear one. When weights of all data were treated equally, the sigmoid model, which requires two fitting parameters, fits results of both the all atom and the continuum models less accurately than the linear model which requires only one fitting parameter. When potential values are chosen as weighting factors, the fitting error of the sigmoid model became smaller, and the slope of both linear fitting curves became smaller. This suggests the screening effect of an aqueous medium within a short range, where potential values are relatively large, is smaller than that expected from the linear fitting curve whose slope is almost 4. To investigate the linear increase of the effective relative dielectric constant, the Poisson equation of a low-dielectric sphere in a high-dielectric medium was solved and charges distributed near the molecular surface were indicated as leading to the apparent linearity.

Passive dendrites enable single neurons to compute linearly non-separable functions.

PubMed

Cazé, Romain Daniel; Humphries, Mark; Gutkin, Boris

2013-01-01

Local supra-linear summation of excitatory inputs occurring in pyramidal cell dendrites, the so-called dendritic spikes, results in independent spiking dendritic sub-units, which turn pyramidal neurons into two-layer neural networks capable of computing linearly non-separable functions, such as the exclusive OR. Other neuron classes, such as interneurons, may possess only a few independent dendritic sub-units, or only passive dendrites where input summation is purely sub-linear, and where dendritic sub-units are only saturating. To determine if such neurons can also compute linearly non-separable functions, we enumerate, for a given parameter range, the Boolean functions implementable by a binary neuron model with a linear sub-unit and either a single spiking or a saturating dendritic sub-unit. We then analytically generalize these numerical results to an arbitrary number of non-linear sub-units. First, we show that a single non-linear dendritic sub-unit, in addition to the somatic non-linearity, is sufficient to compute linearly non-separable functions. Second, we analytically prove that, with a sufficient number of saturating dendritic sub-units, a neuron can compute all functions computable with purely excitatory inputs. Third, we show that these linearly non-separable functions can be implemented with at least two strategies: one where a dendritic sub-unit is sufficient to trigger a somatic spike; another where somatic spiking requires the cooperation of multiple dendritic sub-units. We formally prove that implementing the latter architecture is possible with both types of dendritic sub-units whereas the former is only possible with spiking dendrites. Finally, we show how linearly non-separable functions can be computed by a generic two-compartment biophysical model and a realistic neuron model of the cerebellar stellate cell interneuron. Taken together our results demonstrate that passive dendrites are sufficient to enable neurons to compute linearly non-separable functions.

Passive Dendrites Enable Single Neurons to Compute Linearly Non-separable Functions

PubMed Central

Cazé, Romain Daniel; Humphries, Mark; Gutkin, Boris

2013-01-01

Local supra-linear summation of excitatory inputs occurring in pyramidal cell dendrites, the so-called dendritic spikes, results in independent spiking dendritic sub-units, which turn pyramidal neurons into two-layer neural networks capable of computing linearly non-separable functions, such as the exclusive OR. Other neuron classes, such as interneurons, may possess only a few independent dendritic sub-units, or only passive dendrites where input summation is purely sub-linear, and where dendritic sub-units are only saturating. To determine if such neurons can also compute linearly non-separable functions, we enumerate, for a given parameter range, the Boolean functions implementable by a binary neuron model with a linear sub-unit and either a single spiking or a saturating dendritic sub-unit. We then analytically generalize these numerical results to an arbitrary number of non-linear sub-units. First, we show that a single non-linear dendritic sub-unit, in addition to the somatic non-linearity, is sufficient to compute linearly non-separable functions. Second, we analytically prove that, with a sufficient number of saturating dendritic sub-units, a neuron can compute all functions computable with purely excitatory inputs. Third, we show that these linearly non-separable functions can be implemented with at least two strategies: one where a dendritic sub-unit is sufficient to trigger a somatic spike; another where somatic spiking requires the cooperation of multiple dendritic sub-units. We formally prove that implementing the latter architecture is possible with both types of dendritic sub-units whereas the former is only possible with spiking dendrites. Finally, we show how linearly non-separable functions can be computed by a generic two-compartment biophysical model and a realistic neuron model of the cerebellar stellate cell interneuron. Taken together our results demonstrate that passive dendrites are sufficient to enable neurons to compute linearly non-separable functions. PMID:23468600

Tackling non-linearities with the effective field theory of dark energy and modified gravity

NASA Astrophysics Data System (ADS)

Frusciante, Noemi; Papadomanolakis, Georgios

2017-12-01

We present the extension of the effective field theory framework to the mildly non-linear scales. The effective field theory approach has been successfully applied to the late time cosmic acceleration phenomenon and it has been shown to be a powerful method to obtain predictions about cosmological observables on linear scales. However, mildly non-linear scales need to be consistently considered when testing gravity theories because a large part of the data comes from those scales. Thus, non-linear corrections to predictions on observables coming from the linear analysis can help in discriminating among different gravity theories. We proceed firstly by identifying the necessary operators which need to be included in the effective field theory Lagrangian in order to go beyond the linear order in perturbations and then we construct the corresponding non-linear action. Moreover, we present the complete recipe to map any single field dark energy and modified gravity models into the non-linear effective field theory framework by considering a general action in the Arnowitt-Deser-Misner formalism. In order to illustrate this recipe we proceed to map the beyond-Horndeski theory and low-energy Hořava gravity into the effective field theory formalism. As a final step we derived the 4th order action in term of the curvature perturbation. This allowed us to identify the non-linear contributions coming from the linear order perturbations which at the next order act like source terms. Moreover, we confirm that the stability requirements, ensuring the positivity of the kinetic term and the speed of propagation for scalar mode, are automatically satisfied once the viability of the theory is demanded at linear level. The approach we present here will allow to construct, in a model independent way, all the relevant predictions on observables at mildly non-linear scales.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gearhart, Jared Lee; Adair, Kristin Lynn; Durfee, Justin David.

When developing linear programming models, issues such as budget limitations, customer requirements, or licensing may preclude the use of commercial linear programming solvers. In such cases, one option is to use an open-source linear programming solver. A survey of linear programming tools was conducted to identify potential open-source solvers. From this survey, four open-source solvers were tested using a collection of linear programming test problems and the results were compared to IBM ILOG CPLEX Optimizer (CPLEX) [1], an industry standard. The solvers considered were: COIN-OR Linear Programming (CLP) [2], [3], GNU Linear Programming Kit (GLPK) [4], lp_solve [5] and Modularmore » In-core Nonlinear Optimization System (MINOS) [6]. As no open-source solver outperforms CPLEX, this study demonstrates the power of commercial linear programming software. CLP was found to be the top performing open-source solver considered in terms of capability and speed. GLPK also performed well but cannot match the speed of CLP or CPLEX. lp_solve and MINOS were considerably slower and encountered issues when solving several test problems.« less

Robust estimation for partially linear models with large-dimensional covariates

PubMed Central

Zhu, LiPing; Li, RunZe; Cui, HengJian

2014-01-01

We are concerned with robust estimation procedures to estimate the parameters in partially linear models with large-dimensional covariates. To enhance the interpretability, we suggest implementing a noncon-cave regularization method in the robust estimation procedure to select important covariates from the linear component. We establish the consistency for both the linear and the nonlinear components when the covariate dimension diverges at the rate of o(n), where n is the sample size. We show that the robust estimate of linear component performs asymptotically as well as its oracle counterpart which assumes the baseline function and the unimportant covariates were known a priori. With a consistent estimator of the linear component, we estimate the nonparametric component by a robust local linear regression. It is proved that the robust estimate of nonlinear component performs asymptotically as well as if the linear component were known in advance. Comprehensive simulation studies are carried out and an application is presented to examine the finite-sample performance of the proposed procedures. PMID:24955087

Krylov Subspace Methods for Complex Non-Hermitian Linear Systems. Thesis

NASA Technical Reports Server (NTRS)

Freund, Roland W.

1991-01-01

We consider Krylov subspace methods for the solution of large sparse linear systems Ax = b with complex non-Hermitian coefficient matrices. Such linear systems arise in important applications, such as inverse scattering, numerical solution of time-dependent Schrodinger equations, underwater acoustics, eddy current computations, numerical computations in quantum chromodynamics, and numerical conformal mapping. Typically, the resulting coefficient matrices A exhibit special structures, such as complex symmetry, or they are shifted Hermitian matrices. In this paper, we first describe a Krylov subspace approach with iterates defined by a quasi-minimal residual property, the QMR method, for solving general complex non-Hermitian linear systems. Then, we study special Krylov subspace methods designed for the two families of complex symmetric respectively shifted Hermitian linear systems. We also include some results concerning the obvious approach to general complex linear systems by solving equivalent real linear systems for the real and imaginary parts of x. Finally, numerical experiments for linear systems arising from the complex Helmholtz equation are reported.

Convergent evolution and mimicry of protein linear motifs in host-pathogen interactions.

PubMed

Chemes, Lucía Beatriz; de Prat-Gay, Gonzalo; Sánchez, Ignacio Enrique

2015-06-01

Pathogen linear motif mimics are highly evolvable elements that facilitate rewiring of host protein interaction networks. Host linear motifs and pathogen mimics differ in sequence, leading to thermodynamic and structural differences in the resulting protein-protein interactions. Moreover, the functional output of a mimic depends on the motif and domain repertoire of the pathogen protein. Regulatory evolution mediated by linear motifs can be understood by measuring evolutionary rates, quantifying positive and negative selection and performing phylogenetic reconstructions of linear motif natural history. Convergent evolution of linear motif mimics is widespread among unrelated proteins from viral, prokaryotic and eukaryotic pathogens and can also take place within individual protein phylogenies. Statistics, biochemistry and laboratory models of infection link pathogen linear motifs to phenotypic traits such as tropism, virulence and oncogenicity. In vitro evolution experiments and analysis of natural sequences suggest that changes in linear motif composition underlie pathogen adaptation to a changing environment. Copyright © 2015 Elsevier Ltd. All rights reserved.

Estimating linear effects in ANOVA designs: the easy way.

PubMed

Pinhas, Michal; Tzelgov, Joseph; Ganor-Stern, Dana

2012-09-01

Research in cognitive science has documented numerous phenomena that are approximated by linear relationships. In the domain of numerical cognition, the use of linear regression for estimating linear effects (e.g., distance and SNARC effects) became common following Fias, Brysbaert, Geypens, and d'Ydewalle's (1996) study on the SNARC effect. While their work has become the model for analyzing linear effects in the field, it requires statistical analysis of individual participants and does not provide measures of the proportions of variability accounted for (cf. Lorch & Myers, 1990). In the present methodological note, using both the distance and SNARC effects as examples, we demonstrate how linear effects can be estimated in a simple way within the framework of repeated measures analysis of variance. This method allows for estimating effect sizes in terms of both slope and proportions of variability accounted for. Finally, we show that our method can easily be extended to estimate linear interaction effects, not just linear effects calculated as main effects.

Robust estimation for partially linear models with large-dimensional covariates.

PubMed

Zhu, LiPing; Li, RunZe; Cui, HengJian

2013-10-01

We are concerned with robust estimation procedures to estimate the parameters in partially linear models with large-dimensional covariates. To enhance the interpretability, we suggest implementing a noncon-cave regularization method in the robust estimation procedure to select important covariates from the linear component. We establish the consistency for both the linear and the nonlinear components when the covariate dimension diverges at the rate of [Formula: see text], where n is the sample size. We show that the robust estimate of linear component performs asymptotically as well as its oracle counterpart which assumes the baseline function and the unimportant covariates were known a priori. With a consistent estimator of the linear component, we estimate the nonparametric component by a robust local linear regression. It is proved that the robust estimate of nonlinear component performs asymptotically as well as if the linear component were known in advance. Comprehensive simulation studies are carried out and an application is presented to examine the finite-sample performance of the proposed procedures.

Development and validation of a general purpose linearization program for rigid aircraft models

NASA Technical Reports Server (NTRS)

Duke, E. L.; Antoniewicz, R. F.

1985-01-01

A FORTRAN program that provides the user with a powerful and flexible tool for the linearization of aircraft models is discussed. The program LINEAR numerically determines a linear systems model using nonlinear equations of motion and a user-supplied, nonlinear aerodynamic model. The system model determined by LINEAR consists of matrices for both the state and observation equations. The program has been designed to allow easy selection and definition of the state, control, and observation variables to be used in a particular model. Also, included in the report is a comparison of linear and nonlinear models for a high performance aircraft.

Free-piston engine linear generator for hybrid vehicles modeling study

NASA Astrophysics Data System (ADS)

Callahan, T. J.; Ingram, S. K.

1995-05-01

Development of a free piston engine linear generator was investigated for use as an auxiliary power unit for a hybrid electric vehicle. The main focus of the program was to develop an efficient linear generator concept to convert the piston motion directly into electrical power. Computer modeling techniques were used to evaluate five different designs for linear generators. These designs included permanent magnet generators, reluctance generators, linear DC generators, and two and three-coil induction generators. The efficiency of the linear generator was highly dependent on the design concept. The two-coil induction generator was determined to be the best design, with an efficiency of approximately 90 percent.

Linear or linearizable first-order delay ordinary differential equations and their Lie point symmetries

NASA Astrophysics Data System (ADS)

Dorodnitsyn, Vladimir A.; Kozlov, Roman; Meleshko, Sergey V.; Winternitz, Pavel

2018-05-01

A recent article was devoted to an analysis of the symmetry properties of a class of first-order delay ordinary differential systems (DODSs). Here we concentrate on linear DODSs, which have infinite-dimensional Lie point symmetry groups due to the linear superposition principle. Their symmetry algebra always contains a two-dimensional subalgebra realized by linearly connected vector fields. We identify all classes of linear first-order DODSs that have additional symmetries, not due to linearity alone, and we present representatives of each class. These additional symmetries are then used to construct exact analytical particular solutions using symmetry reduction.

Linear enhancement after radio-frequency ablation for hepatocellular carcinoma: is it a sign of recurrence?

PubMed

Takahashi, Masanori; Maruyama, Hitoshi; Shimada, Taro; Kamezaki, Hidehiro; Okabe, Shinichiro; Kanai, Fumihiko; Yoshikawa, Masaharu; Yokosuka, Osamu

2012-11-01

This prospective study was performed in 179 hepatocellular carcinoma (HCC) lesions treated by radio-frequency ablation (RFA) to explore the clinical outcome of "linear enhancement" on contrast-enhanced sonogram. Thirty-three lesions (18.4%) showed linear enhancement, a linear-shaped positive enhancement in the RFA-treated area. Seventeen of them were followed up with no treatment (remaining 16; dropout in eight, additional RFA in six and ineffective treatment in two) and three lesions (3/17, 17.6%) showed local tumor progression corresponding to linear enhancement at 7, 14, 19 months after RFA. Although there was no significant difference in local recurrence rate between the lesions with (3/17) and without linear enhancement (10/35), local tumor progression inside the ablation zone occurred only in the lesions with linear enhancement. In conclusion, linear enhancement inside the RFA-treated area should be followed up within 7 months because it has a risk of local tumor progression. Histology of linear enhancement and its influence on distant recurrence remain to be solved. Copyright © 2012 World Federation for Ultrasound in Medicine & Biology. Published by Elsevier Inc. All rights reserved.

Investigation on electromechanical properties of a muscle-like linear actuator fabricated by bi-film ionic polymer metal composites

NASA Astrophysics Data System (ADS)

Sun, Zhuangzhi; Zhao, Gang; Qiao, Dongpan; Song, Wenlong

2017-12-01

Artificial muscles have attracted great attention for their potentials in intelligent robots, biomimetic devices, and micro-electromechanical system. However, there are many performance bottlenecks restricting the development of artificial muscles in engineering applications, e.g., the little blocking force and short working life. Focused on the larger requirements of the output force and the lack characteristics of the linear motion, an innovative muscle-like linear actuator based on two segmented IPMC strips was developed to imitate linear motion of artificial muscles. The structures of the segmented IPMC strip of muscle-like linear actuator were developed and the established mathematical model was to determine the appropriate segmented proportion as 1:2:1. The muscle-like linear actuator with two segmented IPMC strips assemble by two supporting link blocks was manufactured for the study of electromechanical properties. Electromechanical properties of muscle-like linear actuator under the different technological factors were obtained to experiment, and the corresponding changing rules of muscle-like linear actuators were presented to research. Results showed that factors of redistributed resistance and surface strain on both end-sides were two main reasons affecting the emergence of different electromechanical properties of muscle-like linear actuators.

Assessment of Advanced Logistics Delivery System (ALDS) Launch Systems Concepts

DTIC Science & Technology

2004-10-01

highest force vs. rotor weight required, allows much higher magnetic field generation than the linear induction or linear permanent magnet motors , and...provides the highest force vs. rotor weight required, allows much higher magnetic generation than the linear induction or linear permanent magnet motors , and

Solving a mixture of many random linear equations by tensor decomposition and alternating minimization.

DOT National Transportation Integrated Search

2016-09-01

We consider the problem of solving mixed random linear equations with k components. This is the noiseless setting of mixed linear regression. The goal is to estimate multiple linear models from mixed samples in the case where the labels (which sample...

Unified Framework for Deriving Simultaneous Equation Algorithms for Water Distribution Networks

EPA Science Inventory

The known formulations for steady state hydraulics within looped water distribution networks are re-derived in terms of linear and non-linear transformations of the original set of partly linear and partly non-linear equations that express conservation of mass and energy. All of ...

Linear quadratic optimization for positive LTI system

NASA Astrophysics Data System (ADS)

Muhafzan, Yenti, Syafrida Wirma; Zulakmal

2017-05-01

Nowaday the linear quadratic optimization subject to positive linear time invariant (LTI) system constitute an interesting study considering it can become a mathematical model of variety of real problem whose variables have to nonnegative and trajectories generated by these variables must be nonnegative. In this paper we propose a method to generate an optimal control of linear quadratic optimization subject to positive linear time invariant (LTI) system. A sufficient condition that guarantee the existence of such optimal control is discussed.

Effects of Stochastic Traffic Flow Model on Expected System Performance

DTIC Science & Technology

2012-12-01

NSWC-PCD has made considerable improvements to their pedestrian flow modeling . In addition to the linear paths, the 2011 version now includes...using stochastic paths. 2.2 Linear Paths vs. Stochastic Paths 2.2.1 Linear Paths and Direct Maximum Pd Calculation Modeling pedestrian traffic flow...as a stochastic process begins with the linear path model . Let the detec- tion area be R x C voxels. This creates C 2 total linear paths, path(Cs

Isotherm investigation for the sorption of fluoride onto Bio-F: comparison of linear and non-linear regression method

NASA Astrophysics Data System (ADS)

Yadav, Manish; Singh, Nitin Kumar

2017-12-01

A comparison of the linear and non-linear regression method in selecting the optimum isotherm among three most commonly used adsorption isotherms (Langmuir, Freundlich, and Redlich-Peterson) was made to the experimental data of fluoride (F) sorption onto Bio-F at a solution temperature of 30 ± 1 °C. The coefficient of correlation (r2) was used to select the best theoretical isotherm among the investigated ones. A total of four Langmuir linear equations were discussed and out of which linear form of most popular Langmuir-1 and Langmuir-2 showed the higher coefficient of determination (0.976 and 0.989) as compared to other Langmuir linear equations. Freundlich and Redlich-Peterson isotherms showed a better fit to the experimental data in linear least-square method, while in non-linear method Redlich-Peterson isotherm equations showed the best fit to the tested data set. The present study showed that the non-linear method could be a better way to obtain the isotherm parameters and represent the most suitable isotherm. Redlich-Peterson isotherm was found to be the best representative (r2 = 0.999) for this sorption system. It is also observed that the values of β are not close to unity, which means the isotherms are approaching the Freundlich but not the Langmuir isotherm.

Technological pedagogical content knowledge of junior high school mathematics teachers in teaching linear equation

NASA Astrophysics Data System (ADS)

Wati, S.; Fitriana, L.; Mardiyana

2018-04-01

Linear equation is one of the topics in mathematics that are considered difficult. Student difficulties of understanding linear equation can be caused by lack of understanding this concept and the way of teachers teach. TPACK is a way to understand the complex relationships between teaching and content taught through the use of specific teaching approaches and supported by the right technology tools. This study aims to identify TPACK of junior high school mathematics teachers in teaching linear equation. The method used in the study was descriptive. In the first phase, a survey using a questionnaire was carried out on 45 junior high school mathematics teachers in teaching linear equation. While in the second phase, the interview involved three teachers. The analysis of data used were quantitative and qualitative technique. The result PCK revealed teachers emphasized developing procedural and conceptual knowledge through reliance on traditional in teaching linear equation. The result of TPK revealed teachers’ lower capacity to deal with the general information and communications technologies goals across the curriculum in teaching linear equation. The result indicated that PowerPoint constitutes TCK modal technological capability in teaching linear equation. The result of TPACK seems to suggest a low standard in teachers’ technological skills across a variety of mathematics education goals in teaching linear equation. This means that the ability of teachers’ TPACK in teaching linear equation still needs to be improved.

A Linearized Prognostic Cloud Scheme in NASAs Goddard Earth Observing System Data Assimilation Tools

NASA Technical Reports Server (NTRS)

Holdaway, Daniel; Errico, Ronald M.; Gelaro, Ronald; Kim, Jong G.; Mahajan, Rahul

2015-01-01

A linearized prognostic cloud scheme has been developed to accompany the linearized convection scheme recently implemented in NASA's Goddard Earth Observing System data assimilation tools. The linearization, developed from the nonlinear cloud scheme, treats cloud variables prognostically so they are subject to linearized advection, diffusion, generation, and evaporation. Four linearized cloud variables are modeled, the ice and water phases of clouds generated by large-scale condensation and, separately, by detraining convection. For each species the scheme models their sources, sublimation, evaporation, and autoconversion. Large-scale, anvil and convective species of precipitation are modeled and evaporated. The cloud scheme exhibits linearity and realistic perturbation growth, except around the generation of clouds through large-scale condensation. Discontinuities and steep gradients are widely used here and severe problems occur in the calculation of cloud fraction. For data assimilation applications this poor behavior is controlled by replacing this part of the scheme with a perturbation model. For observation impacts, where efficiency is less of a concern, a filtering is developed that examines the Jacobian. The replacement scheme is only invoked if Jacobian elements or eigenvalues violate a series of tuned constants. The linearized prognostic cloud scheme is tested by comparing the linear and nonlinear perturbation trajectories for 6-, 12-, and 24-h forecast times. The tangent linear model performs well and perturbations of clouds are well captured for the lead times of interest.

Mixed linear-non-linear inversion of crustal deformation data: Bayesian inference of model, weighting and regularization parameters

NASA Astrophysics Data System (ADS)

Fukuda, Jun'ichi; Johnson, Kaj M.

2010-06-01

We present a unified theoretical framework and solution method for probabilistic, Bayesian inversions of crustal deformation data. The inversions involve multiple data sets with unknown relative weights, model parameters that are related linearly or non-linearly through theoretic models to observations, prior information on model parameters and regularization priors to stabilize underdetermined problems. To efficiently handle non-linear inversions in which some of the model parameters are linearly related to the observations, this method combines both analytical least-squares solutions and a Monte Carlo sampling technique. In this method, model parameters that are linearly and non-linearly related to observations, relative weights of multiple data sets and relative weights of prior information and regularization priors are determined in a unified Bayesian framework. In this paper, we define the mixed linear-non-linear inverse problem, outline the theoretical basis for the method, provide a step-by-step algorithm for the inversion, validate the inversion method using synthetic data and apply the method to two real data sets. We apply the method to inversions of multiple geodetic data sets with unknown relative data weights for interseismic fault slip and locking depth. We also apply the method to the problem of estimating the spatial distribution of coseismic slip on faults with unknown fault geometry, relative data weights and smoothing regularization weight.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Jian; Guo, Pan; University of Chinese Academy of Sciences, Beijing 100049

Using molecular dynamics simulations, we show a fine linear relationship between surface energies and microscopic Lennard-Jones parameters of super-hydrophilic surfaces. The linear slope of the super-hydrophilic surfaces is consistent with the linear slope of the super-hydrophobic, hydrophobic, and hydrophilic surfaces where stable water droplets can stand, indicating that there is a universal linear behavior of the surface energies with the water-surface van der Waals interaction that extends from the super-hydrophobic to super-hydrophilic surfaces. Moreover, we find that the linear relationship exists for various substrate types, and the linear slopes of these different types of substrates are dependent on the surfacemore » atom density, i.e., higher surface atom densities correspond to larger linear slopes. These results enrich our understanding of water behavior on solid surfaces, especially the water wetting behaviors on uncharged super-hydrophilic metal surfaces.« less

Ultrasonic Linear Motor with Two Independent Vibrations

NASA Astrophysics Data System (ADS)

Muneishi, Takeshi; Tomikawa, Yoshiro

2004-09-01

We propose a new structure of an ultrasonic linear motor in order to solve the problems of high-power ultrasonic linear motors that drive the XY-stage for electron beam equipment and to expand the application fields of the motor. We pay special attention to the following three points: (1) the vibration in two directions of the ultrasonic linear motor should not influence mutually each other, (2) the vibration in two directions should be divided into the stage traveling direction and the pressing direction of the ultrasonic linear motor, and (3) the rigidity of the stage traveling direction of the ultrasonic linear motor should be increased. As a result, the supporting method of ultrasonic linear motors is simplified. The efficiency of the motor is improved and temperature rise is reduced. The stage position drift is also improved.

On the modelling of linear-assisted DC-DC voltage regulators for photovoltaic solar energy systems

NASA Astrophysics Data System (ADS)

Martínez-García, Herminio; García-Vílchez, Encarna

2017-11-01

This paper shows the modelling of linear-assisted or hybrid (linear & switching) DC/DC voltage regulators. In this kind of regulators, an auxiliary linear regulator is used, which objective is to cancel the ripple at the output voltage and provide fast responses for load variations. On the other hand, a switching DC/DC converter, connected in parallel with the linear regulator, allows to supply almost the whole output current demanded by the load. The objective of this topology is to take advantage of the suitable regulation characteristics that series linear voltage regulators have, but almost achieving the high efficiency that switching DC/DC converters provide. Linear-assisted DC/DC regulators are feedback systems with potential instability. Therefore, their modelling is mandatory in order to obtain design guidelines and assure stability of the implemented power supply system.

Sparse 4D TomoSAR imaging in the presence of non-linear deformation

NASA Astrophysics Data System (ADS)

Khwaja, Ahmed Shaharyar; ćetin, Müjdat

2018-04-01

In this paper, we present a sparse four-dimensional tomographic synthetic aperture radar (4D TomoSAR) imaging scheme that can estimate elevation and linear as well as non-linear seasonal deformation rates of scatterers using the interferometric phase. Unlike existing sparse processing techniques that use fixed dictionaries based on a linear deformation model, we use a variable dictionary for the non-linear deformation in the form of seasonal sinusoidal deformation, in addition to the fixed dictionary for the linear deformation. We estimate the amplitude of the sinusoidal deformation using an optimization method and create the variable dictionary using the estimated amplitude. We show preliminary results using simulated data that demonstrate the soundness of our proposed technique for sparse 4D TomoSAR imaging in the presence of non-linear deformation.

Linear summation of outputs in a balanced network model of motor cortex

PubMed Central

Capaday, Charles; van Vreeswijk, Carl

2015-01-01

Given the non-linearities of the neural circuitry's elements, we would expect cortical circuits to respond non-linearly when activated. Surprisingly, when two points in the motor cortex are activated simultaneously, the EMG responses are the linear sum of the responses evoked by each of the points activated separately. Additionally, the corticospinal transfer function is close to linear, implying that the synaptic interactions in motor cortex must be effectively linear. To account for this, here we develop a model of motor cortex composed of multiple interconnected points, each comprised of reciprocally connected excitatory and inhibitory neurons. We show how non-linearities in neuronal transfer functions are eschewed by strong synaptic interactions within each point. Consequently, the simultaneous activation of multiple points results in a linear summation of their respective outputs. We also consider the effects of reduction of inhibition at a cortical point when one or more surrounding points are active. The network response in this condition is linear over an approximately two- to three-fold decrease of inhibitory feedback strength. This result supports the idea that focal disinhibition allows linear coupling of motor cortical points to generate movement related muscle activation patterns; albeit with a limitation on gain control. The model also explains why neural activity does not spread as far out as the axonal connectivity allows, whilst also explaining why distant cortical points can be, nonetheless, functionally coupled by focal disinhibition. Finally, we discuss the advantages that linear interactions at the cortical level afford to motor command synthesis. PMID:26097452

Investigating Integer Restrictions in Linear Programming

ERIC Educational Resources Information Center

Edwards, Thomas G.; Chelst, Kenneth R.; Principato, Angela M.; Wilhelm, Thad L.

2015-01-01

Linear programming (LP) is an application of graphing linear systems that appears in many Algebra 2 textbooks. Although not explicitly mentioned in the Common Core State Standards for Mathematics, linear programming blends seamlessly into modeling with mathematics, the fourth Standard for Mathematical Practice (CCSSI 2010, p. 7). In solving a…

40 CFR 721.10217 - Branched and linear alcohols (generic).

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Branched and linear alcohols (generic... Specific Chemical Substances § 721.10217 Branched and linear alcohols (generic). (a) Chemical substance and... linear alcohols (PMN P-09-426) is subject to reporting under this section for the significant new uses...

Piecewise Linear-Linear Latent Growth Mixture Models with Unknown Knots

ERIC Educational Resources Information Center

Kohli, Nidhi; Harring, Jeffrey R.; Hancock, Gregory R.

2013-01-01

Latent growth curve models with piecewise functions are flexible and useful analytic models for investigating individual behaviors that exhibit distinct phases of development in observed variables. As an extension of this framework, this study considers a piecewise linear-linear latent growth mixture model (LGMM) for describing segmented change of…

Cosmological N -body simulations with generic hot dark matter

DOE Office of Scientific and Technical Information (OSTI.GOV)

Brandbyge, Jacob; Hannestad, Steen, E-mail: jacobb@phys.au.dk, E-mail: sth@phys.au.dk

2017-10-01

We have calculated the non-linear effects of generic fermionic and bosonic hot dark matter components in cosmological N -body simulations. For sub-eV masses, the non-linear power spectrum suppression caused by thermal free-streaming resembles the one seen for massive neutrinos, whereas for masses larger than 1 eV, the non-linear relative suppression of power is smaller than in linear theory. We furthermore find that in the non-linear regime, one can map fermionic to bosonic models by performing a simple transformation.

On differential operators generating iterative systems of linear ODEs of maximal symmetry algebra

NASA Astrophysics Data System (ADS)

Ndogmo, J. C.

2017-06-01

Although every iterative scalar linear ordinary differential equation is of maximal symmetry algebra, the situation is different and far more complex for systems of linear ordinary differential equations, and an iterative system of linear equations need not be of maximal symmetry algebra. We illustrate these facts by examples and derive families of vector differential operators whose iterations are all linear systems of equations of maximal symmetry algebra. Some consequences of these results are also discussed.

Cosmological N-body simulations with generic hot dark matter

NASA Astrophysics Data System (ADS)

Brandbyge, Jacob; Hannestad, Steen

2017-10-01

We have calculated the non-linear effects of generic fermionic and bosonic hot dark matter components in cosmological N-body simulations. For sub-eV masses, the non-linear power spectrum suppression caused by thermal free-streaming resembles the one seen for massive neutrinos, whereas for masses larger than 1 eV, the non-linear relative suppression of power is smaller than in linear theory. We furthermore find that in the non-linear regime, one can map fermionic to bosonic models by performing a simple transformation.

Non-linear vibrations of sandwich viscoelastic shells

NASA Astrophysics Data System (ADS)

Benchouaf, Lahcen; Boutyour, El Hassan; Daya, El Mostafa; Potier-Ferry, Michel

2018-04-01

This paper deals with the non-linear vibration of sandwich viscoelastic shell structures. Coupling a harmonic balance method with the Galerkin's procedure, one obtains an amplitude equation depending on two complex coefficients. The latter are determined by solving a classical eigenvalue problem and two linear ones. This permits to get the non-linear frequency and the non-linear loss factor as functions of the displacement amplitude. To validate our approach, these relationships are illustrated in the case of a circular sandwich ring.

Probabilistic quantum cloning of a subset of linearly dependent states

NASA Astrophysics Data System (ADS)

Rui, Pinshu; Zhang, Wen; Liao, Yanlin; Zhang, Ziyun

2018-02-01

It is well known that a quantum state, secretly chosen from a certain set, can be probabilistically cloned with positive cloning efficiencies if and only if all the states in the set are linearly independent. In this paper, we focus on probabilistic quantum cloning of a subset of linearly dependent states. We show that a linearly-independent subset of linearly-dependent quantum states {| Ψ 1⟩,| Ψ 2⟩,…,| Ψ n ⟩} can be probabilistically cloned if and only if any state in the subset cannot be expressed as a linear superposition of the other states in the set {| Ψ 1⟩,| Ψ 2⟩,…,| Ψ n ⟩}. The optimal cloning efficiencies are also investigated.

Asymptotic Stability of Interconnected Passive Non-Linear Systems

NASA Technical Reports Server (NTRS)

Isidori, A.; Joshi, S. M.; Kelkar, A. G.

1999-01-01

This paper addresses the problem of stabilization of a class of internally passive non-linear time-invariant dynamic systems. A class of non-linear marginally strictly passive (MSP) systems is defined, which is less restrictive than input-strictly passive systems. It is shown that the interconnection of a non-linear passive system and a non-linear MSP system is globally asymptotically stable. The result generalizes and weakens the conditions of the passivity theorem, which requires one of the systems to be input-strictly passive. In the case of linear time-invariant systems, it is shown that the MSP property is equivalent to the marginally strictly positive real (MSPR) property, which is much simpler to check.

Neural processing of gravity information

NASA Technical Reports Server (NTRS)

Schor, Robert H.

1992-01-01

The goal of this project was to use the linear acceleration capabilities of the NASA Vestibular Research Facility (VRF) at Ames Research Center to directly examine encoding of linear accelerations in the vestibular system of the cat. Most previous studies, including my own, have utilized tilt stimuli, which at very low frequencies (e.g., 'static tilt') can be considered a reasonably pure linear acceleration (e.g., 'down'); however, higher frequencies of tilt, necessary for understanding the dynamic processing of linear acceleration information, necessarily involves rotations which can stimulate the semicircular canals. The VRF, particularly the Long Linear Sled, has promise to provide controlled pure linear accelerations at a variety of stimulus frequencies, with no confounding angular motion.

The Development of a Dual-Warhead Impact System for Dynamic Linearity Measurement of a High-g Micro-Electro-Mechanical-Systems (MEMS) Accelerometer

PubMed Central

Shi, Yunbo; Yang, Zhicai; Ma, Zongmin; Cao, Huiliang; Kou, Zhiwei; Zhi, Dan; Chen, Yanxiang; Feng, Hengzhen; Liu, Jun

2016-01-01

Despite its extreme significance, dynamic linearity measurement for high-g accelerometers has not been discussed experimentally in previous research. In this study, we developed a novel method using a dual-warhead Hopkinson bar to measure the dynamic linearity of a high-g acceleration sensor with a laser interference impact experiment. First, we theoretically determined that dynamic linearity is a performance indicator that can be used to assess the quality merits of high-g accelerometers and is the basis of the frequency response. We also found that the dynamic linearity of the dual-warhead Hopkinson bar without an accelerometer is 2.5% experimentally. Further, we verify that dynamic linearity of the accelerometer is 3.88% after calibrating the Hopkinson bar with the accelerometer. The results confirm the reliability and feasibility of measuring dynamic linearity for high-g accelerometers using this method. PMID:27338383

Conjugate gradient type methods for linear systems with complex symmetric coefficient matrices

NASA Technical Reports Server (NTRS)

Freund, Roland

1989-01-01

We consider conjugate gradient type methods for the solution of large sparse linear system Ax equals b with complex symmetric coefficient matrices A equals A(T). Such linear systems arise in important applications, such as the numerical solution of the complex Helmholtz equation. Furthermore, most complex non-Hermitian linear systems which occur in practice are actually complex symmetric. We investigate conjugate gradient type iterations which are based on a variant of the nonsymmetric Lanczos algorithm for complex symmetric matrices. We propose a new approach with iterates defined by a quasi-minimal residual property. The resulting algorithm presents several advantages over the standard biconjugate gradient method. We also include some remarks on the obvious approach to general complex linear systems by solving equivalent real linear systems for the real and imaginary parts of x. Finally, numerical experiments for linear systems arising from the complex Helmholtz equation are reported.

Feedback linearizing control of a MIMO power system

NASA Astrophysics Data System (ADS)

Ilyes, Laszlo

Prior research has demonstrated that either the mechanical or electrical subsystem of a synchronous electric generator may be controlled using single-input single-output (SISO) nonlinear feedback linearization. This research suggests a new approach which applies nonlinear feedback linearization to a multi-input multi-output (MIMO) model of the synchronous electric generator connected to an infinite bus load model. In this way, the electrical and mechanical subsystems may be linearized and simultaneously decoupled through the introduction of a pair of auxiliary inputs. This allows well known, linear, SISO control methods to be effectively applied to the resulting systems. The derivation of the feedback linearizing control law is presented in detail, including a discussion on the use of symbolic math processing as a development tool. The linearizing and decoupling properties of the control law are validated through simulation. And finally, the robustness of the control law is demonstrated.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Suhara, Tadahiro; Kanada-En'yo, Yoshiko

We investigate the linear-chain structures in highly excited states of {sup 14}C using a generalized molecular-orbital model, by which we incorporate an asymmetric configuration of three {alpha} clusters in the linear-chain states. By applying this model to the {sup 14}C system, we study the {sup 10}Be+{alpha} correlation in the linear-chain state of {sup 14}C. To clarify the origin of the {sup 10}Be+{alpha} correlation in the {sup 14}C linear-chain state, we analyze linear 3 {alpha} and 3{alpha} + n systems in a similar way. We find that a linear 3{alpha} system prefers the asymmetric 2{alpha} + {alpha} configuration, whose origin ismore » the many-body correlation incorporated by the parity projection. This configuration causes an asymmetric mean field for two valence neutrons, which induces the concentration of valence neutron wave functions around the correlating 2{alpha}. A linear-chain structure of {sup 16}C is also discussed.« less

Analysis of the faster-than-Nyquist optimal linear multicarrier system

NASA Astrophysics Data System (ADS)

Marquet, Alexandre; Siclet, Cyrille; Roque, Damien

2017-02-01

Faster-than-Nyquist signalization enables a better spectral efficiency at the expense of an increased computational complexity. Regarding multicarrier communications, previous work mainly relied on the study of non-linear systems exploiting coding and/or equalization techniques, with no particular optimization of the linear part of the system. In this article, we analyze the performance of the optimal linear multicarrier system when used together with non-linear receiving structures (iterative decoding and direct feedback equalization), or in a standalone fashion. We also investigate the limits of the normality assumption of the interference, used for implementing such non-linear systems. The use of this optimal linear system leads to a closed-form expression of the bit-error probability that can be used to predict the performance and help the design of coded systems. Our work also highlights the great performance/complexity trade-off offered by decision feedback equalization in a faster-than-Nyquist context. xml:lang="fr"

Employment of CB models for non-linear dynamic analysis

NASA Technical Reports Server (NTRS)

Klein, M. R. M.; Deloo, P.; Fournier-Sicre, A.

1990-01-01

The non-linear dynamic analysis of large structures is always very time, effort and CPU consuming. Whenever possible the reduction of the size of the mathematical model involved is of main importance to speed up the computational procedures. Such reduction can be performed for the part of the structure which perform linearly. Most of the time, the classical Guyan reduction process is used. For non-linear dynamic process where the non-linearity is present at interfaces between different structures, Craig-Bampton models can provide a very rich information, and allow easy selection of the relevant modes with respect to the phenomenon driving the non-linearity. The paper presents the employment of Craig-Bampton models combined with Newmark direct integration for solving non-linear friction problems appearing at the interface between the Hubble Space Telescope and its solar arrays during in-orbit maneuvers. Theory, implementation in the FEM code ASKA, and practical results are shown.

Disorder-dominated linear magnetoresistance in topological insulator Bi2Se3 thin films

NASA Astrophysics Data System (ADS)

Wang, Wen Jie; Gao, Kuang Hong; Li, Qiu Lin; Li, Zhi-Qing

2017-12-01

The linear magnetoresistance (MR) effect is an interesting topic due to its potential applications. In topological insulator Bi2Se3, this effect has been reported to be dominated by the carrier mobility (μ) and hence has a classical origin. Here, we study the magnetotransport properties of Bi2Se3 thin films and observe the linear MR effect, which cannot be attributed to the quantum model. Unexpectedly, the linear MR does not show the linear dependence on μ, in conflict with the reported results. However, we find that the observed linear MR is dominated by the inverse disorder parameter 1 /kFl , where kF and l are the Fermi wave vector and the mean free path, respectively. This suggests that its origin is also classical and that no μ-dominated linear MR effect is observed which may be due to the very small μ values in our samples.

Competitive inhibition can linearize dose-response and generate a linear rectifier

PubMed Central

Savir, Yonatan; Tu, Benjamin P.; Springer, Michael

2015-01-01

Summary Many biological responses require a dynamic range that is larger than standard bi-molecular interactions allow, yet the also ability to remain off at low input. Here we mathematically show that an enzyme reaction system involving a combination of competitive inhibition, conservation of the total level of substrate and inhibitor, and positive feedback can behave like a linear rectifier—that is, a network motif with an input-output relationship that is linearly sensitive to substrate above a threshold but unresponsive below the threshold. We propose that the evolutionarily conserved yeast SAGA histone acetylation complex may possess the proper physiological response characteristics and molecular interactions needed to perform as a linear rectifier, and we suggest potential experiments to test this hypothesis. One implication of this work is that linear responses and linear rectifiers might be easier to evolve or synthetically construct than is currently appreciated. PMID:26495436

How linear response shaped models of neural circuits and the quest for alternatives.

PubMed

Herfurth, Tim; Tchumatchenko, Tatjana

2017-10-01

In the past decades, many mathematical approaches to solve complex nonlinear systems in physics have been successfully applied to neuroscience. One of these tools is the concept of linear response functions. However, phenomena observed in the brain emerge from fundamentally nonlinear interactions and feedback loops rather than from a composition of linear filters. Here, we review the successes achieved by applying the linear response formalism to topics, such as rhythm generation and synchrony and by incorporating it into models that combine linear and nonlinear transformations. We also discuss the challenges encountered in the linear response applications and argue that new theoretical concepts are needed to tackle feedback loops and non-equilibrium dynamics which are experimentally observed in neural networks but are outside of the validity regime of the linear response formalism. Copyright © 2017 Elsevier Ltd. All rights reserved.

Latent log-linear models for handwritten digit classification.

PubMed

Deselaers, Thomas; Gass, Tobias; Heigold, Georg; Ney, Hermann

2012-06-01

We present latent log-linear models, an extension of log-linear models incorporating latent variables, and we propose two applications thereof: log-linear mixture models and image deformation-aware log-linear models. The resulting models are fully discriminative, can be trained efficiently, and the model complexity can be controlled. Log-linear mixture models offer additional flexibility within the log-linear modeling framework. Unlike previous approaches, the image deformation-aware model directly considers image deformations and allows for a discriminative training of the deformation parameters. Both are trained using alternating optimization. For certain variants, convergence to a stationary point is guaranteed and, in practice, even variants without this guarantee converge and find models that perform well. We tune the methods on the USPS data set and evaluate on the MNIST data set, demonstrating the generalization capabilities of our proposed models. Our models, although using significantly fewer parameters, are able to obtain competitive results with models proposed in the literature.

Competitive inhibition can linearize dose-response and generate a linear rectifier.

PubMed

Savir, Yonatan; Tu, Benjamin P; Springer, Michael

2015-09-23

Many biological responses require a dynamic range that is larger than standard bi-molecular interactions allow, yet the also ability to remain off at low input. Here we mathematically show that an enzyme reaction system involving a combination of competitive inhibition, conservation of the total level of substrate and inhibitor, and positive feedback can behave like a linear rectifier-that is, a network motif with an input-output relationship that is linearly sensitive to substrate above a threshold but unresponsive below the threshold. We propose that the evolutionarily conserved yeast SAGA histone acetylation complex may possess the proper physiological response characteristics and molecular interactions needed to perform as a linear rectifier, and we suggest potential experiments to test this hypothesis. One implication of this work is that linear responses and linear rectifiers might be easier to evolve or synthetically construct than is currently appreciated.

40 CFR 1066.220 - Linearity verification for chassis dynamometer systems.

Code of Federal Regulations, 2014 CFR

2014-07-01

... dynamometer speed and torque at least as frequently as indicated in Table 1 of § 1066.215. The intent of... linear regression and the linearity criteria specified in Table 1 of this section. (b) Performance requirements. If a measurement system does not meet the applicable linearity criteria in Table 1 of this...

Improvements In Ball-Screw Linear Actuators

NASA Technical Reports Server (NTRS)

Iskenderian, Theodore; Joffe, Benjamin; Summers, Robert

1996-01-01

Report describes modifications of design of type of ball-screw linear actuator driven by dc motor, with linear-displacement feedback via linear variable-differential transformer (LVDT). Actuators used to position spacecraft engines to direct thrust. Modifications directed toward ensuring reliable and predictable operation during planned 12-year cruise and interval of hard use at end of cruise.

A Learning Progression Should Address Regression: Insights from Developing Non-Linear Reasoning in Ecology

ERIC Educational Resources Information Center

Hovardas, Tasos

2016-01-01

Although ecological systems at varying scales involve non-linear interactions, learners insist thinking in a linear fashion when they deal with ecological phenomena. The overall objective of the present contribution was to propose a hypothetical learning progression for developing non-linear reasoning in prey-predator systems and to provide…

Comparison between Linear and Nonlinear Regression in a Laboratory Heat Transfer Experiment

ERIC Educational Resources Information Center

Gonçalves, Carine Messias; Schwaab, Marcio; Pinto, José Carlos

2013-01-01

In order to interpret laboratory experimental data, undergraduate students are used to perform linear regression through linearized versions of nonlinear models. However, the use of linearized models can lead to statistically biased parameter estimates. Even so, it is not an easy task to introduce nonlinear regression and show for the students…

Unpacking the Complexity of Linear Equations from a Cognitive Load Theory Perspective

ERIC Educational Resources Information Center

Ngu, Bing Hiong; Phan, Huy P.

2016-01-01

The degree of element interactivity determines the complexity and therefore the intrinsic cognitive load of linear equations. The unpacking of linear equations at the level of operational and relational lines allows the classification of linear equations in a hierarchical level of complexity. Mapping similar operational and relational lines across…

State-variable analysis of non-linear circuits with a desk computer

NASA Technical Reports Server (NTRS)

Cohen, E.

1981-01-01

State variable analysis was used to analyze the transient performance of non-linear circuits on a desk top computer. The non-linearities considered were not restricted to any circuit element. All that is required for analysis is the relationship defining each non-linearity be known in terms of points on a curve.

Stability of Linear Equations--Algebraic Approach

ERIC Educational Resources Information Center

Cherif, Chokri; Goldstein, Avraham; Prado, Lucio M. G.

2012-01-01

This article could be of interest to teachers of applied mathematics as well as to people who are interested in applications of linear algebra. We give a comprehensive study of linear systems from an application point of view. Specifically, we give an overview of linear systems and problems that can occur with the computed solution when the…

Application of Hierarchical Linear Models/Linear Mixed-Effects Models in School Effectiveness Research

ERIC Educational Resources Information Center

Ker, H. W.

2014-01-01

Multilevel data are very common in educational research. Hierarchical linear models/linear mixed-effects models (HLMs/LMEs) are often utilized to analyze multilevel data nowadays. This paper discusses the problems of utilizing ordinary regressions for modeling multilevel educational data, compare the data analytic results from three regression…

The Next Linear Collider Program

Science.gov Websites

text only International Study Group (ISG) Meetings NLC Home Page NLC Technical SLAC Eleventh Linear Collider International Study Group at KEK, December 16 - 19, 2003 Tenth (X) Linear Collider International Study Group at SLAC, June, 2003 Nineth Linear Collider ,International Study Group at KEK, December 10-13

Introducing Linear Functions: An Alternative Statistical Approach

ERIC Educational Resources Information Center

Nolan, Caroline; Herbert, Sandra

2015-01-01

The introduction of linear functions is the turning point where many students decide if mathematics is useful or not. This means the role of parameters and variables in linear functions could be considered to be "threshold concepts". There is recognition that linear functions can be taught in context through the exploration of linear…

ORACLS: A system for linear-quadratic-Gaussian control law design

NASA Technical Reports Server (NTRS)

Armstrong, E. S.

1978-01-01

A modern control theory design package (ORACLS) for constructing controllers and optimal filters for systems modeled by linear time-invariant differential or difference equations is described. Numerical linear-algebra procedures are used to implement the linear-quadratic-Gaussian (LQG) methodology of modern control theory. Algorithms are included for computing eigensystems of real matrices, the relative stability of a matrix, factored forms for nonnegative definite matrices, the solutions and least squares approximations to the solutions of certain linear matrix algebraic equations, the controllability properties of a linear time-invariant system, and the steady state covariance matrix of an open-loop stable system forced by white noise. Subroutines are provided for solving both the continuous and discrete optimal linear regulator problems with noise free measurements and the sampled-data optimal linear regulator problem. For measurement noise, duality theory and the optimal regulator algorithms are used to solve the continuous and discrete Kalman-Bucy filter problems. Subroutines are also included which give control laws causing the output of a system to track the output of a prescribed model.

Linear and non-linear regression analysis for the sorption kinetics of methylene blue onto activated carbon.

PubMed

Kumar, K Vasanth

2006-10-11

Batch kinetic experiments were carried out for the sorption of methylene blue onto activated carbon. The experimental kinetics were fitted to the pseudo first-order and pseudo second-order kinetics by linear and a non-linear method. The five different types of Ho pseudo second-order expression have been discussed. A comparison of linear least-squares method and a trial and error non-linear method of estimating the pseudo second-order rate kinetic parameters were examined. The sorption process was found to follow a both pseudo first-order kinetic and pseudo second-order kinetic model. Present investigation showed that it is inappropriate to use a type 1 and type pseudo second-order expressions as proposed by Ho and Blanachard et al. respectively for predicting the kinetic rate constants and the initial sorption rate for the studied system. Three correct possible alternate linear expressions (type 2 to type 4) to better predict the initial sorption rate and kinetic rate constants for the studied system (methylene blue/activated carbon) was proposed. Linear method was found to check only the hypothesis instead of verifying the kinetic model. Non-linear regression method was found to be the more appropriate method to determine the rate kinetic parameters.

Expanding the occupational health methodology: A concatenated artificial neural network approach to model the burnout process in Chinese nurses.

PubMed

Ladstätter, Felix; Garrosa, Eva; Moreno-Jiménez, Bernardo; Ponsoda, Vicente; Reales Aviles, José Manuel; Dai, Junming

2016-01-01

Artificial neural networks are sophisticated modelling and prediction tools capable of extracting complex, non-linear relationships between predictor (input) and predicted (output) variables. This study explores this capacity by modelling non-linearities in the hardiness-modulated burnout process with a neural network. Specifically, two multi-layer feed-forward artificial neural networks are concatenated in an attempt to model the composite non-linear burnout process. Sensitivity analysis, a Monte Carlo-based global simulation technique, is then utilised to examine the first-order effects of the predictor variables on the burnout sub-dimensions and consequences. Results show that (1) this concatenated artificial neural network approach is feasible to model the burnout process, (2) sensitivity analysis is a prolific method to study the relative importance of predictor variables and (3) the relationships among variables involved in the development of burnout and its consequences are to different degrees non-linear. Many relationships among variables (e.g., stressors and strains) are not linear, yet researchers use linear methods such as Pearson correlation or linear regression to analyse these relationships. Artificial neural network analysis is an innovative method to analyse non-linear relationships and in combination with sensitivity analysis superior to linear methods.

Linearization instability for generic gravity in AdS spacetime

NASA Astrophysics Data System (ADS)

Altas, Emel; Tekin, Bayram

2018-01-01

In general relativity, perturbation theory about a background solution fails if the background spacetime has a Killing symmetry and a compact spacelike Cauchy surface. This failure, dubbed as linearization instability, shows itself as non-integrability of the perturbative infinitesimal deformation to a finite deformation of the background. Namely, the linearized field equations have spurious solutions which cannot be obtained from the linearization of exact solutions. In practice, one can show the failure of the linear perturbation theory by showing that a certain quadratic (integral) constraint on the linearized solutions is not satisfied. For non-compact Cauchy surfaces, the situation is different and for example, Minkowski space having a non-compact Cauchy surface, is linearization stable. Here we study, the linearization instability in generic metric theories of gravity where Einstein's theory is modified with additional curvature terms. We show that, unlike the case of general relativity, for modified theories even in the non-compact Cauchy surface cases, there are some theories which show linearization instability about their anti-de Sitter backgrounds. Recent D dimensional critical and three dimensional chiral gravity theories are two such examples. This observation sheds light on the paradoxical behavior of vanishing conserved charges (mass, angular momenta) for non-vacuum solutions, such as black holes, in these theories.

Power Amplifier Linearizer for High Frequency Medical Ultrasound Applications

PubMed Central

Choi, Hojong; Jung, Hayong; Shung, K. Kirk

2015-01-01

Power amplifiers (PAs) are used to produce high-voltage excitation signals to drive ultrasonic transducers. A larger dynamic range of linear PAs allows higher contrast resolution, a highly desirable characteristic in ultrasonic imaging. The linearity of PAs can be improved by reducing the nonlinear harmonic distortion components of high-voltage output signals. In this paper, a linearizer circuit is proposed to reduce output signal harmonics when working in conjunction with a PA. The PA performance with and without the linearizer was measured by comparing the output power 1-dB compression point (OP1dB), and the second- and third-order harmonic distortions (HD2 and HD3, respectively). The results show that the PA with the linearizer circuit had higher OP1dB (31.7 dB) and lower HD2 (−61.0 dB) and HD3 (−42.7 dB) compared to those of the PA alone (OP1dB (27.1 dB), HD2 (−38.2 dB), and HD3 (−36.8 dB)) at 140 MHz. A pulse-echo measurement was also performed to further evaluate the capability of the linearizer circuit. The HD2 of the echo signal received by the transducer using a PA with the linearizer (−24.8 dB) was lower than that obtained for the PA alone (−16.6 dB). The linearizer circuit is capable of improving the linearity performance of PA by lowering harmonic distortions. PMID:26622209

Map showing the association of linear features with metallic mines and prospects in the Butte 1 degree by 2 degrees Quadrangle, Montana

USGS Publications Warehouse

Rowan, L.C.; Trautwein, C.M.; Purdy, T.L.

1990-01-01

This study was undertaken as part of the Conterminous U.S. Mineral Assessment Program (CUSMAP). The purpose of the study was to map linear features on Landsat Multispectral Scanner (MSS) images and a proprietary side-looking airborne radar (SLAR) image mosaic and to determine the spatial relationship between these linear features and the locations of metallic mineral occurrE-nces. The results show a close spatial association of linear features with metallic mineral occurrences in parts of the quadrangle, but in other areas the association is less well defined. Linear features are defined as distinct linear and slightly curvilinear elements mappable on MSS and SLAR images. The features generally represent linear segments of streams, ridges, and terminations of topographic features; however, they may also represent tonal patterns that are related to variations in lithology and vegetation. Most linear features in the Butte quadrangle probably represent underlying structural elements, such as fractures (with and without displacement), dikes, and alignment of fold axes. However, in areas underlain by sedimentary rocks, some of the linear features may reflect bedding traces. This report describes the geologic setting of the Butte quadrangle, the procedures used in mapping and analyzing the linear features, and the results of the study. Relationship of these features to placer and non-metal deposits were not analyzed in this study and are not discussed in this report.

From Spiking Neuron Models to Linear-Nonlinear Models

PubMed Central

Ostojic, Srdjan; Brunel, Nicolas

2011-01-01

Neurons transform time-varying inputs into action potentials emitted stochastically at a time dependent rate. The mapping from current input to output firing rate is often represented with the help of phenomenological models such as the linear-nonlinear (LN) cascade, in which the output firing rate is estimated by applying to the input successively a linear temporal filter and a static non-linear transformation. These simplified models leave out the biophysical details of action potential generation. It is not a priori clear to which extent the input-output mapping of biophysically more realistic, spiking neuron models can be reduced to a simple linear-nonlinear cascade. Here we investigate this question for the leaky integrate-and-fire (LIF), exponential integrate-and-fire (EIF) and conductance-based Wang-Buzsáki models in presence of background synaptic activity. We exploit available analytic results for these models to determine the corresponding linear filter and static non-linearity in a parameter-free form. We show that the obtained functions are identical to the linear filter and static non-linearity determined using standard reverse correlation analysis. We then quantitatively compare the output of the corresponding linear-nonlinear cascade with numerical simulations of spiking neurons, systematically varying the parameters of input signal and background noise. We find that the LN cascade provides accurate estimates of the firing rates of spiking neurons in most of parameter space. For the EIF and Wang-Buzsáki models, we show that the LN cascade can be reduced to a firing rate model, the timescale of which we determine analytically. Finally we introduce an adaptive timescale rate model in which the timescale of the linear filter depends on the instantaneous firing rate. This model leads to highly accurate estimates of instantaneous firing rates. PMID:21283777

Linear time-varying models can reveal non-linear interactions of biomolecular regulatory networks using multiple time-series data.

PubMed

Kim, Jongrae; Bates, Declan G; Postlethwaite, Ian; Heslop-Harrison, Pat; Cho, Kwang-Hyun

2008-05-15

Inherent non-linearities in biomolecular interactions make the identification of network interactions difficult. One of the principal problems is that all methods based on the use of linear time-invariant models will have fundamental limitations in their capability to infer certain non-linear network interactions. Another difficulty is the multiplicity of possible solutions, since, for a given dataset, there may be many different possible networks which generate the same time-series expression profiles. A novel algorithm for the inference of biomolecular interaction networks from temporal expression data is presented. Linear time-varying models, which can represent a much wider class of time-series data than linear time-invariant models, are employed in the algorithm. From time-series expression profiles, the model parameters are identified by solving a non-linear optimization problem. In order to systematically reduce the set of possible solutions for the optimization problem, a filtering process is performed using a phase-portrait analysis with random numerical perturbations. The proposed approach has the advantages of not requiring the system to be in a stable steady state, of using time-series profiles which have been generated by a single experiment, and of allowing non-linear network interactions to be identified. The ability of the proposed algorithm to correctly infer network interactions is illustrated by its application to three examples: a non-linear model for cAMP oscillations in Dictyostelium discoideum, the cell-cycle data for Saccharomyces cerevisiae and a large-scale non-linear model of a group of synchronized Dictyostelium cells. The software used in this article is available from http://sbie.kaist.ac.kr/software

Development of a Linear Stirling Model with Varying Heat Inputs

NASA Technical Reports Server (NTRS)

Regan, Timothy F.; Lewandowski, Edward J.

2007-01-01

The linear model of the Stirling system developed by NASA Glenn Research Center (GRC) has been extended to include a user-specified heat input. Previously developed linear models were limited to the Stirling convertor and electrical load. They represented the thermodynamic cycle with pressure factors that remained constant. The numerical values of the pressure factors were generated by linearizing GRC s non-linear System Dynamic Model (SDM) of the convertor at a chosen operating point. The pressure factors were fixed for that operating point, thus, the model lost accuracy if a transition to a different operating point were simulated. Although the previous linear model was used in developing controllers that manipulated current, voltage, and piston position, it could not be used in the development of control algorithms that regulated hot-end temperature. This basic model was extended to include the thermal dynamics associated with a hot-end temperature that varies over time in response to external changes as well as to changes in the Stirling cycle. The linear model described herein includes not only dynamics of the piston, displacer, gas, and electrical circuit, but also the transient effects of the heater head thermal inertia. The linear version algebraically couples two separate linear dynamic models, one model of the Stirling convertor and one model of the thermal system, through the pressure factors. The thermal system model includes heat flow of heat transfer fluid, insulation loss, and temperature drops from the heat source to the Stirling convertor expansion space. The linear model was compared to a nonlinear model, and performance was very similar. The resulting linear model can be implemented in a variety of computing environments, and is suitable for analysis with classical and state space controls analysis techniques.

From spiking neuron models to linear-nonlinear models.

PubMed

Ostojic, Srdjan; Brunel, Nicolas

2011-01-20

Neurons transform time-varying inputs into action potentials emitted stochastically at a time dependent rate. The mapping from current input to output firing rate is often represented with the help of phenomenological models such as the linear-nonlinear (LN) cascade, in which the output firing rate is estimated by applying to the input successively a linear temporal filter and a static non-linear transformation. These simplified models leave out the biophysical details of action potential generation. It is not a priori clear to which extent the input-output mapping of biophysically more realistic, spiking neuron models can be reduced to a simple linear-nonlinear cascade. Here we investigate this question for the leaky integrate-and-fire (LIF), exponential integrate-and-fire (EIF) and conductance-based Wang-Buzsáki models in presence of background synaptic activity. We exploit available analytic results for these models to determine the corresponding linear filter and static non-linearity in a parameter-free form. We show that the obtained functions are identical to the linear filter and static non-linearity determined using standard reverse correlation analysis. We then quantitatively compare the output of the corresponding linear-nonlinear cascade with numerical simulations of spiking neurons, systematically varying the parameters of input signal and background noise. We find that the LN cascade provides accurate estimates of the firing rates of spiking neurons in most of parameter space. For the EIF and Wang-Buzsáki models, we show that the LN cascade can be reduced to a firing rate model, the timescale of which we determine analytically. Finally we introduce an adaptive timescale rate model in which the timescale of the linear filter depends on the instantaneous firing rate. This model leads to highly accurate estimates of instantaneous firing rates.

Mathematical model for the contribution of individual organs to non-zero y-intercepts in single and multi-compartment linear models of whole-body energy expenditure.

PubMed

Kaiyala, Karl J

2014-01-01

Mathematical models for the dependence of energy expenditure (EE) on body mass and composition are essential tools in metabolic phenotyping. EE scales over broad ranges of body mass as a non-linear allometric function. When considered within restricted ranges of body mass, however, allometric EE curves exhibit 'local linearity.' Indeed, modern EE analysis makes extensive use of linear models. Such models typically involve one or two body mass compartments (e.g., fat free mass and fat mass). Importantly, linear EE models typically involve a non-zero (usually positive) y-intercept term of uncertain origin, a recurring theme in discussions of EE analysis and a source of confounding in traditional ratio-based EE normalization. Emerging linear model approaches quantify whole-body resting EE (REE) in terms of individual organ masses (e.g., liver, kidneys, heart, brain). Proponents of individual organ REE modeling hypothesize that multi-organ linear models may eliminate non-zero y-intercepts. This could have advantages in adjusting REE for body mass and composition. Studies reveal that individual organ REE is an allometric function of total body mass. I exploit first-order Taylor linearization of individual organ REEs to model the manner in which individual organs contribute to whole-body REE and to the non-zero y-intercept in linear REE models. The model predicts that REE analysis at the individual organ-tissue level will not eliminate intercept terms. I demonstrate that the parameters of a linear EE equation can be transformed into the parameters of the underlying 'latent' allometric equation. This permits estimates of the allometric scaling of EE in a diverse variety of physiological states that are not represented in the allometric EE literature but are well represented by published linear EE analyses.

Linear Back-Drive Differentials

NASA Technical Reports Server (NTRS)

Waydo, Peter

2003-01-01

Linear back-drive differentials have been proposed as alternatives to conventional gear differentials for applications in which there is only limited rotational motion (e.g., oscillation). The finite nature of the rotation makes it possible to optimize a linear back-drive differential in ways that would not be possible for gear differentials or other differentials that are required to be capable of unlimited rotation. As a result, relative to gear differentials, linear back-drive differentials could be more compact and less massive, could contain fewer complex parts, and could be less sensitive to variations in the viscosities of lubricants. Linear back-drive differentials would operate according to established principles of power ball screws and linear-motion drives, but would utilize these principles in an innovative way. One major characteristic of such mechanisms that would be exploited in linear back-drive differentials is the possibility of designing them to drive or back-drive with similar efficiency and energy input: in other words, such a mechanism can be designed so that a rotating screw can drive a nut linearly or the linear motion of the nut can cause the screw to rotate. A linear back-drive differential (see figure) would include two collinear shafts connected to two parts that are intended to engage in limited opposing rotations. The linear back-drive differential would also include a nut that would be free to translate along its axis but not to rotate. The inner surface of the nut would be right-hand threaded at one end and left-hand threaded at the opposite end to engage corresponding right- and left-handed threads on the shafts. A rotation and torque introduced into the system via one shaft would drive the nut in linear motion. The nut, in turn, would back-drive the other shaft, creating a reaction torque. Balls would reduce friction, making it possible for the shaft/nut coupling on each side to operate with 90 percent efficiency.

Linear excitation and detection in Fourier transform ion cyclotron resonance mass spectrometry

NASA Astrophysics Data System (ADS)

Grosshans, Peter B.; Chen, Ruidan; Limbach, Patrick A.; Marshall, Alan G.

1994-11-01

We present the first Fourier transform ion cyclotron resonance (FT-ICR) ion trap designed to produce both a linear spatial variation of the excitation electric potential field and a linear response of the detection circuit to the motion of the confined ions. With this trap, the magnitude of the detected signal at a given ion cyclotron frequency varies linearly with both the number of ions of given mass-to-charge ratio and also with the magnitude-mode excitation signal at the ion cyclotron orbital frequency; the proportionality constant is mass independent. Interestingly, this linearization may be achieved with any ion trap geometry. The excitation/detection design consists of an array of capacitively coupled electrodes which provide a voltage-divider network that produces a nearly spatially homogeneous excitation electric field throughout the linearized trap; resistive coupling to the electrodes isolates the a.c. excitation (or detection) circuit from the d.c. (trapping) potential. The design is based on analytical expressions for the potential associated with each electrode, from which we are able to compute the deviation from linearity for a trap with a finite number of elements. Based on direct experimental comparisons to an unmodified cubic trap, the linearized trap demonstrates the following performance advantages at the cost of some additional mechanical complexity: (a) signal response linearly proportional to excitation electric field amplitude; (b) vastly reduced axial excitation/ejection for significantly improved ion relative abundance accuracy; (c) elimination of harmonics and sidebands of the fundamental frequencies of ion motion. As a result, FT-ICR mass spectra are now more reproducible. Moreover, the linearized trap should facilitate the characterization of other fundamental aspects of ion behavior in an ICR ion trap, e.g. effects of space charge, non-quadrupolar electrostatic trapping field, etc. Furthermore, this novel design should improve significantly the precision of ion relative abundance and mass accuracy measurements, while removing spectral artifacts of the detection process. We discuss future modifications that linearize the spatial variation of the electrostatic trapping electric field as well, thereby completing the linearization of the entire FT-ICR mass spectrometric techniques. Suggested FT-ICR mass spectrometric applications for the linearized trap are discussed.

Broad-band simulation of M7.2 earthquake on the North Tehran fault, considering non-linear soil effects

NASA Astrophysics Data System (ADS)

Majidinejad, A.; Zafarani, H.; Vahdani, S.

2018-05-01

The North Tehran fault (NTF) is known to be one of the most drastic sources of seismic hazard on the city of Tehran. In this study, we provide broad-band (0-10 Hz) ground motions for the city as a consequence of probable M7.2 earthquake on the NTF. Low-frequency motions (0-2 Hz) are provided from spectral element dynamic simulation of 17 scenario models. High-frequency (2-10 Hz) motions are calculated with a physics-based method based on S-to-S backscattering theory. Broad-band ground motions at the bedrock level show amplifications, both at low and high frequencies, due to the existence of deep Tehran basin in the vicinity of the NTF. By employing soil profiles obtained from regional studies, effect of shallow soil layers on broad-band ground motions is investigated by both linear and non-linear analyses. While linear soil response overestimate ground motion prediction equations, non-linear response predicts plausible results within one standard deviation of empirical relationships. Average Peak Ground Accelerations (PGAs) at the northern, central and southern parts of the city are estimated about 0.93, 0.59 and 0.4 g, respectively. Increased damping caused by non-linear soil behaviour, reduces the soil linear responses considerably, in particular at frequencies above 3 Hz. Non-linear deamplification reduces linear spectral accelerations up to 63 per cent at stations above soft thick sediments. By performing more general analyses, which exclude source-to-site effects on stations, a correction function is proposed for typical site classes of Tehran. Parameters for the function which reduces linear soil response in order to take into account non-linear soil deamplification are provided for various frequencies in the range of engineering interest. In addition to fully non-linear analyses, equivalent-linear calculations were also conducted which their comparison revealed appropriateness of the method for large peaks and low frequencies, but its shortage for small to medium peaks and motions with higher than 3 Hz frequencies.

Anomaly General Circulation Models.

NASA Astrophysics Data System (ADS)

Navarra, Antonio

The feasibility of the anomaly model is assessed using barotropic and baroclinic models. In the barotropic case, both a stationary and a time-dependent model has been formulated and constructed, whereas only the stationary, linear case is considered in the baroclinic case. Results from the barotropic model indicate that a relation between the stationary solution and the time-averaged non-linear solution exists. The stationary linear baroclinic solution can therefore be considered with some confidence. The linear baroclinic anomaly model poses a formidable mathematical problem because it is necessary to solve a gigantic linear system to obtain the solution. A new method to find solution of large linear system, based on a projection on the Krylov subspace is shown to be successful when applied to the linearized baroclinic anomaly model. The scheme consists of projecting the original linear system on the Krylov subspace, thereby reducing the dimensionality of the matrix to be inverted to obtain the solution. With an appropriate setting of the damping parameters, the iterative Krylov method reaches a solution even using a Krylov subspace ten times smaller than the original space of the problem. This generality allows the treatment of the important problem of linear waves in the atmosphere. A larger class (nonzonally symmetric) of basic states can now be treated for the baroclinic primitive equations. These problem leads to large unsymmetrical linear systems of order 10000 and more which can now be successfully tackled by the Krylov method. The (R7) linear anomaly model is used to investigate extensively the linear response to equatorial and mid-latitude prescribed heating. The results indicate that the solution is deeply affected by the presence of the stationary waves in the basic state. The instability of the asymmetric flows, first pointed out by Simmons et al. (1983), is active also in the baroclinic case. However, the presence of baroclinic processes modifies the dominant response. The most sensitive areas are identified; they correspond to north Japan, the Pole and Greenland regions. A limited set of higher resolution (R15) experiments indicate that this situation is still present and enhanced at higher resolution. The linear anomaly model is also applied to a realistic case. (Abstract shortened with permission of author.).

Optical measurement of the weak non-linearity in the eardrum vibration response to auditory stimuli

NASA Astrophysics Data System (ADS)

Aerts, Johan

The mammalian hearing organ consists of the external ear (auricle and ear canal) followed by the middle ear (eardrum and ossicles) and the inner ear (cochlea). Its function is to convert the incoming sound waves and convert them into nerve pulses which are processed in the final stage by the brain. The main task of the external and middle ear is to concentrate the incoming sound waves on a smaller surface to reduce the loss that would normally occur in transmission from air to inner ear fluid. In the past it has been shown that this is a linear process, thus without serious distortions, for sound waves going up to pressures of 130 dB SPL (˜90 Pa). However, at large pressure changes up to several kPa, the middle ear movement clearly shows non-linear behaviour. Thus, it is possible that some small non-linear distortions are also present in the middle ear vibration at lower sound pressures. In this thesis a sensitive measurement set-up is presented to detect this weak non-linear behaviour. Essentially, this set-up consists of a loud-speaker which excites the middle ear, and the resulting vibration is measured with an heterodyne vibrometer. The use of specially designed acoustic excitation signals (odd random phase multisines) enables the separation of the linear and non-linear response. The application of this technique on the middle ear demonstrates that there are already non-linear distortions present in the vibration of the middle ear at a sound pressure of 93 dB SPL. This non-linear component also grows strongly with increasing sound pressure. Knowledge of this non-linear component can contribute to the improvement of modern hearing aids, which operate at higher sound pressures where the non-linearities could distort the signal considerably. It is also important to know the contribution of middle ear non-linearity to otoacoustic emissions. This are non-linearities caused by the active feedback amplifier in the inner ear, and can be detected in the external and middle ear. These signals are used for diagnostic purposes, and therefore it is important to have an estimate the non-linear middle ear contribution to these emissions.

Power MOSFET Linearizer of a High-Voltage Power Amplifier for High-Frequency Pulse-Echo Instrumentation.

PubMed

Choi, Hojong; Woo, Park Chul; Yeom, Jung-Yeol; Yoon, Changhan

2017-04-04

A power MOSFET linearizer is proposed for a high-voltage power amplifier (HVPA) used in high-frequency pulse-echo instrumentation. The power MOSFET linearizer is composed of a DC bias-controlled series power MOSFET shunt with parallel inductors and capacitors. The proposed scheme is designed to improve the gain deviation characteristics of the HVPA at higher input powers. By controlling the MOSFET bias voltage in the linearizer, the gain reduction into the HVPA was compensated, thereby reducing the echo harmonic distortion components generated by the ultrasonic transducers. In order to verify the performance improvement of the HVPA implementing the power MOSFET linearizer, we measured and found that the gain deviation of the power MOSFET linearizer integrated with HVPA under 10 V DC bias voltage was reduced (-1.8 and -0.96 dB, respectively) compared to that of the HVPA without the power MOSFET linearizer (-2.95 and -3.0 dB, respectively) when 70 and 80 MHz, three-cycle, and 26 dB m input pulse waveforms are applied, respectively. The input 1-dB compression point (an index of linearity) of the HVPA with power MOSFET linearizer (24.17 and 26.19 dB m at 70 and 80 MHz, respectively) at 10 V DC bias voltage was increased compared to that of HVPA without the power MOSFET linearizer (22.03 and 22.13 dB m at 70 and 80 MHz, respectively). To further verify the reduction of the echo harmonic distortion components generated by the ultrasonic transducers, the pulse-echo responses in the pulse-echo instrumentation were compared when using HVPA with and without the power MOSFET linearizer. When three-cycle 26 dB m input power was applied, the second, third, fourth, and fifth harmonic distortion components of a 75 MHz transducer driven by the HVPA with power MOSFET linearizer (-48.34, -44.21, -48.34, and -46.56 dB, respectively) were lower than that of the HVPA without the power MOSFET linearizer (-45.61, -41.57, -45.01, and -45.51 dB, respectively). When five-cycle 20 dB m input power was applied, the second, third, fourth, and fifth harmonic distortions of the HVPA with the power MOSFET linearizer (-41.54, -41.80, -48.86, and -46.27 dB, respectively) were also lower than that of the HVPA without the power MOSFET linearizer (-25.85, -43.56, -49.04, and -49.24 dB, respectively). Therefore, we conclude that the power MOSFET linearizer could reduce gain deviation of the HVPA, thus reducing the echo signal harmonic distortions generated by the high-frequency ultrasonic transducers in pulse-echo instrumentation.

Power MOSFET Linearizer of a High-Voltage Power Amplifier for High-Frequency Pulse-Echo Instrumentation

PubMed Central

Choi, Hojong; Woo, Park Chul; Yeom, Jung-Yeol; Yoon, Changhan

2017-01-01

A power MOSFET linearizer is proposed for a high-voltage power amplifier (HVPA) used in high-frequency pulse-echo instrumentation. The power MOSFET linearizer is composed of a DC bias-controlled series power MOSFET shunt with parallel inductors and capacitors. The proposed scheme is designed to improve the gain deviation characteristics of the HVPA at higher input powers. By controlling the MOSFET bias voltage in the linearizer, the gain reduction into the HVPA was compensated, thereby reducing the echo harmonic distortion components generated by the ultrasonic transducers. In order to verify the performance improvement of the HVPA implementing the power MOSFET linearizer, we measured and found that the gain deviation of the power MOSFET linearizer integrated with HVPA under 10 V DC bias voltage was reduced (−1.8 and −0.96 dB, respectively) compared to that of the HVPA without the power MOSFET linearizer (−2.95 and −3.0 dB, respectively) when 70 and 80 MHz, three-cycle, and 26 dBm input pulse waveforms are applied, respectively. The input 1-dB compression point (an index of linearity) of the HVPA with power MOSFET linearizer (24.17 and 26.19 dBm at 70 and 80 MHz, respectively) at 10 V DC bias voltage was increased compared to that of HVPA without the power MOSFET linearizer (22.03 and 22.13 dBm at 70 and 80 MHz, respectively). To further verify the reduction of the echo harmonic distortion components generated by the ultrasonic transducers, the pulse-echo responses in the pulse-echo instrumentation were compared when using HVPA with and without the power MOSFET linearizer. When three-cycle 26 dBm input power was applied, the second, third, fourth, and fifth harmonic distortion components of a 75 MHz transducer driven by the HVPA with power MOSFET linearizer (−48.34, −44.21, −48.34, and −46.56 dB, respectively) were lower than that of the HVPA without the power MOSFET linearizer (−45.61, −41.57, −45.01, and −45.51 dB, respectively). When five-cycle 20 dBm input power was applied, the second, third, fourth, and fifth harmonic distortions of the HVPA with the power MOSFET linearizer (−41.54, −41.80, −48.86, and −46.27 dB, respectively) were also lower than that of the HVPA without the power MOSFET linearizer (−25.85, −43.56, −49.04, and −49.24 dB, respectively). Therefore, we conclude that the power MOSFET linearizer could reduce gain deviation of the HVPA, thus reducing the echo signal harmonic distortions generated by the high-frequency ultrasonic transducers in pulse-echo instrumentation. PMID:28375165

Visuo-manual tracking: does intermittent control with aperiodic sampling explain linear power and non-linear remnant without sensorimotor noise?

PubMed

Gollee, Henrik; Gawthrop, Peter J; Lakie, Martin; Loram, Ian D

2017-11-01

A human controlling an external system is described most easily and conventionally as linearly and continuously translating sensory input to motor output, with the inevitable output remnant, non-linearly related to the input, attributed to sensorimotor noise. Recent experiments show sustained manual tracking involves repeated refractoriness (insensitivity to sensory information for a certain duration), with the temporary 200-500 ms periods of irresponsiveness to sensory input making the control process intrinsically non-linear. This evidence calls for re-examination of the extent to which random sensorimotor noise is required to explain the non-linear remnant. This investigation of manual tracking shows how the full motor output (linear component and remnant) can be explained mechanistically by aperiodic sampling triggered by prediction error thresholds. Whereas broadband physiological noise is general to all processes, aperiodic sampling is associated with sensorimotor decision making within specific frontal, striatal and parietal networks; we conclude that manual tracking utilises such slow serial decision making pathways up to several times per second. The human operator is described adequately by linear translation of sensory input to motor output. Motor output also always includes a non-linear remnant resulting from random sensorimotor noise from multiple sources, and non-linear input transformations, for example thresholds or refractory periods. Recent evidence showed that manual tracking incurs substantial, serial, refractoriness (insensitivity to sensory information of 350 and 550 ms for 1st and 2nd order systems respectively). Our two questions are: (i) What are the comparative merits of explaining the non-linear remnant using noise or non-linear transformations? (ii) Can non-linear transformations represent serial motor decision making within the sensorimotor feedback loop intrinsic to tracking? Twelve participants (instructed to act in three prescribed ways) manually controlled two systems (1st and 2nd order) subject to a periodic multi-sine disturbance. Joystick power was analysed using three models, continuous-linear-control (CC), continuous-linear-control with calculated noise spectrum (CCN), and intermittent control with aperiodic sampling triggered by prediction error thresholds (IC). Unlike the linear mechanism, the intermittent control mechanism explained the majority of total power (linear and remnant) (77-87% vs. 8-48%, IC vs. CC). Between conditions, IC used thresholds and distributions of open loop intervals consistent with, respectively, instructions and previous measured, model independent values; whereas CCN required changes in noise spectrum deviating from broadband, signal dependent noise. We conclude that manual tracking uses open loop predictive control with aperiodic sampling. Because aperiodic sampling is inherent to serial decision making within previously identified, specific frontal, striatal and parietal networks we suggest that these structures are intimately involved in visuo-manual tracking. © 2017 The Authors. The Journal of Physiology published by John Wiley & Sons Ltd on behalf of The Physiological Society.

78 FR 26393 - Certain Linear Actuators; Institution of Investigation Pursuant to 19 U.S.C. 1337

Federal Register 2010, 2011, 2012, 2013, 2014

2013-05-06

... INTERNATIONAL TRADE COMMISSION [Investigation No. 337-TA-880] Certain Linear Actuators... importation, and the sale within the United States after importation of certain linear actuators by reason of... linear actuators by reason of infringement of one or more of claims 1-29 of the '144 patent, and whether...

Recent Updates to the GEOS-5 Linear Model

NASA Technical Reports Server (NTRS)

Holdaway, Dan; Kim, Jong G.; Errico, Ron; Gelaro, Ronald; Mahajan, Rahul

2014-01-01

Global Modeling and Assimilation Office (GMAO) is close to having a working 4DVAR system and has developed a linearized version of GEOS-5.This talk outlines a series of improvements made to the linearized dynamics, physics and trajectory.Of particular interest is the development of linearized cloud microphysics, which provides the framework for 'all-sky' data assimilation.

Using Linear Algebra to Introduce Computer Algebra, Numerical Analysis, Data Structures and Algorithms (and To Teach Linear Algebra, Too).

ERIC Educational Resources Information Center

Gonzalez-Vega, Laureano

1999-01-01

Using a Computer Algebra System (CAS) to help with the teaching of an elementary course in linear algebra can be one way to introduce computer algebra, numerical analysis, data structures, and algorithms. Highlights the advantages and disadvantages of this approach to the teaching of linear algebra. (Author/MM)

New Results on the Linear Equating Methods for the Non-Equivalent-Groups Design

ERIC Educational Resources Information Center

von Davier, Alina A.

2008-01-01

The two most common observed-score equating functions are the linear and equipercentile functions. These are often seen as different methods, but von Davier, Holland, and Thayer showed that any equipercentile equating function can be decomposed into linear and nonlinear parts. They emphasized the dominant role of the linear part of the nonlinear…

The viscoelastic properties of the protein-rich materials from the fermented hard wheat, soft wheat and barley flours

USDA-ARS?s Scientific Manuscript database

The linear and non-linear rheological properties of the suspensions for the hard red spring wheat (HRS) flour, soft wheat (Pastry) flour, barley flour, as well as the remain residues of HRS flour, Pastry flour, and barley flour after fermentation were investigated. The linear and non-linear rheologi...

Linear-Algebra Programs

NASA Technical Reports Server (NTRS)

Lawson, C. L.; Krogh, F. T.; Gold, S. S.; Kincaid, D. R.; Sullivan, J.; Williams, E.; Hanson, R. J.; Haskell, K.; Dongarra, J.; Moler, C. B.

1982-01-01

The Basic Linear Algebra Subprograms (BLAS) library is a collection of 38 FORTRAN-callable routines for performing basic operations of numerical linear algebra. BLAS library is portable and efficient source of basic operations for designers of programs involving linear algebriac computations. BLAS library is supplied in portable FORTRAN and Assembler code versions for IBM 370, UNIVAC 1100 and CDC 6000 series computers.

Linear electric field time-of-flight ion mass spectrometer

DOEpatents

Funsten, Herbert O [Los Alamos, NM; Feldman, William C [Los Alamos, NM

2008-06-10

A linear electric field ion mass spectrometer having an evacuated enclosure with means for generating a linear electric field located in the evacuated enclosure and means for injecting a sample material into the linear electric field. A source of pulsed ionizing radiation injects ionizing radiation into the linear electric field to ionize atoms or molecules of the sample material, and timing means determine the time elapsed between ionization of atoms or molecules and arrival of an ion out of the ionized atoms or molecules at a predetermined position.

ADER schemes for scalar non-linear hyperbolic conservation laws with source terms in three-space dimensions

NASA Astrophysics Data System (ADS)

Toro, E. F.; Titarev, V. A.

2005-01-01

In this paper we develop non-linear ADER schemes for time-dependent scalar linear and non-linear conservation laws in one-, two- and three-space dimensions. Numerical results of schemes of up to fifth order of accuracy in both time and space illustrate that the designed order of accuracy is achieved in all space dimensions for a fixed Courant number and essentially non-oscillatory results are obtained for solutions with discontinuities. We also present preliminary results for two-dimensional non-linear systems.

Towards Stability Analysis of Jump Linear Systems with State-Dependent and Stochastic Switching

NASA Technical Reports Server (NTRS)

Tejada, Arturo; Gonzalez, Oscar R.; Gray, W. Steven

2004-01-01

This paper analyzes the stability of hierarchical jump linear systems where the supervisor is driven by a Markovian stochastic process and by the values of the supervised jump linear system s states. The stability framework for this class of systems is developed over infinite and finite time horizons. The framework is then used to derive sufficient stability conditions for a specific class of hybrid jump linear systems with performance supervision. New sufficient stochastic stability conditions for discrete-time jump linear systems are also presented.

Fault tolerant linear actuator

DOEpatents

Tesar, Delbert

2004-09-14

In varying embodiments, the fault tolerant linear actuator of the present invention is a new and improved linear actuator with fault tolerance and positional control that may incorporate velocity summing, force summing, or a combination of the two. In one embodiment, the invention offers a velocity summing arrangement with a differential gear between two prime movers driving a cage, which then drives a linear spindle screw transmission. Other embodiments feature two prime movers driving separate linear spindle screw transmissions, one internal and one external, in a totally concentric and compact integrated module.

Linear phase compressive filter

DOEpatents

McEwan, Thomas E.

1995-01-01

A phase linear filter for soliton suppression is in the form of a laddered series of stages of non-commensurate low pass filters with each low pass filter having a series coupled inductance (L) and a reverse biased, voltage dependent varactor diode, to ground which acts as a variable capacitance (C). L and C values are set to levels which correspond to a linear or conventional phase linear filter. Inductance is mapped directly from that of an equivalent nonlinear transmission line and capacitance is mapped from the linear case using a large signal equivalent of a nonlinear transmission line.

Ultra-high vacuum photoelectron linear accelerator

DOEpatents

Yu, David U.L.; Luo, Yan

2013-07-16

An rf linear accelerator for producing an electron beam. The outer wall of the rf cavity of said linear accelerator being perforated to allow gas inside said rf cavity to flow to a pressure chamber surrounding said rf cavity and having means of ultra high vacuum pumping of the cathode of said rf linear accelerator. Said rf linear accelerator is used to accelerate polarized or unpolarized electrons produced by a photocathode, or to accelerate thermally heated electrons produced by a thermionic cathode, or to accelerate rf heated field emission electrons produced by a field emission cathode.

A simple smoothness indicator for the WENO scheme with adaptive order

NASA Astrophysics Data System (ADS)

Huang, Cong; Chen, Li Li

2018-01-01

The fifth order WENO scheme with adaptive order is competent for solving hyperbolic conservation laws, its reconstruction is a convex combination of a fifth order linear reconstruction and three third order linear reconstructions. Note that, on uniform mesh, the computational cost of smoothness indicator for fifth order linear reconstruction is comparable with the sum of ones for three third order linear reconstructions, thus it is too heavy; on non-uniform mesh, the explicit form of smoothness indicator for fifth order linear reconstruction is difficult to be obtained, and its computational cost is much heavier than the one on uniform mesh. In order to overcome these problems, a simple smoothness indicator for fifth order linear reconstruction is proposed in this paper.

Gain optimization with non-linear controls

NASA Technical Reports Server (NTRS)

Slater, G. L.; Kandadai, R. D.

1984-01-01

An algorithm has been developed for the analysis and design of controls for non-linear systems. The technical approach is to use statistical linearization to model the non-linear dynamics of a system by a quasi-Gaussian model. A covariance analysis is performed to determine the behavior of the dynamical system and a quadratic cost function. Expressions for the cost function and its derivatives are determined so that numerical optimization techniques can be applied to determine optimal feedback laws. The primary application for this paper is centered about the design of controls for nominally linear systems but where the controls are saturated or limited by fixed constraints. The analysis is general, however, and numerical computation requires only that the specific non-linearity be considered in the analysis.

Large-scale linear rankSVM.

PubMed

Lee, Ching-Pei; Lin, Chih-Jen

2014-04-01

Linear rankSVM is one of the widely used methods for learning to rank. Although its performance may be inferior to nonlinear methods such as kernel rankSVM and gradient boosting decision trees, linear rankSVM is useful to quickly produce a baseline model. Furthermore, following its recent development for classification, linear rankSVM may give competitive performance for large and sparse data. A great deal of works have studied linear rankSVM. The focus is on the computational efficiency when the number of preference pairs is large. In this letter, we systematically study existing works, discuss their advantages and disadvantages, and propose an efficient algorithm. We discuss different implementation issues and extensions with detailed experiments. Finally, we develop a robust linear rankSVM tool for public use.

A double B1-mode 4-layer laminated piezoelectric linear motor.

PubMed

Li, Xiaotian; Chen, Zhijiang; Dong, Shuxiang

2012-12-01

We report a miniature piezoelectric ultrasonic linear motor that is made of four Pb(Zr,Ti)O(3) (PZT) piezoelectric ceramic layers for low-voltage work. The 4-layer piezoelectric laminate works in two orthogonal first-bending modes for producing elliptical oscillations, which are then used to drive a contacting slider into continuous linear motion. Experimental results show that the miniature linear motor (size: 4 × 4 × 12 mm, weight: 1.7 g) can generate a large driving force of 0.48 N and a linear motion speed of up to 160 mm/s, using a 40 V(pp)/mm voltage drive at its resonance frequency of 64.5 kHz. The maximum efficiency of the linear motor is 30%.

Diode end pumped laser and harmonic generator using same

NASA Technical Reports Server (NTRS)

Byer, Robert L. (Inventor); Dixon, George J. (Inventor); Kane, Thomas J. (Inventor)

1988-01-01

A second harmonic, optical generator is disclosed in which a laser diode produces an output pumping beam which is focused by means of a graded, refractive index rod lens into a rod of lasant material, such as Nd:YAG, disposed within an optical resonator to pump the lasant material and to excite the optical resonator at a fundamental wavelength. A non-linear electro-optic material such as MgO:LiNbO.sub.3 is coupled to the excited, fundamental mode of the optical resonator to produce a non-linear interaction with the fundamental wavelength producing a harmonic. In one embodiment, the gain medium and the non-linear material are disposed within an optical resonator defined by a pair of reflectors, one of which is formed on a face of the gain medium and the second of which is formed on a face of the non-linear medium. In another embodiment, the non-linear, electro-optic material is doped with the lasant ion such that the gain medium and the non-linear doubling material are co-extensive in volume. In another embodiment, a non-linear, doubling material is disposed in an optical resonator external of the laser gai medium for improved stability of the second harmonic generation process. In another embodiment, the laser gain medium andthe non-linear material are bonded together by means of an optically transparent cement to form a mechanically stable, monolithic structure. In another embodiment, the non-linear material has reflective faces formed thereon to define a ring resonator to decouple reflections from the non-linear medium back to the gain medium for improved stability.

Face-selective regions show invariance to linear, but not to non-linear, changes in facial images.

PubMed

Baseler, Heidi A; Young, Andrew W; Jenkins, Rob; Mike Burton, A; Andrews, Timothy J

2016-12-01

Familiar face recognition is remarkably invariant across huge image differences, yet little is understood concerning how image-invariant recognition is achieved. To investigate the neural correlates of invariance, we localized the core face-responsive regions and then compared the pattern of fMR-adaptation to different stimulus transformations in each region to behavioural data demonstrating the impact of the same transformations on familiar face recognition. In Experiment 1, we compared linear transformations of size and aspect ratio to a non-linear transformation affecting only part of the face. We found that adaptation to facial identity in face-selective regions showed invariance to linear changes, but there was no invariance to non-linear changes. In Experiment 2, we measured the sensitivity to non-linear changes that fell within the normal range of variation across face images. We found no adaptation to facial identity for any of the non-linear changes in the image, including to faces that varied in different levels of caricature. These results show a compelling difference in the sensitivity to linear compared to non-linear image changes in face-selective regions of the human brain that is only partially consistent with their effect on behavioural judgements of identity. We conclude that while regions such as the FFA may well be involved in the recognition of face identity, they are more likely to contribute to some form of normalisation that underpins subsequent recognition than to form the neural substrate of recognition per se. Copyright © 2016 Elsevier Ltd. All rights reserved.

Inclusion of Linearized Moist Physics in Nasa's Goddard Earth Observing System Data Assimilation Tools

NASA Technical Reports Server (NTRS)

Holdaway, Daniel; Errico, Ronald; Gelaro, Ronaldo; Kim, Jong G.

2013-01-01

Inclusion of moist physics in the linearized version of a weather forecast model is beneficial in terms of variational data assimilation. Further, it improves the capability of important tools, such as adjoint-based observation impacts and sensitivity studies. A linearized version of the relaxed Arakawa-Schubert (RAS) convection scheme has been developed and tested in NASA's Goddard Earth Observing System data assimilation tools. A previous study of the RAS scheme showed it to exhibit reasonable linearity and stability. This motivates the development of a linearization of a near-exact version of the RAS scheme. Linearized large-scale condensation is included through simple conversion of supersaturation into precipitation. The linearization of moist physics is validated against the full nonlinear model for 6- and 24-h intervals, relevant to variational data assimilation and observation impacts, respectively. For a small number of profiles, sudden large growth in the perturbation trajectory is encountered. Efficient filtering of these profiles is achieved by diagnosis of steep gradients in a reduced version of the operator of the tangent linear model. With filtering turned on, the inclusion of linearized moist physics increases the correlation between the nonlinear perturbation trajectory and the linear approximation of the perturbation trajectory. A month-long observation impact experiment is performed and the effect of including moist physics on the impacts is discussed. Impacts from moist-sensitive instruments and channels are increased. The effect of including moist physics is examined for adjoint sensitivity studies. A case study examining an intensifying Northern Hemisphere Atlantic storm is presented. The results show a significant sensitivity with respect to moisture.

Non-linear scaling of a musculoskeletal model of the lower limb using statistical shape models.

PubMed

Nolte, Daniel; Tsang, Chui Kit; Zhang, Kai Yu; Ding, Ziyun; Kedgley, Angela E; Bull, Anthony M J

2016-10-03

Accurate muscle geometry for musculoskeletal models is important to enable accurate subject-specific simulations. Commonly, linear scaling is used to obtain individualised muscle geometry. More advanced methods include non-linear scaling using segmented bone surfaces and manual or semi-automatic digitisation of muscle paths from medical images. In this study, a new scaling method combining non-linear scaling with reconstructions of bone surfaces using statistical shape modelling is presented. Statistical Shape Models (SSMs) of femur and tibia/fibula were used to reconstruct bone surfaces of nine subjects. Reference models were created by morphing manually digitised muscle paths to mean shapes of the SSMs using non-linear transformations and inter-subject variability was calculated. Subject-specific models of muscle attachment and via points were created from three reference models. The accuracy was evaluated by calculating the differences between the scaled and manually digitised models. The points defining the muscle paths showed large inter-subject variability at the thigh and shank - up to 26mm; this was found to limit the accuracy of all studied scaling methods. Errors for the subject-specific muscle point reconstructions of the thigh could be decreased by 9% to 20% by using the non-linear scaling compared to a typical linear scaling method. We conclude that the proposed non-linear scaling method is more accurate than linear scaling methods. Thus, when combined with the ability to reconstruct bone surfaces from incomplete or scattered geometry data using statistical shape models our proposed method is an alternative to linear scaling methods. Copyright © 2016 The Author. Published by Elsevier Ltd.. All rights reserved.

Predicting musically induced emotions from physiological inputs: linear and neural network models.

PubMed

Russo, Frank A; Vempala, Naresh N; Sandstrom, Gillian M

2013-01-01

Listening to music often leads to physiological responses. Do these physiological responses contain sufficient information to infer emotion induced in the listener? The current study explores this question by attempting to predict judgments of "felt" emotion from physiological responses alone using linear and neural network models. We measured five channels of peripheral physiology from 20 participants-heart rate (HR), respiration, galvanic skin response, and activity in corrugator supercilii and zygomaticus major facial muscles. Using valence and arousal (VA) dimensions, participants rated their felt emotion after listening to each of 12 classical music excerpts. After extracting features from the five channels, we examined their correlation with VA ratings, and then performed multiple linear regression to see if a linear relationship between the physiological responses could account for the ratings. Although linear models predicted a significant amount of variance in arousal ratings, they were unable to do so with valence ratings. We then used a neural network to provide a non-linear account of the ratings. The network was trained on the mean ratings of eight of the 12 excerpts and tested on the remainder. Performance of the neural network confirms that physiological responses alone can be used to predict musically induced emotion. The non-linear model derived from the neural network was more accurate than linear models derived from multiple linear regression, particularly along the valence dimension. A secondary analysis allowed us to quantify the relative contributions of inputs to the non-linear model. The study represents a novel approach to understanding the complex relationship between physiological responses and musically induced emotion.

Singularities of interference of three waves with different polarization states.

PubMed

Kurzynowski, Piotr; Woźniak, Władysław A; Zdunek, Marzena; Borwińska, Monika

2012-11-19

We presented the interference setup which can produce interesting two-dimensional patterns in polarization state of the resulting light wave emerging from the setup. The main element of our setup is the Wollaston prism which gives two plane, linearly polarized waves (eigenwaves of both Wollaston's wedges) with linearly changed phase difference between them (along the x-axis). The third wave coming from the second arm of proposed polarization interferometer is linearly or circularly polarized with linearly changed phase difference along the y-axis. The interference of three plane waves with different polarization states (LLL - linear-linear-linear or LLC - linear-linear-circular) and variable change difference produce two-dimensional light polarization and phase distributions with some characteristic points and lines which can be claimed to constitute singularities of different types. The aim of this article is to find all kind of these phase and polarization singularities as well as their classification. We postulated in our theoretical simulations and verified in our experiments different kinds of polarization singularities, depending on which polarization parameter was considered (the azimuth and ellipticity angles or the diagonal and phase angles). We also observed the phase singularities as well as the isolated zero intensity points which resulted from the polarization singularities when the proper analyzer was used at the end of the setup. The classification of all these singularities as well as their relationships were analyzed and described.

Comparisons of linear and nonlinear pyramid schemes for signal and image processing

NASA Astrophysics Data System (ADS)

Morales, Aldo W.; Ko, Sung-Jea

1997-04-01

Linear filters banks are being used extensively in image and video applications. New research results in wavelet applications for compression and de-noising are constantly appearing in the technical literature. On the other hand, non-linear filter banks are also being used regularly in image pyramid algorithms. There are some inherent advantages in using non-linear filters instead of linear filters when non-Gaussian processes are present in images. However, a consistent way of comparing performance criteria between these two schemes has not been fully developed yet. In this paper a recently discovered tool, sample selection probabilities, is used to compare the behavior of linear and non-linear filters. In the conversion from weights of order statistics (OS) filters to coefficients of the impulse response is obtained through these probabilities. However, the reverse problem: the conversion from coefficients of the impulse response to the weights of OS filters is not yet fully understood. One of the reasons for this difficulty is the highly non-linear nature of the partitions and generating function used. In the present paper the problem is posed as an optimization of integer linear programming subject to constraints directly obtained from the coefficients of the impulse response. Although the technique to be presented in not completely refined, it certainly appears to be promising. Some results will be shown.

Linear signatures in nonlinear gyrokinetics: interpreting turbulence with pseudospectra

DOE PAGES

Hatch, D. R.; Jenko, F.; Navarro, A. Banon; ...

2016-07-26

A notable feature of plasma turbulence is its propensity to retain features of the underlying linear eigenmodes in a strongly turbulent state—a property that can be exploited to predict various aspects of the turbulence using only linear information. In this context, this work examines gradient-driven gyrokinetic plasma turbulence through three lenses—linear eigenvalue spectra, pseudospectra, and singular value decomposition (SVD). We study a reduced gyrokinetic model whose linear eigenvalue spectra include ion temperature gradient driven modes, stable drift waves, and kinetic modes representing Landau damping. The goal is to characterize in which ways, if any, these familiar ingredients are manifest inmore » the nonlinear turbulent state. This pursuit is aided by the use of pseudospectra, which provide a more nuanced view of the linear operator by characterizing its response to perturbations. We introduce a new technique whereby the nonlinearly evolved phase space structures extracted with SVD are linked to the linear operator using concepts motivated by pseudospectra. Using this technique, we identify nonlinear structures that have connections to not only the most unstable eigenmode but also subdominant modes that are nonlinearly excited. The general picture that emerges is a system in which signatures of the linear physics persist in the turbulence, albeit in ways that cannot be fully explained by the linear eigenvalue approach; a non-modal treatment is necessary to understand key features of the turbulence.« less

Assessing the Tangent Linear Behaviour of Common Tracer Transport Schemes and Their Use in a Linearised Atmospheric General Circulation Model

NASA Technical Reports Server (NTRS)

Holdaway, Daniel; Kent, James

2015-01-01

The linearity of a selection of common advection schemes is tested and examined with a view to their use in the tangent linear and adjoint versions of an atmospheric general circulation model. The schemes are tested within a simple offline one-dimensional periodic domain as well as using a simplified and complete configuration of the linearised version of NASA's Goddard Earth Observing System version 5 (GEOS-5). All schemes which prevent the development of negative values and preserve the shape of the solution are confirmed to have nonlinear behaviour. The piecewise parabolic method (PPM) with certain flux limiters, including that used by default in GEOS-5, is found to support linear growth near the shocks. This property can cause the rapid development of unrealistically large perturbations within the tangent linear and adjoint models. It is shown that these schemes with flux limiters should not be used within the linearised version of a transport scheme. The results from tests using GEOS-5 show that the current default scheme (a version of PPM) is not suitable for the tangent linear and adjoint model, and that using a linear third-order scheme for the linearised model produces better behaviour. Using the third-order scheme for the linearised model improves the correlations between the linear and non-linear perturbation trajectories for cloud liquid water and cloud liquid ice in GEOS-5.

Stoichiometric Lithium Niobate (SLN) Based Linearized Electro-Optic (EO) Modulator

DTIC Science & Technology

2006-01-01

AFRL-SN-RS-TR-2006-15 Final Technical Report January 2006 STOICHIOMETRIC LITHIUM NIOBATE (SLN) BASED LINEARIZED ELECTRO - OPTIC (EO...LITHIUM NIOBATE (SLN) BASED LINEARIZED ELECTRO - OPTIC (EO) MODULATOR 6. AUTHOR(S) Dr Stuart Kingsley, Dr Sri Sriram 5. FUNDING NUMBERS C...SUBJECT TERMS electro - optic modulator, linearization, directional coupler, variable coupling, optical waveguide, Mach-Zehnder, photonic link, lithium

Multiple Intelligence Scores of Science Stream Students and Their Relation with Reading Competency in Malaysian University English Test (MUET)

ERIC Educational Resources Information Center

Razak, Norizan Abdul; Zaini, Nuramirah

2014-01-01

Many researches have shown that different approach needed in analysing linear and non-linear reading comprehension texts and different cognitive skills are required. This research attempts to discover the relationship between Science Stream students' reading competency on linear and non-linear texts in Malaysian University English Test (MUET) with…

End State: The Fallacy of Modern Military Planning

DTIC Science & Technology

2017-04-06

operational planning for non -linear, complex scenarios requires application of non -linear, advanced planning techniques such as design methodology ...cannot be approached in a linear, mechanistic manner by a universal planning methodology . Theater/global campaign plans and theater strategies offer no...strategic environments, and instead prescribes a universal linear methodology that pays no mind to strategic complexity. This universal application

A Simple Piece of Apparatus to Aid the Understanding of the Relationship between Angular Velocity and Linear Velocity

ERIC Educational Resources Information Center

Unsal, Yasin

2011-01-01

One of the subjects that is confusing and difficult for students to fully comprehend is the concept of angular velocity and linear velocity. It is the relationship between linear and angular velocity that students find difficult; most students understand linear motion in isolation. In this article, we detail the design, construction and…

Linear System of Equations, Matrix Inversion, and Linear Programming Using MS Excel

ERIC Educational Resources Information Center

El-Gebeily, M.; Yushau, B.

2008-01-01

In this note, we demonstrate with illustrations two different ways that MS Excel can be used to solve Linear Systems of Equation, Linear Programming Problems, and Matrix Inversion Problems. The advantage of using MS Excel is its availability and transparency (the user is responsible for most of the details of how a problem is solved). Further, we…

LINEARIZATION OF EMPIRICAL RHEOLOGICAL DATA FOR USE IN COMPOSITION CONTROL OF MULTICOMPONENT FOODSTUFFS.

PubMed

Drake, Birger; Nádai, Béla

1970-03-01

An empirical measure of viscosity, which is often far from being a linear function of composition, was used together with refractive index to build up a function which bears a linear relationship to the composition of tomato paste-water-sucrose mixtures. The new function can be used directly for rapid composition control by linear vector-vector transformation.

From linear mechanics to nonlinear mechanics

NASA Technical Reports Server (NTRS)

Loeb, Julian

1955-01-01

Consideration is given to the techniques used in telecommunication where a nonlinear system (the modulator) results in a linear transposition of a signal. It is then shown that a similar method permits linearization of electromechanical devices or nonlinear mechanical devices. A sweep function plays the same role as the carrier wave in radio-electricity. The linearizations of certain nonlinear functionals are presented.

An Inquiry-Oriented Approach to Span and Linear Independence: The Case of the Magic Carpet Ride Sequence

ERIC Educational Resources Information Center

Wawro, Megan; Rasmussen, Chris; Zandieh, Michelle; Sweeney, George Franklin; Larson, Christine

2012-01-01

In this paper we present an innovative instructional sequence for an introductory linear algebra course that supports students' reinvention of the concepts of span, linear dependence, and linear independence. Referred to as the Magic Carpet Ride sequence, the problems begin with an imaginary scenario that allows students to build rich imagery and…

Electronic Non-Contacting Linear Position Measuring System

DOEpatents

Post, Richard F.

2005-06-14

A non-contacting linear position location system employs a special transmission line to encode and transmit magnetic signals to a receiver on the object whose position is to be measured. The invention is useful as a non-contact linear locator of moving objects, e.g., to determine the location of a magnetic-levitation train for the operation of the linear-synchronous motor drive system.

Comparing The Effectiveness of a90/95 Calculations (Preprint)

DTIC Science & Technology

2006-09-01

Nachtsheim, John Neter, William Li, Applied Linear Statistical Models , 5th ed., McGraw-Hill/Irwin, 2005 5. Mood, Graybill and Boes, Introduction...curves is based on methods that are only valid for ordinary linear regression. Requirements for a valid Ordinary Least-Squares Regression Model There... linear . For example is a linear model ; is not. 2. Uniform variance (homoscedasticity

Some comparisons of complexity in dictionary-based and linear computational models.

PubMed

Gnecco, Giorgio; Kůrková, Věra; Sanguineti, Marcello

2011-03-01

Neural networks provide a more flexible approximation of functions than traditional linear regression. In the latter, one can only adjust the coefficients in linear combinations of fixed sets of functions, such as orthogonal polynomials or Hermite functions, while for neural networks, one may also adjust the parameters of the functions which are being combined. However, some useful properties of linear approximators (such as uniqueness, homogeneity, and continuity of best approximation operators) are not satisfied by neural networks. Moreover, optimization of parameters in neural networks becomes more difficult than in linear regression. Experimental results suggest that these drawbacks of neural networks are offset by substantially lower model complexity, allowing accuracy of approximation even in high-dimensional cases. We give some theoretical results comparing requirements on model complexity for two types of approximators, the traditional linear ones and so called variable-basis types, which include neural networks, radial, and kernel models. We compare upper bounds on worst-case errors in variable-basis approximation with lower bounds on such errors for any linear approximator. Using methods from nonlinear approximation and integral representations tailored to computational units, we describe some cases where neural networks outperform any linear approximator. Copyright © 2010 Elsevier Ltd. All rights reserved.

Vestibular coriolis effect differences modeled with three-dimensional linear-angular interactions.

PubMed

Holly, Jan E

2004-01-01

The vestibular coriolis (or "cross-coupling") effect is traditionally explained by cross-coupled angular vectors, which, however, do not explain the differences in perceptual disturbance under different acceleration conditions. For example, during head roll tilt in a rotating chair, the magnitude of perceptual disturbance is affected by a number of factors, including acceleration or deceleration of the chair rotation or a zero-g environment. Therefore, it has been suggested that linear-angular interactions play a role. The present research investigated whether these perceptual differences and others involving linear coriolis accelerations could be explained under one common framework: the laws of motion in three dimensions, which include all linear-angular interactions among all six components of motion (three angular and three linear). The results show that the three-dimensional laws of motion predict the differences in perceptual disturbance. No special properties of the vestibular system or nervous system are required. In addition, simulations were performed with angular, linear, and tilt time constants inserted into the model, giving the same predictions. Three-dimensional graphics were used to highlight the manner in which linear-angular interaction causes perceptual disturbance, and a crucial component is the Stretch Factor, which measures the "unexpected" linear component.

Efficient Algorithms for Estimating the Absorption Spectrum within Linear Response TDDFT

DOE Office of Scientific and Technical Information (OSTI.GOV)

Brabec, Jiri; Lin, Lin; Shao, Meiyue

We present two iterative algorithms for approximating the absorption spectrum of molecules within linear response of time-dependent density functional theory (TDDFT) framework. These methods do not attempt to compute eigenvalues or eigenvectors of the linear response matrix. They are designed to approximate the absorption spectrum as a function directly. They take advantage of the special structure of the linear response matrix. Neither method requires the linear response matrix to be constructed explicitly. They only require a procedure that performs the multiplication of the linear response matrix with a vector. These methods can also be easily modified to efficiently estimate themore » density of states (DOS) of the linear response matrix without computing the eigenvalues of this matrix. We show by computational experiments that the methods proposed in this paper can be much more efficient than methods that are based on the exact diagonalization of the linear response matrix. We show that they can also be more efficient than real-time TDDFT simulations. We compare the pros and cons of these methods in terms of their accuracy as well as their computational and storage cost.« less

State-Dependent Pseudo-Linear Filter for Spacecraft Attitude and Rate Estimation

NASA Technical Reports Server (NTRS)

Bar-Itzhack, Itzhack Y.; Harman, Richard R.

2001-01-01

This paper presents the development and performance of a special algorithm for estimating the attitude and angular rate of a spacecraft. The algorithm is a pseudo-linear Kalman filter, which is an ordinary linear Kalman filter that operates on a linear model whose matrices are current state estimate dependent. The nonlinear rotational dynamics equation of the spacecraft is presented in the state space as a state-dependent linear system. Two types of measurements are considered. One type is a measurement of the quaternion of rotation, which is obtained from a newly introduced star tracker based apparatus. The other type of measurement is that of vectors, which permits the use of a variety of vector measuring sensors like sun sensors and magnetometers. While quaternion measurements are related linearly to the state vector, vector measurements constitute a nonlinear function of the state vector. Therefore, in this paper, a state-dependent linear measurement equation is developed for the vector measurement case. The state-dependent pseudo linear filter is applied to simulated spacecraft rotations and adequate estimates of the spacecraft attitude and rate are obtained for the case of quaternion measurements as well as of vector measurements.

Testing the existence of optical linear polarization in young brown dwarfs

NASA Astrophysics Data System (ADS)

Manjavacas, E.; Miles-Páez, P. A.; Zapatero-Osorio, M. R.; Goldman, B.; Buenzli, E.; Henning, T.; Pallé, E.; Fang, M.

2017-07-01

Linear polarization can be used as a probe of the existence of atmospheric condensates in ultracool dwarfs. Models predict that the observed linear polarization increases with the degree of oblateness, which is inversely proportional to the surface gravity. We aimed to test the existence of optical linear polarization in a sample of bright young brown dwarfs, with spectral types between M6 and L2, observable from the Calar Alto Observatory, and cataloged previously as low gravity objects using spectroscopy. Linear polarimetric images were collected in I and R band using CAFOS at the 2.2-m telescope in Calar Alto Observatory (Spain). The flux ratio method was employed to determine the linear polarization degrees. With a confidence of 3σ, our data indicate that all targets have a linear polarimetry degree in average below 0.69 per cent in the I band, and below 1.0 per cent in the R band, at the time they were observed. We detected significant (I.e. P/σ ≥ 3) linear polarization for the young M6 dwarf 2MASS J04221413+1530525 in the R band, with a degree of p* = 0.81 ± 0.17 per cent.

Comparison of the Tangent Linear Properties of Tracer Transport Schemes Applied to Geophysical Problems.

NASA Technical Reports Server (NTRS)

Kent, James; Holdaway, Daniel

2015-01-01

A number of geophysical applications require the use of the linearized version of the full model. One such example is in numerical weather prediction, where the tangent linear and adjoint versions of the atmospheric model are required for the 4DVAR inverse problem. The part of the model that represents the resolved scale processes of the atmosphere is known as the dynamical core. Advection, or transport, is performed by the dynamical core. It is a central process in many geophysical applications and is a process that often has a quasi-linear underlying behavior. However, over the decades since the advent of numerical modelling, significant effort has gone into developing many flavors of high-order, shape preserving, nonoscillatory, positive definite advection schemes. These schemes are excellent in terms of transporting the quantities of interest in the dynamical core, but they introduce nonlinearity through the use of nonlinear limiters. The linearity of the transport schemes used in Goddard Earth Observing System version 5 (GEOS-5), as well as a number of other schemes, is analyzed using a simple 1D setup. The linearized version of GEOS-5 is then tested using a linear third order scheme in the tangent linear version.

Analysis of baseline, average, and longitudinally measured blood pressure data using linear mixed models.

PubMed

Hossain, Ahmed; Beyene, Joseph

2014-01-01

This article compares baseline, average, and longitudinal data analysis methods for identifying genetic variants in genome-wide association study using the Genetic Analysis Workshop 18 data. We apply methods that include (a) linear mixed models with baseline measures, (b) random intercept linear mixed models with mean measures outcome, and (c) random intercept linear mixed models with longitudinal measurements. In the linear mixed models, covariates are included as fixed effects, whereas relatedness among individuals is incorporated as the variance-covariance structure of the random effect for the individuals. The overall strategy of applying linear mixed models decorrelate the data is based on Aulchenko et al.'s GRAMMAR. By analyzing systolic and diastolic blood pressure, which are used separately as outcomes, we compare the 3 methods in identifying a known genetic variant that is associated with blood pressure from chromosome 3 and simulated phenotype data. We also analyze the real phenotype data to illustrate the methods. We conclude that the linear mixed model with longitudinal measurements of diastolic blood pressure is the most accurate at identifying the known single-nucleotide polymorphism among the methods, but linear mixed models with baseline measures perform best with systolic blood pressure as the outcome.

Systematic study of doping dependence on linear magnetoresistance in p-PbTe

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schneider, J. M.; Chitta, V. A.; Oliveira, N. F.

2014-10-20

We report on a large linear magnetoresistance effect observed in doped p-PbTe films. While undoped p-PbTe reveals a sublinear magnetoresistance, p-PbTe films doped with BaF{sub 2} exhibit a transition to a nearly perfect linear magnetoresistance behaviour that is persistent up to 30 T. The linear magnetoresistance slope ΔR/ΔB is to a good approximation, independent of temperature. This is in agreement with the theory of Quantum Linear Magnetoresistance. We also performed magnetoresistance simulations using a classical model of linear magnetoresistance. We found that this model fails to explain the experimental data. A systematic study of the doping dependence reveals that the linearmore » magnetoresistance response has a maximum for small BaF{sub 2} doping levels and diminishes rapidly for increasing doping levels. Exploiting the huge impact of doping on the linear magnetoresistance signal could lead to new classes of devices with giant magnetoresistance behavior.« less

Newton's method: A link between continuous and discrete solutions of nonlinear problems

NASA Technical Reports Server (NTRS)

Thurston, G. A.

1980-01-01

Newton's method for nonlinear mechanics problems replaces the governing nonlinear equations by an iterative sequence of linear equations. When the linear equations are linear differential equations, the equations are usually solved by numerical methods. The iterative sequence in Newton's method can exhibit poor convergence properties when the nonlinear problem has multiple solutions for a fixed set of parameters, unless the iterative sequences are aimed at solving for each solution separately. The theory of the linear differential operators is often a better guide for solution strategies in applying Newton's method than the theory of linear algebra associated with the numerical analogs of the differential operators. In fact, the theory for the differential operators can suggest the choice of numerical linear operators. In this paper the method of variation of parameters from the theory of linear ordinary differential equations is examined in detail in the context of Newton's method to demonstrate how it might be used as a guide for numerical solutions.

Linear and nonlinear response in sheared soft spheres

NASA Astrophysics Data System (ADS)

Tighe, Brian

2013-11-01

Packings of soft spheres provide an idealized model of foams, emulsions, and grains, while also serving as the canonical example of a system undergoing a jamming transition. Packings' mechanical response has now been studied exhaustively in the context of ``strict linear response,'' i.e. by linearizing about a stable static packing and solving the resulting equations of motion. Both because the system is close to a critical point and because the soft sphere pair potential is non-analytic at the point of contact, it is reasonable to ask under what circumstances strict linear response provides a good approximation to the actual response. We simulate sheared soft sphere packings close to jamming and identify two distinct strain scales: (i) the scale on which strict linear response fails, coinciding with a topological change in the packing's contact network; and (ii) the scale on which linear superposition of the averaged stress-strain curve breaks down. This latter scale provides a ``weak linear response'' criterion and is likely to be more experimentally relevant.

Students’ difficulties in solving linear equation problems

NASA Astrophysics Data System (ADS)

Wati, S.; Fitriana, L.; Mardiyana

2018-03-01

A linear equation is an algebra material that exists in junior high school to university. It is a very important material for students in order to learn more advanced mathematics topics. Therefore, linear equation material is essential to be mastered. However, the result of 2016 national examination in Indonesia showed that students’ achievement in solving linear equation problem was low. This fact became a background to investigate students’ difficulties in solving linear equation problems. This study used qualitative descriptive method. An individual written test on linear equation tasks was administered, followed by interviews. Twenty-one sample students of grade VIII of SMPIT Insan Kamil Karanganyar did the written test, and 6 of them were interviewed afterward. The result showed that students with high mathematics achievement donot have difficulties, students with medium mathematics achievement have factual difficulties, and students with low mathematics achievement have factual, conceptual, operational, and principle difficulties. Based on the result there is a need of meaningfulness teaching strategy to help students to overcome difficulties in solving linear equation problems.

Linearized Programming of Memristors for Artificial Neuro-Sensor Signal Processing

PubMed Central

Yang, Changju; Kim, Hyongsuk

2016-01-01

A linearized programming method of memristor-based neural weights is proposed. Memristor is known as an ideal element to implement a neural synapse due to its embedded functions of analog memory and analog multiplication. Its resistance variation with a voltage input is generally a nonlinear function of time. Linearization of memristance variation about time is very important for the easiness of memristor programming. In this paper, a method utilizing an anti-serial architecture for linear programming is proposed. The anti-serial architecture is composed of two memristors with opposite polarities. It linearizes the variation of memristance due to complimentary actions of two memristors. For programming a memristor, additional memristor with opposite polarity is employed. The linearization effect of weight programming of an anti-serial architecture is investigated and memristor bridge synapse which is built with two sets of anti-serial memristor architecture is taken as an application example of the proposed method. Simulations are performed with memristors of both linear drift model and nonlinear model. PMID:27548186

Subpixel Mapping of Hyperspectral Image Based on Linear Subpixel Feature Detection and Object Optimization

NASA Astrophysics Data System (ADS)

Liu, Zhaoxin; Zhao, Liaoying; Li, Xiaorun; Chen, Shuhan

2018-04-01

Owing to the limitation of spatial resolution of the imaging sensor and the variability of ground surfaces, mixed pixels are widesperead in hyperspectral imagery. The traditional subpixel mapping algorithms treat all mixed pixels as boundary-mixed pixels while ignoring the existence of linear subpixels. To solve this question, this paper proposed a new subpixel mapping method based on linear subpixel feature detection and object optimization. Firstly, the fraction value of each class is obtained by spectral unmixing. Secondly, the linear subpixel features are pre-determined based on the hyperspectral characteristics and the linear subpixel feature; the remaining mixed pixels are detected based on maximum linearization index analysis. The classes of linear subpixels are determined by using template matching method. Finally, the whole subpixel mapping results are iteratively optimized by binary particle swarm optimization algorithm. The performance of the proposed subpixel mapping method is evaluated via experiments based on simulated and real hyperspectral data sets. The experimental results demonstrate that the proposed method can improve the accuracy of subpixel mapping.

Linearized aerodynamic and control law models of the X-29A airplane and comparison with flight data

NASA Technical Reports Server (NTRS)

Bosworth, John T.

1992-01-01

Flight control system design and analysis for aircraft rely on mathematical models of the vehicle dynamics. In addition to a six degree of freedom nonlinear simulation, the X-29A flight controls group developed a set of programs that calculate linear perturbation models throughout the X-29A flight envelope. The models include the aerodynamics as well as flight control system dynamics and were used for stability, controllability, and handling qualities analysis. These linear models were compared to flight test results to help provide a safe flight envelope expansion. A description is given of the linear models at three flight conditions and two flight control system modes. The models are presented with a level of detail that would allow the reader to reproduce the linear results if desired. Comparison between the response of the linear model and flight measured responses are presented to demonstrate the strengths and weaknesses of the linear models' ability to predict flight dynamics.

Efficiency of energy conversion in model biological pumps. Optimization by linear nonequilibrium thermodynamic relations.

PubMed

Stucki, J W; Compiani, M; Caplan, S R

1983-09-01

Experimental investigations showed linear relations between flows and forces in some biological energy converters operating far from equilibrium. This observation cannot be understood on the basis of conventional nonequilibrium thermodynamics. Therefore, the efficiencies of a linear and a nonlinear mode of operation of an energy converter (a hypothetical redox-driven H+ pump) were compared. This comparison revealed that at physiological values of the forces and degrees of coupling (1) the force ratio permitting optimal efficiency was much higher in the linear than in the nonlinear mode and (2) the linear mode of operation was at least 10(6)-times more efficient that the nonlinear one. These observations suggest that the experimentally observed linear relations between flows and forces, particularly in the case of oxidative phosphorylation, may be due to a feedback regulation maintaining linear thermodynamic relations far from equilibrium. This regulation may have come about as the consequence of an evolutionary drive towards higher efficiency.

Computational process to study the wave propagation In a non-linear medium by quasi- linearization

NASA Astrophysics Data System (ADS)

Sharath Babu, K.; Venkata Brammam, J.; Baby Rani, CH

2018-03-01

Two objects having distinct velocities come into contact an impact can occur. The impact study i.e., in the displacement of the objects after the impact, the impact force is function of time‘t’ which is behaves similar to compression force. The impact tenure is very short so impulses must be generated subsequently high stresses are generated. In this work we are examined the wave propagation inside the object after collision and measured the object non-linear behavior in the one-dimensional case. Wave transmission is studied by means of material acoustic parameter value. The objective of this paper is to present a computational study of propagating pulsation and harmonic waves in nonlinear media using quasi-linearization and subsequently utilized the central difference scheme. This study gives focus on longitudinal, one- dimensional wave propagation. In the finite difference scheme Non-linear system is reduced to a linear system by applying quasi-linearization method. The computed results exhibit good agreement on par with the selected non-liner wave propagation.

Linearized Programming of Memristors for Artificial Neuro-Sensor Signal Processing.

PubMed

Yang, Changju; Kim, Hyongsuk

2016-08-19

A linearized programming method of memristor-based neural weights is proposed. Memristor is known as an ideal element to implement a neural synapse due to its embedded functions of analog memory and analog multiplication. Its resistance variation with a voltage input is generally a nonlinear function of time. Linearization of memristance variation about time is very important for the easiness of memristor programming. In this paper, a method utilizing an anti-serial architecture for linear programming is proposed. The anti-serial architecture is composed of two memristors with opposite polarities. It linearizes the variation of memristance due to complimentary actions of two memristors. For programming a memristor, additional memristor with opposite polarity is employed. The linearization effect of weight programming of an anti-serial architecture is investigated and memristor bridge synapse which is built with two sets of anti-serial memristor architecture is taken as an application example of the proposed method. Simulations are performed with memristors of both linear drift model and nonlinear model.

Evaluation of aircraft microwave data for locating zones for well stimulation and enhanced gas recovery. [Arkansas Arkoma Basin

NASA Technical Reports Server (NTRS)

Macdonald, H.; Waite, W.; Elachi, C.; Babcock, R.; Konig, R.; Gattis, J.; Borengasser, M.; Tolman, D.

1980-01-01

Imaging radar was evaluated as an adjunct to conventional petroleum exploration techniques, especially linear mapping. Linear features were mapped from several remote sensor data sources including stereo photography, enhanced LANDSAT imagery, SLAR radar imagery, enhanced SAR radar imagery, and SAR radar/LANDSAT combinations. Linear feature maps were compared with surface joint data, subsurface and geophysical data, and gas production in the Arkansas part of the Arkoma basin. The best LANDSAT enhanced product for linear detection was found to be a winter scene, band 7, uniform distribution stretch. Of the individual SAR data products, the VH (cross polarized) SAR radar mosaic provides for detection of most linears; however, none of the SAR enhancements is significantly better than the others. Radar/LANDSAT merges may provide better linear detection than a single sensor mapping mode, but because of operator variability, the results are inconclusive. Radar/LANDSAT combinations appear promising as an optimum linear mapping technique, if the advantages and disadvantages of each remote sensor are considered.

Design and performance testing of an ultrasonic linear motor with dual piezoelectric actuators.

PubMed

Smithmaitrie, Pruittikorn; Suybangdum, Panumas; Laoratanakul, Pitak; Muensit, Nantakan

2012-05-01

In this work, design and performance testing of an ultrasonic linear motor with dual piezoelectric actuator patches are studied. The motor system consists of a linear stator, a pre-load weight, and two piezoelectric actuator patches. The piezoelectric actuators are bonded with the linear elastic stator at specific locations. The stator generates propagating waves when the piezoelectric actuators are subjected to harmonic excitations. Vibration characteristics of the linear stator are analyzed and compared with finite element and experimental results. The analytical, finite element, and experimental results show agreement. In the experiments, performance of the ultrasonic linear motor is tested. Relationships between velocity and pre-load weight, velocity and applied voltage, driving force and applied voltage, and velocity and driving force are reported. The design of the dual piezoelectric actuators yields a simpler structure with a smaller number of actuators and lower stator stiffness compared with a conventional design of an ultrasonic linear motor with fully laminated piezoelectric actuators.

Anisotropies in the linear polarization of vacancy photoluminescence in diamond induced by crystal rotations and strong magnetic fields

NASA Astrophysics Data System (ADS)

Braukmann, D.; Popov, V. P.; Glaser, E. R.; Kennedy, T. A.; Bayer, M.; Debus, J.

2018-03-01

We study the linear polarization properties of the photoluminescence of ensembles of neutral and negatively charged nitrogen vacancies and neutral vacancies in diamond crystals as a function of their symmetry and their response to strong external magnetic fields. The linear polarization degree, which exceeds 10% at room temperature, and rotation of the polarization plane of their zero-phonon lines significantly depend on the crystal rotation around specific axes demonstrating anisotropic angular evolutions. The sign of the polarization plane rotation is changed periodically through the crystal rotation, which indicates a switching between electron excited states of orthogonal linear polarizations. At external magnetic fields of up to 10 T, the angular dependencies of the linear polarization degree experience a remarkable phase shift. Moreover, the rotation of the linear polarization plane increases linearly with rising magnetic field at 6 K and room temperature, for the negatively charged nitrogen vacancies, which is attributed to magneto-optical Faraday rotation.

Ranking Forestry Investments With Parametric Linear Programming

Treesearch

Paul A. Murphy

1976-01-01

Parametric linear programming is introduced as a technique for ranking forestry investments under multiple constraints; it combines the advantages of simple tanking and linear programming as capital budgeting tools.

Implementation of software-based sensor linearization algorithms on low-cost microcontrollers.

PubMed

Erdem, Hamit

2010-10-01

Nonlinear sensors and microcontrollers are used in many embedded system designs. As the input-output characteristic of most sensors is nonlinear in nature, obtaining data from a nonlinear sensor by using an integer microcontroller has always been a design challenge. This paper discusses the implementation of six software-based sensor linearization algorithms for low-cost microcontrollers. The comparative study of the linearization algorithms is performed by using a nonlinear optical distance-measuring sensor. The performance of the algorithms is examined with respect to memory space usage, linearization accuracy and algorithm execution time. The implementation and comparison results can be used for selection of a linearization algorithm based on the sensor transfer function, expected linearization accuracy and microcontroller capacity. Copyright © 2010 ISA. Published by Elsevier Ltd. All rights reserved.

Analysis of separation test for automatic brake adjuster based on linear radon transformation

NASA Astrophysics Data System (ADS)

Luo, Zai; Jiang, Wensong; Guo, Bin; Fan, Weijun; Lu, Yi

2015-01-01

The linear Radon transformation is applied to extract inflection points for online test system under the noise conditions. The linear Radon transformation has a strong ability of anti-noise and anti-interference by fitting the online test curve in several parts, which makes it easy to handle consecutive inflection points. We applied the linear Radon transformation to the separation test system to solve the separating clearance of automatic brake adjuster. The experimental results show that the feature point extraction error of the gradient maximum optimal method is approximately equal to ±0.100, while the feature point extraction error of linear Radon transformation method can reach to ±0.010, which has a lower error than the former one. In addition, the linear Radon transformation is robust.

Adjustment of Adaptive Gain with Bounded Linear Stability Analysis to Improve Time-Delay Margin for Metrics-Driven Adaptive Control

NASA Technical Reports Server (NTRS)

Bakhtiari-Nejad, Maryam; Nguyen, Nhan T.; Krishnakumar, Kalmanje Srinvas

2009-01-01

This paper presents the application of Bounded Linear Stability Analysis (BLSA) method for metrics driven adaptive control. The bounded linear stability analysis method is used for analyzing stability of adaptive control models, without linearizing the adaptive laws. Metrics-driven adaptive control introduces a notion that adaptation should be driven by some stability metrics to achieve robustness. By the application of bounded linear stability analysis method the adaptive gain is adjusted during the adaptation in order to meet certain phase margin requirements. Analysis of metrics-driven adaptive control is evaluated for a linear damaged twin-engine generic transport model of aircraft. The analysis shows that the system with the adjusted adaptive gain becomes more robust to unmodeled dynamics or time delay.

Non-linear interaction of a detonation/vorticity wave

NASA Technical Reports Server (NTRS)

Lasseigne, D. G.; Jackson, T. L.; Hussaini, M. Y.

1991-01-01

The interaction of an oblique, overdriven detonation wave with a vorticity disturbance is investigated by a direct two-dimensional numerical simulation using a multi-domain, finite-difference solution of the compressible Euler equations. The results are compared to those of linear theory, which predict that the effect of exothermicity on the interaction is relatively small except possibly near a critical angle where linear theory no longer holds. It is found that the steady-state computational results agree with the results of linear theory. However, for cases with incident angle near the critical angle, moderate disturbance amplitudes, and/or sudden transient encounter with a disturbance, the effects of exothermicity are more pronounced than predicted by linear theory. Finally, it is found that linear theory correctly determines the critical angle.

On supporting students' understanding of solving linear equation by using flowchart

NASA Astrophysics Data System (ADS)

Toyib, Muhamad; Kusmayadi, Tri Atmojo; Riyadi

2017-05-01

The aim of this study was to support 7th graders to gradually understand the concepts and procedures of solving linear equation. Thirty-two 7th graders of a Junior High School in Surakarta, Indonesia were involved in this study. Design research was used as the research approach to achieve the aim. A set of learning activities in solving linear equation with one unknown were designed based on Realistic Mathematics Education (RME) approach. The activities were started by playing LEGO to find a linear equation then solve the equation by using flowchart. The results indicate that using the realistic problems, playing LEGO could stimulate students to construct linear equation. Furthermore, Flowchart used to encourage students' reasoning and understanding on the concepts and procedures of solving linear equation with one unknown.

Design and analysis of linear cascade DNA hybridization chain reactions using DNA hairpins

NASA Astrophysics Data System (ADS)

Bui, Hieu; Garg, Sudhanshu; Miao, Vincent; Song, Tianqi; Mokhtar, Reem; Reif, John

2017-01-01

DNA self-assembly has been employed non-conventionally to construct nanoscale structures and dynamic nanoscale machines. The technique of hybridization chain reactions by triggered self-assembly has been shown to form various interesting nanoscale structures ranging from simple linear DNA oligomers to dendritic DNA structures. Inspired by earlier triggered self-assembly works, we present a system for controlled self-assembly of linear cascade DNA hybridization chain reactions using nine distinct DNA hairpins. NUPACK is employed to assist in designing DNA sequences and Matlab has been used to simulate DNA hairpin interactions. Gel electrophoresis and ensemble fluorescence reaction kinetics data indicate strong evidence of linear cascade DNA hybridization chain reactions. The half-time completion of the proposed linear cascade reactions indicates a linear dependency on the number of hairpins.

Constructing an Efficient Self-Tuning Aircraft Engine Model for Control and Health Management Applications

NASA Technical Reports Server (NTRS)

Armstrong, Jeffrey B.; Simon, Donald L.

2012-01-01

Self-tuning aircraft engine models can be applied for control and health management applications. The self-tuning feature of these models minimizes the mismatch between any given engine and the underlying engineering model describing an engine family. This paper provides details of the construction of a self-tuning engine model centered on a piecewise linear Kalman filter design. Starting from a nonlinear transient aerothermal model, a piecewise linear representation is first extracted. The linearization procedure creates a database of trim vectors and state-space matrices that are subsequently scheduled for interpolation based on engine operating point. A series of steady-state Kalman gains can next be constructed from a reduced-order form of the piecewise linear model. Reduction of the piecewise linear model to an observable dimension with respect to available sensed engine measurements can be achieved using either a subset or an optimal linear combination of "health" parameters, which describe engine performance. The resulting piecewise linear Kalman filter is then implemented for faster-than-real-time processing of sensed engine measurements, generating outputs appropriate for trending engine performance, estimating both measured and unmeasured parameters for control purposes, and performing on-board gas-path fault diagnostics. Computational efficiency is achieved by designing multidimensional interpolation algorithms that exploit the shared scheduling of multiple trim vectors and system matrices. An example application illustrates the accuracy of a self-tuning piecewise linear Kalman filter model when applied to a nonlinear turbofan engine simulation. Additional discussions focus on the issue of transient response accuracy and the advantages of a piecewise linear Kalman filter in the context of validation and verification. The techniques described provide a framework for constructing efficient self-tuning aircraft engine models from complex nonlinear simulations.Self-tuning aircraft engine models can be applied for control and health management applications. The self-tuning feature of these models minimizes the mismatch between any given engine and the underlying engineering model describing an engine family. This paper provides details of the construction of a self-tuning engine model centered on a piecewise linear Kalman filter design. Starting from a nonlinear transient aerothermal model, a piecewise linear representation is first extracted. The linearization procedure creates a database of trim vectors and state-space matrices that are subsequently scheduled for interpolation based on engine operating point. A series of steady-state Kalman gains can next be constructed from a reduced-order form of the piecewise linear model. Reduction of the piecewise linear model to an observable dimension with respect to available sensed engine measurements can be achieved using either a subset or an optimal linear combination of "health" parameters, which describe engine performance. The resulting piecewise linear Kalman filter is then implemented for faster-than-real-time processing of sensed engine measurements, generating outputs appropriate for trending engine performance, estimating both measured and unmeasured parameters for control purposes, and performing on-board gas-path fault diagnostics. Computational efficiency is achieved by designing multidimensional interpolation algorithms that exploit the shared scheduling of multiple trim vectors and system matrices. An example application illustrates the accuracy of a self-tuning piecewise linear Kalman filter model when applied to a nonlinear turbofan engine simulation. Additional discussions focus on the issue of transient response accuracy and the advantages of a piecewise linear Kalman filter in the context of validation and verification. The techniques described provide a framework for constructing efficient self-tuning aircraft engine models from complex nonlinear simulatns.

Intense beams at the micron level for the Next Linear Collider

DOE Office of Scientific and Technical Information (OSTI.GOV)

Seeman, J.T.

1991-08-01

High brightness beams with sub-micron dimensions are needed to produce a high luminosity for electron-positron collisions in the Next Linear Collider (NLC). To generate these small beam sizes, a large number of issues dealing with intense beams have to be resolved. Over the past few years many have been successfully addressed but most need experimental verification. Some of these issues are beam dynamics, emittance control, instrumentation, collimation, and beam-beam interactions. Recently, the Stanford Linear Collider (SLC) has proven the viability of linear collider technology and is an excellent test facility for future linear collider studies.

A computationally efficient scheme for the non-linear diffusion equation

NASA Astrophysics Data System (ADS)

Termonia, P.; Van de Vyver, H.

2009-04-01

This Letter proposes a new numerical scheme for integrating the non-linear diffusion equation. It is shown that it is linearly stable. Some tests are presented comparing this scheme to a popular decentered version of the linearized Crank-Nicholson scheme, showing that, although this scheme is slightly less accurate in treating the highly resolved waves, (i) the new scheme better treats highly non-linear systems, (ii) better handles the short waves, (iii) for a given test bed turns out to be three to four times more computationally cheap, and (iv) is easier in implementation.

Analysis, design, and testing of a low cost, direct force command linear proof mass actuator for structural control

NASA Technical Reports Server (NTRS)

Slater, G. L.; Shelley, Stuart; Jacobson, Mark

1993-01-01

In this paper, the design, analysis, and test of a low cost, linear proof mass actuator for vibration control is presented. The actuator is based on a linear induction coil from a large computer disk drive. Such disk drives are readily available and provide the linear actuator, current feedback amplifier, and power supply for a highly effective, yet inexpensive, experimental laboratory actuator. The device is implemented as a force command input system, and the performance is virtually the same as other, more sophisticated, linear proof mass systems.

Linear ordinary differential equations with constant coefficients. Revisiting the impulsive response method using factorization

NASA Astrophysics Data System (ADS)

Camporesi, Roberto

2011-06-01

We present an approach to the impulsive response method for solving linear constant-coefficient ordinary differential equations based on the factorization of the differential operator. The approach is elementary, we only assume a basic knowledge of calculus and linear algebra. In particular, we avoid the use of distribution theory, as well as of the other more advanced approaches: Laplace transform, linear systems, the general theory of linear equations with variable coefficients and the variation of constants method. The approach presented here can be used in a first course on differential equations for science and engineering majors.

Resultant as the determinant of a Koszul complex

NASA Astrophysics Data System (ADS)

Anokhina, A. S.; Morozov, A. Yu.; Shakirov, Sh. R.

2009-09-01

The determinant is a very important characteristic of a linear map between vector spaces. Two generalizations of linear maps are intensively used in modern theory: linear complexes (nilpotent chains of linear maps) and nonlinear maps. The determinant of a complex and the resultant are then the corresponding generalizations of the determinant of a linear map. It turns out that these two quantities are related: the resultant of a nonlinear map is the determinant of the corresponding Koszul complex. We give an elementary introduction into these notions and relations, which will definitely play a role in the future development of theoretical physics.

Linear phase compressive filter

DOEpatents

McEwan, T.E.

1995-06-06

A phase linear filter for soliton suppression is in the form of a laddered series of stages of non-commensurate low pass filters with each low pass filter having a series coupled inductance (L) and a reverse biased, voltage dependent varactor diode, to ground which acts as a variable capacitance (C). L and C values are set to levels which correspond to a linear or conventional phase linear filter. Inductance is mapped directly from that of an equivalent nonlinear transmission line and capacitance is mapped from the linear case using a large signal equivalent of a nonlinear transmission line. 2 figs.

Mixed Linear/Square-Root Encoded Single Slope Ramp Provides a Fast, Low Noise Analog to Digital Converter with Very High Linearity for Focal Plane Arrays

NASA Technical Reports Server (NTRS)

Wrigley, Christopher James (Inventor); Hancock, Bruce R. (Inventor); Cunningham, Thomas J. (Inventor); Newton, Kenneth W. (Inventor)

2014-01-01

An analog-to-digital converter (ADC) converts pixel voltages from a CMOS image into a digital output. A voltage ramp generator generates a voltage ramp that has a linear first portion and a non-linear second portion. A digital output generator generates a digital output based on the voltage ramp, the pixel voltages, and comparator output from an array of comparators that compare the voltage ramp to the pixel voltages. A return lookup table linearizes the digital output values.

On solutions of the fifth-order dispersive equations with porous medium type non-linearity

NASA Astrophysics Data System (ADS)

Kocak, Huseyin; Pinar, Zehra

2018-07-01

In this work, we focus on obtaining the exact solutions of the fifth-order semi-linear and non-linear dispersive partial differential equations, which have the second-order diffusion-like (porous-type) non-linearity. The proposed equations were not studied in the literature in the sense of the exact solutions. We reveal solutions of the proposed equations using the classical Riccati equations method. The obtained exact solutions, which can play a key role to simulate non-linear waves in the medium with dispersion and diffusion, are illustrated and discussed in details.

Visuo‐manual tracking: does intermittent control with aperiodic sampling explain linear power and non‐linear remnant without sensorimotor noise?

PubMed Central

Gawthrop, Peter J.; Lakie, Martin; Loram, Ian D.

2017-01-01

Key points A human controlling an external system is described most easily and conventionally as linearly and continuously translating sensory input to motor output, with the inevitable output remnant, non‐linearly related to the input, attributed to sensorimotor noise.Recent experiments show sustained manual tracking involves repeated refractoriness (insensitivity to sensory information for a certain duration), with the temporary 200–500 ms periods of irresponsiveness to sensory input making the control process intrinsically non‐linear.This evidence calls for re‐examination of the extent to which random sensorimotor noise is required to explain the non‐linear remnant.This investigation of manual tracking shows how the full motor output (linear component and remnant) can be explained mechanistically by aperiodic sampling triggered by prediction error thresholds.Whereas broadband physiological noise is general to all processes, aperiodic sampling is associated with sensorimotor decision making within specific frontal, striatal and parietal networks; we conclude that manual tracking utilises such slow serial decision making pathways up to several times per second. Abstract The human operator is described adequately by linear translation of sensory input to motor output. Motor output also always includes a non‐linear remnant resulting from random sensorimotor noise from multiple sources, and non‐linear input transformations, for example thresholds or refractory periods. Recent evidence showed that manual tracking incurs substantial, serial, refractoriness (insensitivity to sensory information of 350 and 550 ms for 1st and 2nd order systems respectively). Our two questions are: (i) What are the comparative merits of explaining the non‐linear remnant using noise or non‐linear transformations? (ii) Can non‐linear transformations represent serial motor decision making within the sensorimotor feedback loop intrinsic to tracking? Twelve participants (instructed to act in three prescribed ways) manually controlled two systems (1st and 2nd order) subject to a periodic multi‐sine disturbance. Joystick power was analysed using three models, continuous‐linear‐control (CC), continuous‐linear‐control with calculated noise spectrum (CCN), and intermittent control with aperiodic sampling triggered by prediction error thresholds (IC). Unlike the linear mechanism, the intermittent control mechanism explained the majority of total power (linear and remnant) (77–87% vs. 8–48%, IC vs. CC). Between conditions, IC used thresholds and distributions of open loop intervals consistent with, respectively, instructions and previous measured, model independent values; whereas CCN required changes in noise spectrum deviating from broadband, signal dependent noise. We conclude that manual tracking uses open loop predictive control with aperiodic sampling. Because aperiodic sampling is inherent to serial decision making within previously identified, specific frontal, striatal and parietal networks we suggest that these structures are intimately involved in visuo‐manual tracking. PMID:28833126

Protein linear indices of the 'macromolecular pseudograph alpha-carbon atom adjacency matrix' in bioinformatics. Part 1: prediction of protein stability effects of a complete set of alanine substitutions in Arc repressor.

PubMed

Marrero-Ponce, Yovani; Medina-Marrero, Ricardo; Castillo-Garit, Juan A; Romero-Zaldivar, Vicente; Torrens, Francisco; Castro, Eduardo A

2005-04-15

A novel approach to bio-macromolecular design from a linear algebra point of view is introduced. A protein's total (whole protein) and local (one or more amino acid) linear indices are a new set of bio-macromolecular descriptors of relevance to protein QSAR/QSPR studies. These amino-acid level biochemical descriptors are based on the calculation of linear maps on Rn[f k(xmi):Rn-->Rn] in canonical basis. These bio-macromolecular indices are calculated from the kth power of the macromolecular pseudograph alpha-carbon atom adjacency matrix. Total linear indices are linear functional on Rn. That is, the kth total linear indices are linear maps from Rn to the scalar R[f k(xm):Rn-->R]. Thus, the kth total linear indices are calculated by summing the amino-acid linear indices of all amino acids in the protein molecule. A study of the protein stability effects for a complete set of alanine substitutions in the Arc repressor illustrates this approach. A quantitative model that discriminates near wild-type stability alanine mutants from the reduced-stability ones in a training series was obtained. This model permitted the correct classification of 97.56% (40/41) and 91.67% (11/12) of proteins in the training and test set, respectively. It shows a high Matthews correlation coefficient (MCC=0.952) for the training set and an MCC=0.837 for the external prediction set. Additionally, canonical regression analysis corroborated the statistical quality of the classification model (Rcanc=0.824). This analysis was also used to compute biological stability canonical scores for each Arc alanine mutant. On the other hand, the linear piecewise regression model compared favorably with respect to the linear regression one on predicting the melting temperature (tm) of the Arc alanine mutants. The linear model explains almost 81% of the variance of the experimental tm (R=0.90 and s=4.29) and the LOO press statistics evidenced its predictive ability (q2=0.72 and scv=4.79). Moreover, the TOMOCOMD-CAMPS method produced a linear piecewise regression (R=0.97) between protein backbone descriptors and tm values for alanine mutants of the Arc repressor. A break-point value of 51.87 degrees C characterized two mutant clusters and coincided perfectly with the experimental scale. For this reason, we can use the linear discriminant analysis and piecewise models in combination to classify and predict the stability of the mutant Arc homodimers. These models also permitted the interpretation of the driving forces of such folding process, indicating that topologic/topographic protein backbone interactions control the stability profile of wild-type Arc and its alanine mutants.

Computer Program For Linear Algebra

NASA Technical Reports Server (NTRS)

Krogh, F. T.; Hanson, R. J.

1987-01-01

Collection of routines provided for basic vector operations. Basic Linear Algebra Subprogram (BLAS) library is collection from FORTRAN-callable routines for employing standard techniques to perform basic operations of numerical linear algebra.

Linear Accelerator (LINAC)

MedlinePlus

... equipment? How is safety ensured? What is this equipment used for? A linear accelerator (LINAC) is the ... Therapy (SBRT) . top of page How does the equipment work? The linear accelerator uses microwave technology (similar ...

State Estimation for Humanoid Robots

DTIC Science & Technology

2015-07-01

21 2.2.1 Linear Inverted Pendulum Model . . . . . . . . . . . . . . . . . . . 21 2.2.2 Planar Five-link Model...Linear Inverted Pendulum Model. LVDT Linear Variable Differential Transformers. MEMS Microelectromechanical Systems. MHE Moving Horizon Estimator. QP...

A linear programming manual

NASA Technical Reports Server (NTRS)

Tuey, R. C.

1972-01-01

Computer solutions of linear programming problems are outlined. Information covers vector spaces, convex sets, and matrix algebra elements for solving simultaneous linear equations. Dual problems, reduced cost analysis, ranges, and error analysis are illustrated.

Are Successive Investments in Education Equally Worthwhile? Endogenous Schooling Decisions and Non-Linearities in the Earnings-Schooling Relationship

ERIC Educational Resources Information Center

Skalli, Ali

2007-01-01

Most of the studies that account for the endogeneity bias when estimating the returns to schooling assume that the relationship between education and earnings is linear. Studies that assume the latter relationship to be non-linear simply ignore the endogeneity bias. Moreover, they either assume an ad-hoc non-linear relationship or argue that…

High Accuracy Attitude Control of a Spacecraft Using Feedback Linearization

DTIC Science & Technology

1992-05-01

High Accuracy Attitude Control of a Spacecraft Using Feedback Linearization A Thesis Presented by Louis Joseph PoehIman, Captain, USAF B.S., U.S. Air...High Accuracy Attitude Control of a Spacecraft Using Feedback Linearization by Louis Joseph Poehlman, Captain, USAF Submitted to the Department of...31 2-4 Attitude Determination and Control System Architecture ................. 33 3-1 Exact Linearization Using Nonlinear Feedback

Linear dynamic range enhancement in a CMOS imager

NASA Technical Reports Server (NTRS)

Pain, Bedabrata (Inventor)

2008-01-01

A CMOS imager with increased linear dynamic range but without degradation in noise, responsivity, linearity, fixed-pattern noise, or photometric calibration comprises a linear calibrated dual gain pixel in which the gain is reduced after a pre-defined threshold level by switching in an additional capacitance. The pixel may include a novel on-pixel latch circuit that is used to switch in the additional capacitance.

Neuromuscular Control of Rapid Linear Accelerations in Fish

DTIC Science & Technology

2016-06-22

2014 30-Apr-2015 Approved for Public Release; Distribution Unlimited Final Report: Neuromuscular Control of Rapid Linear Accelerations in Fish The...it does not display a currently valid OMB control number. PLEASE DO NOT RETURN YOUR FORM TO THE ABOVE ADDRESS. Tufts University Research... Control of Rapid Linear Accelerations in Fish Report Title In this project, we measured muscle activity, body movements, and flow patterns during linear

Evaluation of the Coreless Linear Conduction Pump for Thermoelectromagnetic Pumps,

DTIC Science & Technology

1991-08-01

Accession Number: 4466 Publication Date: Aug 01, 1991 Title: Evaluation of the Coreless Linear Conduction Pump for Thermoelectromagnetic Pumps ...083191 Report Prepared for: SDIO/T/SL, Washington, DC 20301-7100 Descriptors, Keywords: Coreless Linear Conduction Pump Thermoelectromagnetic...000001 Record ID: 26727 SUMMARY The purpose of the Coreless Linear Conduction Pump (CLCP) was to evaluate the feasibility of the CLCP as a means of

A Comparison of Linear versus Non-Linear Models of Aversive Self-Awareness, Dissociation, and Non-Suicidal Self-Injury among Young Adults

ERIC Educational Resources Information Center

Armey, Michael F.; Crowther, Janis H.

2008-01-01

Research has identified a significant increase in both the incidence and prevalence of non-suicidal self-injury (NSSI). The present study sought to test both linear and non-linear cusp catastrophe models by using aversive self-awareness, which was operationalized as a composite of aversive self-relevant affect and cognitions, and dissociation as…

Those Do What? Connecting Eigenvectors and Eigenvalues to the Rest of Linear Algebra: Using Visual Enhancements to Help Students Connect Eigenvectors to the Rest of Linear Algebra

ERIC Educational Resources Information Center

Nyman, Melvin A.; Lapp, Douglas A.; St. John, Dennis; Berry, John S.

2010-01-01

This paper discusses student difficulties in grasping concepts from Linear Algebra--in particular, the connection of eigenvalues and eigenvectors to other important topics in linear algebra. Based on our prior observations from student interviews, we propose technology-enhanced instructional approaches that might positively impact student…

Digital Image Restoration Under a Regression Model - The Unconstrained, Linear Equality and Inequality Constrained Approaches

DTIC Science & Technology

1974-01-01

REGRESSION MODEL - THE UNCONSTRAINED, LINEAR EQUALITY AND INEQUALITY CONSTRAINED APPROACHES January 1974 Nelson Delfino d’Avila Mascarenha;? Image...Report 520 DIGITAL IMAGE RESTORATION UNDER A REGRESSION MODEL THE UNCONSTRAINED, LINEAR EQUALITY AND INEQUALITY CONSTRAINED APPROACHES January...a two- dimensional form adequately describes the linear model . A dis- cretization is performed by using quadrature methods. By trans

Characterizing driver-response relationships in marine pelagic ecosystems for improved ocean management.

PubMed

Hunsicker, Mary E; Kappel, Carrie V; Selkoe, Kimberly A; Halpern, Benjamin S; Scarborough, Courtney; Mease, Lindley; Amrhein, Alisan

2016-04-01

Scientists and resource managers often use methods and tools that assume ecosystem components respond linearly to environmental drivers and human stressors. However, a growing body of literature demonstrates that many relationships are-non-linear, where small changes in a driver prompt a disproportionately large ecological response. We aim to provide a comprehensive assessment of the relationships between drivers and ecosystem components to identify where and when non-linearities are likely to occur. We focused our analyses on one of the best-studied marine systems, pelagic ecosystems, which allowed us to apply robust statistical techniques on a large pool of previously published studies. In this synthesis, we (1) conduct a wide literature review on single driver-response relationships in pelagic systems, (2) use statistical models to identify the degree of non-linearity in these relationships, and (3) assess whether general patterns exist in the strengths and shapes of non-linear relationships across drivers. Overall we found that non-linearities are common in pelagic ecosystems, comprising at least 52% of all driver-response relation- ships. This is likely an underestimate, as papers with higher quality data and analytical approaches reported non-linear relationships at a higher frequency (on average 11% more). Consequently, in the absence of evidence for a linear relationship, it is safer to assume a relationship is non-linear. Strong non-linearities can lead to greater ecological and socioeconomic consequences if they are unknown (and/or unanticipated), but if known they may provide clear thresholds to inform management targets. In pelagic systems, strongly non-linear relationships are often driven by climate and trophodynamic variables but are also associated with local stressors, such as overfishing and pollution, that can be more easily controlled by managers. Even when marine resource managers cannot influence ecosystem change, they can use information about threshold responses to guide how other stressors are managed and to adapt to new ocean conditions. As methods to detect and reduce uncertainty around threshold values improve, managers will be able to better understand and account for ubiquitous non-linear relationships.

On the interaction of small-scale linear waves with nonlinear solitary waves

NASA Astrophysics Data System (ADS)

Xu, Chengzhu; Stastna, Marek

2017-04-01

In the study of environmental and geophysical fluid flows, linear wave theory is well developed and its application has been considered for phenomena of various length and time scales. However, due to the nonlinear nature of fluid flows, in many cases results predicted by linear theory do not agree with observations. One of such cases is internal wave dynamics. While small-amplitude wave motion may be approximated by linear theory, large amplitude waves tend to be solitary-like. In some cases, when the wave is highly nonlinear, even weakly nonlinear theories fail to predict the wave properties correctly. We study the interaction of small-scale linear waves with nonlinear solitary waves using highly accurate pseudo spectral simulations that begin with a fully nonlinear solitary wave and a train of small-amplitude waves initialized from linear waves. The solitary wave then interacts with the linear waves through either an overtaking collision or a head-on collision. During the collision, there is a net energy transfer from the linear wave train to the solitary wave, resulting in an increase in the kinetic energy carried by the solitary wave and a phase shift of the solitary wave with respect to a freely propagating solitary wave. At the same time the linear waves are greatly reduced in amplitude. The percentage of energy transferred depends primarily on the wavelength of the linear waves. We found that after one full collision cycle, the longest waves may retain as much as 90% of the kinetic energy they had initially, while the shortest waves lose almost all of their initial energy. We also found that a head-on collision is more efficient in destroying the linear waves than an overtaking collision. On the other hand, the initial amplitude of the linear waves has very little impact on the percentage of energy that can be transferred to the solitary wave. Because of the nonlinearity of the solitary wave, these results provide us some insight into wave-mean flow interaction in a fully nonlinear framework.

A phenomenological biological dose model for proton therapy based on linear energy transfer spectra.

PubMed

Rørvik, Eivind; Thörnqvist, Sara; Stokkevåg, Camilla H; Dahle, Tordis J; Fjaera, Lars Fredrik; Ytre-Hauge, Kristian S

2017-06-01

The relative biological effectiveness (RBE) of protons varies with the radiation quality, quantified by the linear energy transfer (LET). Most phenomenological models employ a linear dependency of the dose-averaged LET (LET d ) to calculate the biological dose. However, several experiments have indicated a possible non-linear trend. Our aim was to investigate if biological dose models including non-linear LET dependencies should be considered, by introducing a LET spectrum based dose model. The RBE-LET relationship was investigated by fitting of polynomials from 1st to 5th degree to a database of 85 data points from aerobic in vitro experiments. We included both unweighted and weighted regression, the latter taking into account experimental uncertainties. Statistical testing was performed to decide whether higher degree polynomials provided better fits to the data as compared to lower degrees. The newly developed models were compared to three published LET d based models for a simulated spread out Bragg peak (SOBP) scenario. The statistical analysis of the weighted regression analysis favored a non-linear RBE-LET relationship, with the quartic polynomial found to best represent the experimental data (P = 0.010). The results of the unweighted regression analysis were on the borderline of statistical significance for non-linear functions (P = 0.053), and with the current database a linear dependency could not be rejected. For the SOBP scenario, the weighted non-linear model estimated a similar mean RBE value (1.14) compared to the three established models (1.13-1.17). The unweighted model calculated a considerably higher RBE value (1.22). The analysis indicated that non-linear models could give a better representation of the RBE-LET relationship. However, this is not decisive, as inclusion of the experimental uncertainties in the regression analysis had a significant impact on the determination and ranking of the models. As differences between the models were observed for the SOBP scenario, both non-linear LET spectrum- and linear LET d based models should be further evaluated in clinically realistic scenarios. © 2017 American Association of Physicists in Medicine.

Linear CCD attitude measurement system based on the identification of the auxiliary array CCD

NASA Astrophysics Data System (ADS)

Hu, Yinghui; Yuan, Feng; Li, Kai; Wang, Yan

2015-10-01

Object to the high precision flying target attitude measurement issues of a large space and large field of view, comparing existing measurement methods, the idea is proposed of using two array CCD to assist in identifying the three linear CCD with multi-cooperative target attitude measurement system, and to address the existing nonlinear system errors and calibration parameters and more problems with nine linear CCD spectroscopic test system of too complicated constraints among camera position caused by excessive. The mathematical model of binocular vision and three linear CCD test system are established, co-spot composition triangle utilize three red LED position light, three points' coordinates are given in advance by Cooperate Measuring Machine, the red LED in the composition of the three sides of a triangle adds three blue LED light points as an auxiliary, so that array CCD is easier to identify three red LED light points, and linear CCD camera is installed of a red filter to filter out the blue LED light points while reducing stray light. Using array CCD to measure the spot, identifying and calculating the spatial coordinates solutions of red LED light points, while utilizing linear CCD to measure three red LED spot for solving linear CCD test system, which can be drawn from 27 solution. Measured with array CCD coordinates auxiliary linear CCD has achieved spot identification, and has solved the difficult problems of multi-objective linear CCD identification. Unique combination of linear CCD imaging features, linear CCD special cylindrical lens system is developed using telecentric optical design, the energy center of the spot position in the depth range of convergence in the direction is perpendicular to the optical axis of the small changes ensuring highprecision image quality, and the entire test system improves spatial object attitude measurement speed and precision.

Universal Linear Fit Identification: A Method Independent of Data, Outliers and Noise Distribution Model and Free of Missing or Removed Data Imputation.

PubMed

Adikaram, K K L B; Hussein, M A; Effenberger, M; Becker, T

2015-01-01

Data processing requires a robust linear fit identification method. In this paper, we introduce a non-parametric robust linear fit identification method for time series. The method uses an indicator 2/n to identify linear fit, where n is number of terms in a series. The ratio Rmax of amax - amin and Sn - amin*n and that of Rmin of amax - amin and amax*n - Sn are always equal to 2/n, where amax is the maximum element, amin is the minimum element and Sn is the sum of all elements. If any series expected to follow y = c consists of data that do not agree with y = c form, Rmax > 2/n and Rmin > 2/n imply that the maximum and minimum elements, respectively, do not agree with linear fit. We define threshold values for outliers and noise detection as 2/n * (1 + k1) and 2/n * (1 + k2), respectively, where k1 > k2 and 0 ≤ k1 ≤ n/2 - 1. Given this relation and transformation technique, which transforms data into the form y = c, we show that removing all data that do not agree with linear fit is possible. Furthermore, the method is independent of the number of data points, missing data, removed data points and nature of distribution (Gaussian or non-Gaussian) of outliers, noise and clean data. These are major advantages over the existing linear fit methods. Since having a perfect linear relation between two variables in the real world is impossible, we used artificial data sets with extreme conditions to verify the method. The method detects the correct linear fit when the percentage of data agreeing with linear fit is less than 50%, and the deviation of data that do not agree with linear fit is very small, of the order of ±10-4%. The method results in incorrect detections only when numerical accuracy is insufficient in the calculation process.

Mathematical Model for the Contribution of Individual Organs to Non-Zero Y-Intercepts in Single and Multi-Compartment Linear Models of Whole-Body Energy Expenditure

PubMed Central

Kaiyala, Karl J.

2014-01-01

Mathematical models for the dependence of energy expenditure (EE) on body mass and composition are essential tools in metabolic phenotyping. EE scales over broad ranges of body mass as a non-linear allometric function. When considered within restricted ranges of body mass, however, allometric EE curves exhibit ‘local linearity.’ Indeed, modern EE analysis makes extensive use of linear models. Such models typically involve one or two body mass compartments (e.g., fat free mass and fat mass). Importantly, linear EE models typically involve a non-zero (usually positive) y-intercept term of uncertain origin, a recurring theme in discussions of EE analysis and a source of confounding in traditional ratio-based EE normalization. Emerging linear model approaches quantify whole-body resting EE (REE) in terms of individual organ masses (e.g., liver, kidneys, heart, brain). Proponents of individual organ REE modeling hypothesize that multi-organ linear models may eliminate non-zero y-intercepts. This could have advantages in adjusting REE for body mass and composition. Studies reveal that individual organ REE is an allometric function of total body mass. I exploit first-order Taylor linearization of individual organ REEs to model the manner in which individual organs contribute to whole-body REE and to the non-zero y-intercept in linear REE models. The model predicts that REE analysis at the individual organ-tissue level will not eliminate intercept terms. I demonstrate that the parameters of a linear EE equation can be transformed into the parameters of the underlying ‘latent’ allometric equation. This permits estimates of the allometric scaling of EE in a diverse variety of physiological states that are not represented in the allometric EE literature but are well represented by published linear EE analyses. PMID:25068692

Comparative Study of SVM Methods Combined with Voxel Selection for Object Category Classification on fMRI Data

PubMed Central

Song, Sutao; Zhan, Zhichao; Long, Zhiying; Zhang, Jiacai; Yao, Li

2011-01-01

Background Support vector machine (SVM) has been widely used as accurate and reliable method to decipher brain patterns from functional MRI (fMRI) data. Previous studies have not found a clear benefit for non-linear (polynomial kernel) SVM versus linear one. Here, a more effective non-linear SVM using radial basis function (RBF) kernel is compared with linear SVM. Different from traditional studies which focused either merely on the evaluation of different types of SVM or the voxel selection methods, we aimed to investigate the overall performance of linear and RBF SVM for fMRI classification together with voxel selection schemes on classification accuracy and time-consuming. Methodology/Principal Findings Six different voxel selection methods were employed to decide which voxels of fMRI data would be included in SVM classifiers with linear and RBF kernels in classifying 4-category objects. Then the overall performances of voxel selection and classification methods were compared. Results showed that: (1) Voxel selection had an important impact on the classification accuracy of the classifiers: in a relative low dimensional feature space, RBF SVM outperformed linear SVM significantly; in a relative high dimensional space, linear SVM performed better than its counterpart; (2) Considering the classification accuracy and time-consuming holistically, linear SVM with relative more voxels as features and RBF SVM with small set of voxels (after PCA) could achieve the better accuracy and cost shorter time. Conclusions/Significance The present work provides the first empirical result of linear and RBF SVM in classification of fMRI data, combined with voxel selection methods. Based on the findings, if only classification accuracy was concerned, RBF SVM with appropriate small voxels and linear SVM with relative more voxels were two suggested solutions; if users concerned more about the computational time, RBF SVM with relative small set of voxels when part of the principal components were kept as features was a better choice. PMID:21359184

Comparative study of SVM methods combined with voxel selection for object category classification on fMRI data.

PubMed

Song, Sutao; Zhan, Zhichao; Long, Zhiying; Zhang, Jiacai; Yao, Li

2011-02-16

Support vector machine (SVM) has been widely used as accurate and reliable method to decipher brain patterns from functional MRI (fMRI) data. Previous studies have not found a clear benefit for non-linear (polynomial kernel) SVM versus linear one. Here, a more effective non-linear SVM using radial basis function (RBF) kernel is compared with linear SVM. Different from traditional studies which focused either merely on the evaluation of different types of SVM or the voxel selection methods, we aimed to investigate the overall performance of linear and RBF SVM for fMRI classification together with voxel selection schemes on classification accuracy and time-consuming. Six different voxel selection methods were employed to decide which voxels of fMRI data would be included in SVM classifiers with linear and RBF kernels in classifying 4-category objects. Then the overall performances of voxel selection and classification methods were compared. Results showed that: (1) Voxel selection had an important impact on the classification accuracy of the classifiers: in a relative low dimensional feature space, RBF SVM outperformed linear SVM significantly; in a relative high dimensional space, linear SVM performed better than its counterpart; (2) Considering the classification accuracy and time-consuming holistically, linear SVM with relative more voxels as features and RBF SVM with small set of voxels (after PCA) could achieve the better accuracy and cost shorter time. The present work provides the first empirical result of linear and RBF SVM in classification of fMRI data, combined with voxel selection methods. Based on the findings, if only classification accuracy was concerned, RBF SVM with appropriate small voxels and linear SVM with relative more voxels were two suggested solutions; if users concerned more about the computational time, RBF SVM with relative small set of voxels when part of the principal components were kept as features was a better choice.

Frequency-domain full-waveform inversion with non-linear descent directions

NASA Astrophysics Data System (ADS)

Geng, Yu; Pan, Wenyong; Innanen, Kristopher A.

2018-05-01

Full-waveform inversion (FWI) is a highly non-linear inverse problem, normally solved iteratively, with each iteration involving an update constructed through linear operations on the residuals. Incorporating a flexible degree of non-linearity within each update may have important consequences for convergence rates, determination of low model wavenumbers and discrimination of parameters. We examine one approach for doing so, wherein higher order scattering terms are included within the sensitivity kernel during the construction of the descent direction, adjusting it away from that of the standard Gauss-Newton approach. These scattering terms are naturally admitted when we construct the sensitivity kernel by varying not the current but the to-be-updated model at each iteration. Linear and/or non-linear inverse scattering methodologies allow these additional sensitivity contributions to be computed from the current data residuals within any given update. We show that in the presence of pre-critical reflection data, the error in a second-order non-linear update to a background of s0 is, in our scheme, proportional to at most (Δs/s0)3 in the actual parameter jump Δs causing the reflection. In contrast, the error in a standard Gauss-Newton FWI update is proportional to (Δs/s0)2. For numerical implementation of more complex cases, we introduce a non-linear frequency-domain scheme, with an inner and an outer loop. A perturbation is determined from the data residuals within the inner loop, and a descent direction based on the resulting non-linear sensitivity kernel is computed in the outer loop. We examine the response of this non-linear FWI using acoustic single-parameter synthetics derived from the Marmousi model. The inverted results vary depending on data frequency ranges and initial models, but we conclude that the non-linear FWI has the capability to generate high-resolution model estimates in both shallow and deep regions, and to converge rapidly, relative to a benchmark FWI approach involving the standard gradient.

Predicting oropharyngeal tumor volume throughout the course of radiation therapy from pretreatment computed tomography data using general linear models.

PubMed

Yock, Adam D; Rao, Arvind; Dong, Lei; Beadle, Beth M; Garden, Adam S; Kudchadker, Rajat J; Court, Laurence E

2014-05-01

The purpose of this work was to develop and evaluate the accuracy of several predictive models of variation in tumor volume throughout the course of radiation therapy. Nineteen patients with oropharyngeal cancers were imaged daily with CT-on-rails for image-guided alignment per an institutional protocol. The daily volumes of 35 tumors in these 19 patients were determined and used to generate (1) a linear model in which tumor volume changed at a constant rate, (2) a general linear model that utilized the power fit relationship between the daily and initial tumor volumes, and (3) a functional general linear model that identified and exploited the primary modes of variation between time series describing the changing tumor volumes. Primary and nodal tumor volumes were examined separately. The accuracy of these models in predicting daily tumor volumes were compared with those of static and linear reference models using leave-one-out cross-validation. In predicting the daily volume of primary tumors, the general linear model and the functional general linear model were more accurate than the static reference model by 9.9% (range: -11.6%-23.8%) and 14.6% (range: -7.3%-27.5%), respectively, and were more accurate than the linear reference model by 14.2% (range: -6.8%-40.3%) and 13.1% (range: -1.5%-52.5%), respectively. In predicting the daily volume of nodal tumors, only the 14.4% (range: -11.1%-20.5%) improvement in accuracy of the functional general linear model compared to the static reference model was statistically significant. A general linear model and a functional general linear model trained on data from a small population of patients can predict the primary tumor volume throughout the course of radiation therapy with greater accuracy than standard reference models. These more accurate models may increase the prognostic value of information about the tumor garnered from pretreatment computed tomography images and facilitate improved treatment management.

Powerful Electromechanical Linear Actuator

NASA Technical Reports Server (NTRS)

Cowan, John R.; Myers, William N.

1994-01-01

Powerful electromechanical linear actuator designed to replace hydraulic actuator. Cleaner, simpler, and needs less maintenance. Features rotary-to-linear-motion converter with antibacklash gearing and position feedback via shaft-angle resolvers, which measure rotary motion.

40 CFR 60.667 - Chemicals affected by subpart NNN.

Code of Federal Regulations, 2010 CFR

2010-07-01

... alcohols, ethoxylated, mixed Linear alcohols, ethoxylated, and sulfated, sodium salt, mixed Linear alcohols, sulfated, sodium salt, mixed Linear alkylbenzene 123-01-3 Magnesium acetate 142-72-3 Maleic anhydride 108...

40 CFR 60.667 - Chemicals affected by subpart NNN.

Code of Federal Regulations, 2011 CFR

2011-07-01

... alcohols, ethoxylated, mixed Linear alcohols, ethoxylated, and sulfated, sodium salt, mixed Linear alcohols, sulfated, sodium salt, mixed Linear alkylbenzene 123-01-3 Magnesium acetate 142-72-3 Maleic anhydride 108...

The non-linear power spectrum of the Lyman alpha forest

DOE Office of Scientific and Technical Information (OSTI.GOV)

Arinyo-i-Prats, Andreu; Miralda-Escudé, Jordi; Viel, Matteo

2015-12-01

The Lyman alpha forest power spectrum has been measured on large scales by the BOSS survey in SDSS-III at z∼ 2.3, has been shown to agree well with linear theory predictions, and has provided the first measurement of Baryon Acoustic Oscillations at this redshift. However, the power at small scales, affected by non-linearities, has not been well examined so far. We present results from a variety of hydrodynamic simulations to predict the redshift space non-linear power spectrum of the Lyα transmission for several models, testing the dependence on resolution and box size. A new fitting formula is introduced to facilitate themore » comparison of our simulation results with observations and other simulations. The non-linear power spectrum has a generic shape determined by a transition scale from linear to non-linear anisotropy, and a Jeans scale below which the power drops rapidly. In addition, we predict the two linear bias factors of the Lyα forest and provide a better physical interpretation of their values and redshift evolution. The dependence of these bias factors and the non-linear power on the amplitude and slope of the primordial fluctuations power spectrum, the temperature-density relation of the intergalactic medium, and the mean Lyα transmission, as well as the redshift evolution, is investigated and discussed in detail. A preliminary comparison to the observations shows that the predicted redshift distortion parameter is in good agreement with the recent determination of Blomqvist et al., but the density bias factor is lower than observed. We make all our results publicly available in the form of tables of the non-linear power spectrum that is directly obtained from all our simulations, and parameters of our fitting formula.« less

The Role of Linear Acceleration in Visual-Vestibular Interactions and Implications in Aircraft Operations

NASA Technical Reports Server (NTRS)

Correia, Manning J.; Luke, Brian L.; McGrath, Braden J.; Clark, John B.; Rupert, Angus H.

1996-01-01

While considerable attention has been given to visual-vestibular interaction (VVI) during angular motion of the head as might occur during an aircraft spin, much less attention has been given to VVI during linear motion of the head. Such interaction might occur, for example, while viewing a stationary or moving display during vertical take-off and landing operations Research into linear VVI, particularly during prolonged periods of linear acceleration, has been hampered by the unavailability of a programmable translator capable of large excursions We collaborated with Otis Elevator Co. and used their research tower and elevator, whose motion could be digitally programmed, to vertically translate human subjects over a distance of 92.3 meters with a peak linear acceleration of 2 meters/sec(exp 2) During pulsatile or sinusoidal translation, the subjects viewed moving stripes (optokinetic stimulus) or a fixed point source (light emitting diode, led, display), respectively and it was generally found that. The direction of linear acceleration relative to the cardinal head axes and the direction of the slow component of optokinetic nystagmus (OKN) determined the extent of VVI during concomitant stripe motion and linear acceleration. Acceleration along the z head axis (A(sub z)) produced the largest VVI, particularly when the slow component of OKN was in the same direction as eye movements produced by the linear acceleration and Eye movements produced by linear acceleration are suppressed by viewing a fixed target at frequencies below 10 Hz But, above this frequency the suppression produced by VVI is removed. Finally, as demonstrated in non-human primates, vergence of the eyes appears to modulate the vertical eye movement response to linear acceleration in humans.

The Elementary Operations of Human Vision Are Not Reducible to Template-Matching

PubMed Central

Neri, Peter

2015-01-01

It is generally acknowledged that biological vision presents nonlinear characteristics, yet linear filtering accounts of visual processing are ubiquitous. The template-matching operation implemented by the linear-nonlinear cascade (linear filter followed by static nonlinearity) is the most widely adopted computational tool in systems neuroscience. This simple model achieves remarkable explanatory power while retaining analytical tractability, potentially extending its reach to a wide range of systems and levels in sensory processing. The extent of its applicability to human behaviour, however, remains unclear. Because sensory stimuli possess multiple attributes (e.g. position, orientation, size), the issue of applicability may be asked by considering each attribute one at a time in relation to a family of linear-nonlinear models, or by considering all attributes collectively in relation to a specified implementation of the linear-nonlinear cascade. We demonstrate that human visual processing can operate under conditions that are indistinguishable from linear-nonlinear transduction with respect to substantially different stimulus attributes of a uniquely specified target signal with associated behavioural task. However, no specific implementation of a linear-nonlinear cascade is able to account for the entire collection of results across attributes; a satisfactory account at this level requires the introduction of a small gain-control circuit, resulting in a model that no longer belongs to the linear-nonlinear family. Our results inform and constrain efforts at obtaining and interpreting comprehensive characterizations of the human sensory process by demonstrating its inescapably nonlinear nature, even under conditions that have been painstakingly fine-tuned to facilitate template-matching behaviour and to produce results that, at some level of inspection, do conform to linear filtering predictions. They also suggest that compliance with linear transduction may be the targeted outcome of carefully crafted nonlinear circuits, rather than default behaviour exhibited by basic components. PMID:26556758

Development of a Linear Stirling System Model with Varying Heat Inputs

NASA Technical Reports Server (NTRS)

Regan, Timothy F.; Lewandowski, Edward J.

2007-01-01

The linear model of the Stirling system developed by NASA Glenn Research Center (GRC) has been extended to include a user-specified heat input. Previously developed linear models were limited to the Stirling convertor and electrical load. They represented the thermodynamic cycle with pressure factors that remained constant. The numerical values of the pressure factors were generated by linearizing GRC's nonlinear System Dynamic Model (SDM) of the convertor at a chosen operating point. The pressure factors were fixed for that operating point, thus, the model lost accuracy if a transition to a different operating point were simulated. Although the previous linear model was used in developing controllers that manipulated current, voltage, and piston position, it could not be used in the development of control algorithms that regulated hot-end temperature. This basic model was extended to include the thermal dynamics associated with a hot-end temperature that varies over time in response to external changes as well as to changes in the Stirling cycle. The linear model described herein includes not only dynamics of the piston, displacer, gas, and electrical circuit, but also the transient effects of the heater head thermal inertia. The linear version algebraically couples two separate linear dynamic models, one model of the Stirling convertor and one model of the thermal system, through the pressure factors. The thermal system model includes heat flow of heat transfer fluid, insulation loss, and temperature drops from the heat source to the Stirling convertor expansion space. The linear model was compared to a nonlinear model, and performance was very similar. The resulting linear model can be implemented in a variety of computing environments, and is suitable for analysis with classical and state space controls analysis techniques.

Non-linear stochastic growth rates and redshift space distortions

DOE PAGES

Jennings, Elise; Jennings, David

2015-04-09

The linear growth rate is commonly defined through a simple deterministic relation between the velocity divergence and the matter overdensity in the linear regime. We introduce a formalism that extends this to a non-linear, stochastic relation between θ = ∇ ∙ v(x,t)/aH and δ. This provides a new phenomenological approach that examines the conditional mean , together with the fluctuations of θ around this mean. We also measure these stochastic components using N-body simulations and find they are non-negative and increase with decreasing scale from ~10 per cent at k < 0.2 h Mpc -1 to 25 per cent atmore » k ~ 0.45 h Mpc -1 at z = 0. Both the stochastic relation and non-linearity are more pronounced for haloes, M ≤ 5 × 10 12 M ⊙ h -1, compared to the dark matter at z = 0 and 1. Non-linear growth effects manifest themselves as a rotation of the mean away from the linear theory prediction -f LTδ, where f LT is the linear growth rate. This rotation increases with wavenumber, k, and we show that it can be well-described by second-order Lagrangian perturbation theory (2LPT) fork < 0.1 h Mpc -1. Furthermore, the stochasticity in the θ – δ relation is not so simply described by 2LPT, and we discuss its impact on measurements of f LT from two-point statistics in redshift space. Furthermore, given that the relationship between δ and θ is stochastic and non-linear, this will have implications for the interpretation and precision of f LT extracted using models which assume a linear, deterministic expression.« less

Axial linear patellar displacement: a new measurement of patellofemoral congruence.

PubMed

Urch, Scott E; Tritle, Benjamin A; Shelbourne, K Donald; Gray, Tinker

2009-05-01

The tools for measuring the congruence angle with digital radiography software can be difficult to use; therefore, the authors sought to develop a new, easy, and reliable method for measuring patellofemoral congruence. The abstract goes here and covers two columns. The abstract goes The linear displacement measurement will correlate well with the congruence angle measurement. here and covers two columns. Cohort study (diagnosis); Level of evidence, 2. On Merchant view radiographs obtained digitally, the authors measured the congruence angle and a new linear displacement measurement on preoperative and postoperative radiographs of 31 patients who suffered unilateral patellar dislocations and 100 uninjured subjects. The linear displacement measurement was obtained by drawing a reference line across the medial and lateral trochlear facets. Perpendicular lines were drawn from the depth of the sulcus through the reference line and from the apex of the posterior tip of the patella through the reference line. The distance between the perpendicular lines was the linear displacement measurement. The measurements were obtained twice at different sittings. The observer was blinded as to the previous measurements to establish reliability. Measurements were compared to determine whether the linear displacement measurement correlated with congruence angle. Intraobserver reliability was above r(2) = .90 for all measurements. In patients with patellar dislocations, the mean congruence angle preoperatively was 33.5 degrees , compared with 12.1 mm for linear displacement (r(2) = .92). The mean congruence angle postoperatively was 11.2 degrees, compared with 4.0 mm for linear displacement (r(2) = .89). For normal subjects, the mean congruence angle was -3 degrees and the mean linear displacement was 0.2 mm. The linear displacement measurement was found to correlate with congruence angle measurements and may be an easy and useful tool for clinicians to evaluate patellofemoral congruence objectively.

Estimating cosmic velocity fields from density fields and tidal tensors

NASA Astrophysics Data System (ADS)

Kitaura, Francisco-Shu; Angulo, Raul E.; Hoffman, Yehuda; Gottlöber, Stefan

2012-10-01

In this work we investigate the non-linear and non-local relation between cosmological density and peculiar velocity fields. Our goal is to provide an algorithm for the reconstruction of the non-linear velocity field from the fully non-linear density. We find that including the gravitational tidal field tensor using second-order Lagrangian perturbation theory based upon an estimate of the linear component of the non-linear density field significantly improves the estimate of the cosmic flow in comparison to linear theory not only in the low density, but also and more dramatically in the high-density regions. In particular we test two estimates of the linear component: the lognormal model and the iterative Lagrangian linearization. The present approach relies on a rigorous higher order Lagrangian perturbation theory analysis which incorporates a non-local relation. It does not require additional fitting from simulations being in this sense parameter free, it is independent of statistical-geometrical optimization and it is straightforward and efficient to compute. The method is demonstrated to yield an unbiased estimator of the velocity field on scales ≳5 h-1 Mpc with closely Gaussian distributed errors. Moreover, the statistics of the divergence of the peculiar velocity field is extremely well recovered showing a good agreement with the true one from N-body simulations. The typical errors of about 10 km s-1 (1σ confidence intervals) are reduced by more than 80 per cent with respect to linear theory in the scale range between 5 and 10 h-1 Mpc in high-density regions (δ > 2). We also find that iterative Lagrangian linearization is significantly superior in the low-density regime with respect to the lognormal model.

The Next Linear Collider Program

Science.gov Websites

The Next Linear Collider at SLAC Navbar NLC Playpen Warning: This page is provided as a place for Comments & Suggestions | Desktop Trouble Call | Linear Collider Group at FNAL || This page was updated

Estimating monotonic rates from biological data using local linear regression.

PubMed

Olito, Colin; White, Craig R; Marshall, Dustin J; Barneche, Diego R

2017-03-01

Accessing many fundamental questions in biology begins with empirical estimation of simple monotonic rates of underlying biological processes. Across a variety of disciplines, ranging from physiology to biogeochemistry, these rates are routinely estimated from non-linear and noisy time series data using linear regression and ad hoc manual truncation of non-linearities. Here, we introduce the R package LoLinR, a flexible toolkit to implement local linear regression techniques to objectively and reproducibly estimate monotonic biological rates from non-linear time series data, and demonstrate possible applications using metabolic rate data. LoLinR provides methods to easily and reliably estimate monotonic rates from time series data in a way that is statistically robust, facilitates reproducible research and is applicable to a wide variety of research disciplines in the biological sciences. © 2017. Published by The Company of Biologists Ltd.

Amplitudes for multiphoton quantum processes in linear optics

NASA Astrophysics Data System (ADS)

Urías, Jesús

2011-07-01

The prominent role that linear optical networks have acquired in the engineering of photon states calls for physically intuitive and automatic methods to compute the probability amplitudes for the multiphoton quantum processes occurring in linear optics. A version of Wick's theorem for the expectation value, on any vector state, of products of linear operators, in general, is proved. We use it to extract the combinatorics of any multiphoton quantum processes in linear optics. The result is presented as a concise rule to write down directly explicit formulae for the probability amplitude of any multiphoton process in linear optics. The rule achieves a considerable simplification and provides an intuitive physical insight about quantum multiphoton processes. The methodology is applied to the generation of high-photon-number entangled states by interferometrically mixing coherent light with spontaneously down-converted light.

Data-driven discovery of Koopman eigenfunctions using deep learning

NASA Astrophysics Data System (ADS)

Lusch, Bethany; Brunton, Steven L.; Kutz, J. Nathan

2017-11-01

Koopman operator theory transforms any autonomous non-linear dynamical system into an infinite-dimensional linear system. Since linear systems are well-understood, a mapping of non-linear dynamics to linear dynamics provides a powerful approach to understanding and controlling fluid flows. However, finding the correct change of variables remains an open challenge. We present a strategy to discover an approximate mapping using deep learning. Our neural networks find this change of variables, its inverse, and a finite-dimensional linear dynamical system defined on the new variables. Our method is completely data-driven and only requires measurements of the system, i.e. it does not require derivatives or knowledge of the governing equations. We find a minimal set of approximate Koopman eigenfunctions that are sufficient to reconstruct and advance the system to future states. We demonstrate the method on several dynamical systems.

gpICA: A Novel Nonlinear ICA Algorithm Using Geometric Linearization

NASA Astrophysics Data System (ADS)

Nguyen, Thang Viet; Patra, Jagdish Chandra; Emmanuel, Sabu

2006-12-01

A new geometric approach for nonlinear independent component analysis (ICA) is presented in this paper. Nonlinear environment is modeled by the popular post nonlinear (PNL) scheme. To eliminate the nonlinearity in the observed signals, a novel linearizing method named as geometric post nonlinear ICA (gpICA) is introduced. Thereafter, a basic linear ICA is applied on these linearized signals to estimate the unknown sources. The proposed method is motivated by the fact that in a multidimensional space, a nonlinear mixture is represented by a nonlinear surface while a linear mixture is represented by a plane, a special form of the surface. Therefore, by geometrically transforming the surface representing a nonlinear mixture into a plane, the mixture can be linearized. Through simulations on different data sets, superior performance of gpICA algorithm has been shown with respect to other algorithms.

Fourier imaging of non-linear structure formation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Brandbyge, Jacob; Hannestad, Steen, E-mail: jacobb@phys.au.dk, E-mail: sth@phys.au.dk

We perform a Fourier space decomposition of the dynamics of non-linear cosmological structure formation in ΛCDM models. From N -body simulations involving only cold dark matter we calculate 3-dimensional non-linear density, velocity divergence and vorticity Fourier realizations, and use these to calculate the fully non-linear mode coupling integrals in the corresponding fluid equations. Our approach allows for a reconstruction of the amount of mode coupling between any two wavenumbers as a function of redshift. With our Fourier decomposition method we identify the transfer of power from larger to smaller scales, the stable clustering regime, the scale where vorticity becomes important,more » and the suppression of the non-linear divergence power spectrum as compared to linear theory. Our results can be used to improve and calibrate semi-analytical structure formation models.« less

Prediction of Undsteady Flows in Turbomachinery Using the Linearized Euler Equations on Deforming Grids

NASA Technical Reports Server (NTRS)

Clark, William S.; Hall, Kenneth C.

1994-01-01

A linearized Euler solver for calculating unsteady flows in turbomachinery blade rows due to both incident gusts and blade motion is presented. The model accounts for blade loading, blade geometry, shock motion, and wake motion. Assuming that the unsteadiness in the flow is small relative to the nonlinear mean solution, the unsteady Euler equations can be linearized about the mean flow. This yields a set of linear variable coefficient equations that describe the small amplitude harmonic motion of the fluid. These linear equations are then discretized on a computational grid and solved using standard numerical techniques. For transonic flows, however, one must use a linear discretization which is a conservative linearization of the non-linear discretized Euler equations to ensure that shock impulse loads are accurately captured. Other important features of this analysis include a continuously deforming grid which eliminates extrapolation errors and hence, increases accuracy, and a new numerically exact, nonreflecting far-field boundary condition treatment based on an eigenanalysis of the discretized equations. Computational results are presented which demonstrate the computational accuracy and efficiency of the method and demonstrate the effectiveness of the deforming grid, far-field nonreflecting boundary conditions, and shock capturing techniques. A comparison of the present unsteady flow predictions to other numerical, semi-analytical, and experimental methods shows excellent agreement. In addition, the linearized Euler method presented requires one or two orders-of-magnitude less computational time than traditional time marching techniques making the present method a viable design tool for aeroelastic analyses.

Follow the line: Mysterious bright streaks on Dione and Rhea

NASA Astrophysics Data System (ADS)

Martin, E. S.; Patthoff, D. A.

2017-12-01

Our recent mapping of the wispy terrains of Saturn's moons Dione and Rhea has revealed unique linear features that are generally long (10s-100s km), narrow (1-10 km), brighter than the surrounding terrains, and their detection may be sensitive to lighting geometries. We refer to these features as `linear virgae.' Wherever linear virgae are observed, they appear to crosscut all other structures, suggesting that they are the youngest features on these satellites. Despite their young age and wide distribution, linear virgae on Rhea and Dione have largely been overlooked in the literature. Linear virgae on Dione have previously been identified in Voyager and Cassini Data, but their formation remains an open question. If linear virgae are found to be endogenic, it would suggest that the surfaces of Dione and Rhea have been active recently. Alternatively, if linear virgae are exogenic it would suggest that the surfaces have been modified by a possibly common mechanism. Further work would be necessary to determine both a source of material and the dynamical environment that could produce these features. Here we present detailed morphometric measurements to further constrain whether linear virgae on Rhea and Dione share common origins. We complete an in-depth assessment of the lighting geometries where these features are visible. If linear virgae in the Saturnian system show common morphologies and distributions, a new, recently active, possibly system-wide mechanism may be revealed, thereby improving our understanding of the recent dynamical environment around Saturn.

Improving the nutritional quality and shelf life of broiler meat by feeding diets supplemented with fermented pomegranate (Punica granatum L.) by-products.

PubMed

Ahmed, S T; Ko, S-Y; Yang, C-J

2017-12-01

1. Four experimental diets containing 0, 0.5, 1.0 and 2.0% fermented pomegranate by-products (FPB) were supplied to 320d-old broilers to evaluate the effects of FPB on growth performance, nutritional composition, fatty acid profile and oxidative stability of meat. 2. Dietary supplementation of FPB linearly increased the weight gain and feed intake of broilers with linear reduction in feed conversion ratio. 3. The crude protein, iron, magnesium, and sodium content were linearly higher, whereas cholesterol was linearly lower in the breast meat of FPB-supplemented broilers. In thigh meat, linearly lower ether extract and cholesterol with higher moisture was noted in response to increasing levels of FPB. 4. The proportion of saturated fatty acids was both linearly and quadratically lower in breast and thigh meat, whereas those of monounsaturated fatty acids of breast (linear and quadratic) and n-3 fatty acids of breast and thigh (linear) meat was higher in the FPB-supplemented broilers. The n-6/n-3 ratio of breast meat was linearly lower in response to FPB supplementation. The hypocholesterolaemic to hypercholesterolaemic ratio of thigh meat was higher in the FPB-supplemented groups. 5. The thiobarbituric acid reactive substances and pH value were lower in the breast and thigh meat of FPB-supplemented broilers. 6. Thus, additive supplementation of the diet with up to 2% FPB improved the nutritional quality, fatty acid profile and shelf life of broiler meat.

Linear morphoea follows Blaschko's lines.

PubMed

Weibel, L; Harper, J I

2008-07-01

The aetiology of morphoea (or localized scleroderma) remains unknown. It has previously been suggested that lesions of linear morphoea may follow Blaschko's lines and thus reflect an embryological development. However, the distribution of linear morphoea has never been accurately evaluated. We aimed to identify common patterns of clinical presentation in children with linear morphoea and to establish whether linear morphoea follows the lines of Blaschko. A retrospective chart review of 65 children with linear morphoea was performed. According to clinical photographs the skin lesions of these patients were plotted on to standardized head and body charts. With the aid of Adobe Illustrator a final figure was produced including an overlay of all individual lesions which was used for comparison with the published lines of Blaschko. Thirty-four (53%) patients had the en coup de sabre subtype, 27 (41%) presented with linear morphoea on the trunk and/or limbs and four (6%) children had a combination of the two. In 55 (85%) children the skin lesions were confined to one side of the body, showing no preference for either left or right side. On comparing the overlays of all body and head lesions with the original lines of Blaschko there was an excellent correlation. Our data indicate that linear morphoea follows the lines of Blaschko. We hypothesize that in patients with linear morphoea susceptible cells are present in a mosaic state and that exposure to some trigger factor may result in the development of this condition.

Local hyperspectral data multisharpening based on linear/linear-quadratic nonnegative matrix factorization by integrating lidar data

NASA Astrophysics Data System (ADS)

Benhalouche, Fatima Zohra; Karoui, Moussa Sofiane; Deville, Yannick; Ouamri, Abdelaziz

2015-10-01

In this paper, a new Spectral-Unmixing-based approach, using Nonnegative Matrix Factorization (NMF), is proposed to locally multi-sharpen hyperspectral data by integrating a Digital Surface Model (DSM) obtained from LIDAR data. In this new approach, the nature of the local mixing model is detected by using the local variance of the object elevations. The hyper/multispectral images are explored using small zones. In each zone, the variance of the object elevations is calculated from the DSM data in this zone. This variance is compared to a threshold value and the adequate linear/linearquadratic spectral unmixing technique is used in the considered zone to independently unmix hyperspectral and multispectral data, using an adequate linear/linear-quadratic NMF-based approach. The obtained spectral and spatial information thus respectively extracted from the hyper/multispectral images are then recombined in the considered zone, according to the selected mixing model. Experiments based on synthetic hyper/multispectral data are carried out to evaluate the performance of the proposed multi-sharpening approach and literature linear/linear-quadratic approaches used on the whole hyper/multispectral data. In these experiments, real DSM data are used to generate synthetic data containing linear and linear-quadratic mixed pixel zones. The DSM data are also used for locally detecting the nature of the mixing model in the proposed approach. Globally, the proposed approach yields good spatial and spectral fidelities for the multi-sharpened data and significantly outperforms the used literature methods.

Koopman Invariant Subspaces and Finite Linear Representations of Nonlinear Dynamical Systems for Control.

PubMed

Brunton, Steven L; Brunton, Bingni W; Proctor, Joshua L; Kutz, J Nathan

2016-01-01

In this wIn this work, we explore finite-dimensional linear representations of nonlinear dynamical systems by restricting the Koopman operator to an invariant subspace spanned by specially chosen observable functions. The Koopman operator is an infinite-dimensional linear operator that evolves functions of the state of a dynamical system. Dominant terms in the Koopman expansion are typically computed using dynamic mode decomposition (DMD). DMD uses linear measurements of the state variables, and it has recently been shown that this may be too restrictive for nonlinear systems. Choosing the right nonlinear observable functions to form an invariant subspace where it is possible to obtain linear reduced-order models, especially those that are useful for control, is an open challenge. Here, we investigate the choice of observable functions for Koopman analysis that enable the use of optimal linear control techniques on nonlinear problems. First, to include a cost on the state of the system, as in linear quadratic regulator (LQR) control, it is helpful to include these states in the observable subspace, as in DMD. However, we find that this is only possible when there is a single isolated fixed point, as systems with multiple fixed points or more complicated attractors are not globally topologically conjugate to a finite-dimensional linear system, and cannot be represented by a finite-dimensional linear Koopman subspace that includes the state. We then present a data-driven strategy to identify relevant observable functions for Koopman analysis by leveraging a new algorithm to determine relevant terms in a dynamical system by ℓ1-regularized regression of the data in a nonlinear function space; we also show how this algorithm is related to DMD. Finally, we demonstrate the usefulness of nonlinear observable subspaces in the design of Koopman operator optimal control laws for fully nonlinear systems using techniques from linear optimal control.ork, we explore finite-dimensional linear representations of nonlinear dynamical systems by restricting the Koopman operator to an invariant subspace spanned by specially chosen observable functions. The Koopman operator is an infinite-dimensional linear operator that evolves functions of the state of a dynamical system. Dominant terms in the Koopman expansion are typically computed using dynamic mode decomposition (DMD). DMD uses linear measurements of the state variables, and it has recently been shown that this may be too restrictive for nonlinear systems. Choosing the right nonlinear observable functions to form an invariant subspace where it is possible to obtain linear reduced-order models, especially those that are useful for control, is an open challenge. Here, we investigate the choice of observable functions for Koopman analysis that enable the use of optimal linear control techniques on nonlinear problems. First, to include a cost on the state of the system, as in linear quadratic regulator (LQR) control, it is helpful to include these states in the observable subspace, as in DMD. However, we find that this is only possible when there is a single isolated fixed point, as systems with multiple fixed points or more complicated attractors are not globally topologically conjugate to a finite-dimensional linear system, and cannot be represented by a finite-dimensional linear Koopman subspace that includes the state. We then present a data-driven strategy to identify relevant observable functions for Koopman analysis by leveraging a new algorithm to determine relevant terms in a dynamical system by ℓ1-regularized regression of the data in a nonlinear function space; we also show how this algorithm is related to DMD. Finally, we demonstrate the usefulness of nonlinear observable subspaces in the design of Koopman operator optimal control laws for fully nonlinear systems using techniques from linear optimal control.

A reducing of a chaotic movement to a periodic orbit, of a micro-electro-mechanical system, by using an optimal linear control design

NASA Astrophysics Data System (ADS)

Chavarette, Fábio Roberto; Balthazar, José Manoel; Felix, Jorge L. P.; Rafikov, Marat

2009-05-01

This paper analyzes the non-linear dynamics, with a chaotic behavior of a particular micro-electro-mechanical system. We used a technique of the optimal linear control for reducing the irregular (chaotic) oscillatory movement of the non-linear systems to a periodic orbit. We use the mathematical model of a (MEMS) proposed by Luo and Wang.

Schwarz maps of algebraic linear ordinary differential equations

NASA Astrophysics Data System (ADS)

Sanabria Malagón, Camilo

2017-12-01

A linear ordinary differential equation is called algebraic if all its solution are algebraic over its field of definition. In this paper we solve the problem of finding closed form solution to algebraic linear ordinary differential equations in terms of standard equations. Furthermore, we obtain a method to compute all algebraic linear ordinary differential equations with rational coefficients by studying their associated Schwarz map through the Picard-Vessiot Theory.

Lack of anomalous diffusion in linear translationally-invariant systems determined by only one initial condition

NASA Astrophysics Data System (ADS)

Khorrami, Mohammad; Shariati, Ahmad; Aghamohammadi, Amir; Fatollahi, Amir H.

2012-01-01

It is shown that as far as the linear diffusion equation meets both time- and space-translational invariance, the time dependence of a moment of degree α is a polynomial of degree at most equal to α, while all connected moments are at most linear functions of time. As a special case, the variance is an at most linear function of time.

The Matrix Pencil and its Applications to Speech Processing

DTIC Science & Technology

2007-03-01

Elementary Linear Algebra ” 8th edition, pp. 278, 2000 John Wiley & Sons, Inc., New York [37] Wai C. Chu, “Speech Coding Algorithms”, New Jeresy: John...Ben; Daniel, James W.; “Applied Linear Algebra ”, pp. 342-345, 1988 Prentice Hall, Englewood Cliffs, NJ [35] Haykin, Simon “Applied Linear Adaptive...ABSTRACT Matrix Pencils facilitate the study of differential equations resulting from oscillating systems. Certain problems in linear ordinary

Valuation of financial models with non-linear state spaces

NASA Astrophysics Data System (ADS)

Webber, Nick

2001-02-01

A common assumption in valuation models for derivative securities is that the underlying state variables take values in a linear state space. We discuss numerical implementation issues in an interest rate model with a simple non-linear state space, formulating and comparing Monte Carlo, finite difference and lattice numerical solution methods. We conclude that, at least in low dimensional spaces, non-linear interest rate models may be viable.

Informativeness of Wind Data in Linear Madden-Julian Oscillation Prediction

DTIC Science & Technology

2016-08-15

Linear inverse models (LIMs) are used to explore predictability and information content of the Madden–Julian Oscillation (MJO). Hindcast skill for...mostly at the largest scales, adds 1–2 days of skill. Keywords: linear inverse modeling; Madden–Julian Oscillation; sub-seasonal prediction 1...tion that may reflect on the MJO’s incompletely under- stood dynamics. Cavanaugh et al. (2014, hereafter C14) explored the skill of linear inverse

Optimization of isotherm models for pesticide sorption on biopolymer-nanoclay composite by error analysis.

PubMed

Narayanan, Neethu; Gupta, Suman; Gajbhiye, V T; Manjaiah, K M

2017-04-01

A carboxy methyl cellulose-nano organoclay (nano montmorillonite modified with 35-45 wt % dimethyl dialkyl (C 14 -C 18 ) amine (DMDA)) composite was prepared by solution intercalation method. The prepared composite was characterized by infrared spectroscopy (FTIR), X-Ray diffraction spectroscopy (XRD) and scanning electron microscopy (SEM). The composite was utilized for its pesticide sorption efficiency for atrazine, imidacloprid and thiamethoxam. The sorption data was fitted into Langmuir and Freundlich isotherms using linear and non linear methods. The linear regression method suggested best fitting of sorption data into Type II Langmuir and Freundlich isotherms. In order to avoid the bias resulting from linearization, seven different error parameters were also analyzed by non linear regression method. The non linear error analysis suggested that the sorption data fitted well into Langmuir model rather than in Freundlich model. The maximum sorption capacity, Q 0 (μg/g) was given by imidacloprid (2000) followed by thiamethoxam (1667) and atrazine (1429). The study suggests that the degree of determination of linear regression alone cannot be used for comparing the best fitting of Langmuir and Freundlich models and non-linear error analysis needs to be done to avoid inaccurate results. Copyright © 2017 Elsevier Ltd. All rights reserved.

Non-linear dual-phase-lag model for analyzing heat transfer phenomena in living tissues during thermal ablation.

PubMed

Kumar, P; Kumar, Dinesh; Rai, K N

2016-08-01

In this article, a non-linear dual-phase-lag (DPL) bio-heat transfer model based on temperature dependent metabolic heat generation rate is derived to analyze the heat transfer phenomena in living tissues during thermal ablation treatment. The numerical solution of the present non-linear problem has been done by finite element Runge-Kutta (4,5) method which combines the essence of Runge-Kutta (4,5) method together with finite difference scheme. Our study demonstrates that at the thermal ablation position temperature predicted by non-linear and linear DPL models show significant differences. A comparison has been made among non-linear DPL, thermal wave and Pennes model and it has been found that non-linear DPL and thermal wave bio-heat model show almost same nature whereas non-linear Pennes model shows significantly different temperature profile at the initial stage of thermal ablation treatment. The effect of Fourier number and Vernotte number (relaxation Fourier number) on temperature profile in presence and absence of externally applied heat source has been studied in detail and it has been observed that the presence of externally applied heat source term highly affects the efficiency of thermal treatment method. Copyright © 2016 Elsevier Ltd. All rights reserved.

A robust approach to measuring the detective quantum efficiency of radiographic detectors in a clinical setting

NASA Astrophysics Data System (ADS)

McDonald, Michael C.; Kim, H. K.; Henry, J. R.; Cunningham, I. A.

2012-03-01

The detective quantum efficiency (DQE) is widely accepted as a primary measure of x-ray detector performance in the scientific community. A standard method for measuring the DQE, based on IEC 62220-1, requires the system to have a linear response meaning that the detector output signals are proportional to the incident x-ray exposure. However, many systems have a non-linear response due to characteristics of the detector, or post processing of the detector signals, that cannot be disabled and may involve unknown algorithms considered proprietary by the manufacturer. For these reasons, the DQE has not been considered as a practical candidate for routine quality assurance testing in a clinical setting. In this article we described a method that can be used to measure the DQE of both linear and non-linear systems that employ only linear image processing algorithms. The method was validated on a Cesium Iodide based flat panel system that simultaneously stores a raw (linear) and processed (non-linear) image for each exposure. It was found that the resulting DQE was equivalent to a conventional standards-compliant DQE with measurement precision, and the gray-scale inversion and linear edge enhancement did not affect the DQE result. While not IEC 62220-1 compliant, it may be adequate for QA programs.

Monotonic non-linear transformations as a tool to investigate age-related effects on brain white matter integrity: A Box-Cox investigation.

PubMed

Morozova, Maria; Koschutnig, Karl; Klein, Elise; Wood, Guilherme

2016-01-15

Non-linear effects of age on white matter integrity are ubiquitous in the brain and indicate that these effects are more pronounced in certain brain regions at specific ages. Box-Cox analysis is a technique to increase the log-likelihood of linear relationships between variables by means of monotonic non-linear transformations. Here we employ Box-Cox transformations to flexibly and parsimoniously determine the degree of non-linearity of age-related effects on white matter integrity by means of model comparisons using a voxel-wise approach. Analysis of white matter integrity in a sample of adults between 20 and 89years of age (n=88) revealed that considerable portions of the white matter in the corpus callosum, cerebellum, pallidum, brainstem, superior occipito-frontal fascicle and optic radiation show non-linear effects of age. Global analyses revealed an increase in the average non-linearity from fractional anisotropy to radial diffusivity, axial diffusivity, and mean diffusivity. These results suggest that Box-Cox transformations are a useful and flexible tool to investigate more complex non-linear effects of age on white matter integrity and extend the functionality of the Box-Cox analysis in neuroimaging. Copyright © 2015 Elsevier Inc. All rights reserved.

ALPS: A Linear Program Solver

NASA Technical Reports Server (NTRS)

Ferencz, Donald C.; Viterna, Larry A.

1991-01-01

ALPS is a computer program which can be used to solve general linear program (optimization) problems. ALPS was designed for those who have minimal linear programming (LP) knowledge and features a menu-driven scheme to guide the user through the process of creating and solving LP formulations. Once created, the problems can be edited and stored in standard DOS ASCII files to provide portability to various word processors or even other linear programming packages. Unlike many math-oriented LP solvers, ALPS contains an LP parser that reads through the LP formulation and reports several types of errors to the user. ALPS provides a large amount of solution data which is often useful in problem solving. In addition to pure linear programs, ALPS can solve for integer, mixed integer, and binary type problems. Pure linear programs are solved with the revised simplex method. Integer or mixed integer programs are solved initially with the revised simplex, and the completed using the branch-and-bound technique. Binary programs are solved with the method of implicit enumeration. This manual describes how to use ALPS to create, edit, and solve linear programming problems. Instructions for installing ALPS on a PC compatible computer are included in the appendices along with a general introduction to linear programming. A programmers guide is also included for assistance in modifying and maintaining the program.

Least squares reconstruction of non-linear RF phase encoded MR data.

PubMed

Salajeghe, Somaie; Babyn, Paul; Sharp, Jonathan C; Sarty, Gordon E

2016-09-01

The numerical feasibility of reconstructing MRI signals generated by RF coils that produce B1 fields with a non-linearly varying spatial phase is explored. A global linear spatial phase variation of B1 is difficult to produce from current confined to RF coils. Here we use regularized least squares inversion, in place of the usual Fourier transform, to reconstruct signals generated in B1 fields with non-linear phase variation. RF encoded signals were simulated for three RF coil configurations: ideal linear, parallel conductors and, circular coil pairs. The simulated signals were reconstructed by Fourier transform and by regularized least squares. The Fourier reconstruction of simulated RF encoded signals from the parallel conductor coil set showed minor distortions over the reconstruction of signals from the ideal linear coil set but the Fourier reconstruction of signals from the circular coil set produced severe geometric distortion. Least squares inversion in all cases produced reconstruction errors comparable to the Fourier reconstruction of the simulated signal from the ideal linear coil set. MRI signals encoded in B1 fields with non-linearly varying spatial phase may be accurately reconstructed using regularized least squares thus pointing the way to the use of simple RF coil designs for RF encoded MRI. Crown Copyright © 2016. Published by Elsevier Inc. All rights reserved.

Does linear separability really matter? Complex visual search is explained by simple search

PubMed Central

Vighneshvel, T.; Arun, S. P.

2013-01-01

Visual search in real life involves complex displays with a target among multiple types of distracters, but in the laboratory, it is often tested using simple displays with identical distracters. Can complex search be understood in terms of simple searches? This link may not be straightforward if complex search has emergent properties. One such property is linear separability, whereby search is hard when a target cannot be separated from its distracters using a single linear boundary. However, evidence in favor of linear separability is based on testing stimulus configurations in an external parametric space that need not be related to their true perceptual representation. We therefore set out to assess whether linear separability influences complex search at all. Our null hypothesis was that complex search performance depends only on classical factors such as target-distracter similarity and distracter homogeneity, which we measured using simple searches. Across three experiments involving a variety of artificial and natural objects, differences between linearly separable and nonseparable searches were explained using target-distracter similarity and distracter heterogeneity. Further, simple searches accurately predicted complex search regardless of linear separability (r = 0.91). Our results show that complex search is explained by simple search, refuting the widely held belief that linear separability influences visual search. PMID:24029822

Multidimensional indexing structure for use with linear optimization queries

NASA Technical Reports Server (NTRS)

Bergman, Lawrence David (Inventor); Castelli, Vittorio (Inventor); Chang, Yuan-Chi (Inventor); Li, Chung-Sheng (Inventor); Smith, John Richard (Inventor)

2002-01-01

Linear optimization queries, which usually arise in various decision support and resource planning applications, are queries that retrieve top N data records (where N is an integer greater than zero) which satisfy a specific optimization criterion. The optimization criterion is to either maximize or minimize a linear equation. The coefficients of the linear equation are given at query time. Methods and apparatus are disclosed for constructing, maintaining and utilizing a multidimensional indexing structure of database records to improve the execution speed of linear optimization queries. Database records with numerical attributes are organized into a number of layers and each layer represents a geometric structure called convex hull. Such linear optimization queries are processed by searching from the outer-most layer of this multi-layer indexing structure inwards. At least one record per layer will satisfy the query criterion and the number of layers needed to be searched depends on the spatial distribution of records, the query-issued linear coefficients, and N, the number of records to be returned. When N is small compared to the total size of the database, answering the query typically requires searching only a small fraction of all relevant records, resulting in a tremendous speedup as compared to linearly scanning the entire dataset.

Comparison of linear and non-linear method in estimating the sorption isotherm parameters for safranin onto activated carbon.

PubMed

Kumar, K Vasanth; Sivanesan, S

2005-08-31

Comparison analysis of linear least square method and non-linear method for estimating the isotherm parameters was made using the experimental equilibrium data of safranin onto activated carbon at two different solution temperatures 305 and 313 K. Equilibrium data were fitted to Freundlich, Langmuir and Redlich-Peterson isotherm equations. All the three isotherm equations showed a better fit to the experimental equilibrium data. The results showed that non-linear method could be a better way to obtain the isotherm parameters. Redlich-Peterson isotherm is a special case of Langmuir isotherm when the Redlich-Peterson isotherm constant g was unity.

Miniaturized Stretchable and High-Rate Linear Supercapacitors

NASA Astrophysics Data System (ADS)

Zhu, Wenjun; Zhang, Yang; Zhou, Xiaoshuang; Xu, Jiang; Liu, Zunfeng; Yuan, Ningyi; Ding, Jianning

2017-07-01

Linear stretchable supercapacitors have attracted much attention because they are well suited to applications in the rapidly expanding field of wearable electronics. However, poor conductivity of the electrode material, which limits the transfer of electrons in the axial direction of the linear supercapacitors, leads to a serious loss of capacity at high rates. To solve this problem, we use gold nanoparticles to decorate aligned multiwall carbon nanotube to fabricate stretchable linear electrodes. Furthermore, we have developed fine stretchable linear supercapacitors, which exhibited an extremely high elasticity up to 400% strain with a high capacitance of about 8.7 F g-1 at the discharge current of 1 A g-1.

Miniaturized Stretchable and High-Rate Linear Supercapacitors.

PubMed

Zhu, Wenjun; Zhang, Yang; Zhou, Xiaoshuang; Xu, Jiang; Liu, Zunfeng; Yuan, Ningyi; Ding, Jianning

2017-12-01

Linear stretchable supercapacitors have attracted much attention because they are well suited to applications in the rapidly expanding field of wearable electronics. However, poor conductivity of the electrode material, which limits the transfer of electrons in the axial direction of the linear supercapacitors, leads to a serious loss of capacity at high rates. To solve this problem, we use gold nanoparticles to decorate aligned multiwall carbon nanotube to fabricate stretchable linear electrodes. Furthermore, we have developed fine stretchable linear supercapacitors, which exhibited an extremely high elasticity up to 400% strain with a high capacitance of about 8.7 F g -1 at the discharge current of 1 A g -1 .

Tip-tilt disturbance model identification based on non-linear least squares fitting for Linear Quadratic Gaussian control

NASA Astrophysics Data System (ADS)

Yang, Kangjian; Yang, Ping; Wang, Shuai; Dong, Lizhi; Xu, Bing

2018-05-01

We propose a method to identify tip-tilt disturbance model for Linear Quadratic Gaussian control. This identification method based on Levenberg-Marquardt method conducts with a little prior information and no auxiliary system and it is convenient to identify the tip-tilt disturbance model on-line for real-time control. This identification method makes it easy that Linear Quadratic Gaussian control runs efficiently in different adaptive optics systems for vibration mitigation. The validity of the Linear Quadratic Gaussian control associated with this tip-tilt disturbance model identification method is verified by experimental data, which is conducted in replay mode by simulation.

New exact solutions of the Tzitzéica-type equations in non-linear optics using the expa function method

NASA Astrophysics Data System (ADS)

Hosseini, K.; Ayati, Z.; Ansari, R.

2018-04-01

One specific class of non-linear evolution equations, known as the Tzitzéica-type equations, has received great attention from a group of researchers involved in non-linear science. In this article, new exact solutions of the Tzitzéica-type equations arising in non-linear optics, including the Tzitzéica, Dodd-Bullough-Mikhailov and Tzitzéica-Dodd-Bullough equations, are obtained using the expa function method. The integration technique actually suggests a useful and reliable method to extract new exact solutions of a wide range of non-linear evolution equations.

A study of the use of linear programming techniques to improve the performance in design optimization problems

NASA Technical Reports Server (NTRS)

Young, Katherine C.; Sobieszczanski-Sobieski, Jaroslaw

1988-01-01

This project has two objectives. The first is to determine whether linear programming techniques can improve performance when handling design optimization problems with a large number of design variables and constraints relative to the feasible directions algorithm. The second purpose is to determine whether using the Kreisselmeier-Steinhauser (KS) function to replace the constraints with one constraint will reduce the cost of total optimization. Comparisons are made using solutions obtained with linear and non-linear methods. The results indicate that there is no cost saving using the linear method or in using the KS function to replace constraints.

A fresh look at linear ordinary differential equations with constant coefficients. Revisiting the impulsive response method using factorization

NASA Astrophysics Data System (ADS)

Camporesi, Roberto

2016-01-01

We present an approach to the impulsive response method for solving linear constant-coefficient ordinary differential equations of any order based on the factorization of the differential operator. The approach is elementary, we only assume a basic knowledge of calculus and linear algebra. In particular, we avoid the use of distribution theory, as well as of the other more advanced approaches: Laplace transform, linear systems, the general theory of linear equations with variable coefficients and variation of parameters. The approach presented here can be used in a first course on differential equations for science and engineering majors.

Improved LTVMPC design for steering control of autonomous vehicle

NASA Astrophysics Data System (ADS)

Velhal, Shridhar; Thomas, Susy

2017-01-01

An improved linear time varying model predictive control for steering control of autonomous vehicle running on slippery road is presented. Control strategy is designed such that the vehicle will follow the predefined trajectory with highest possible entry speed. In linear time varying model predictive control, nonlinear vehicle model is successively linearized at each sampling instant. This linear time varying model is used to design MPC which will predict the future horizon. By incorporating predicted input horizon in each successive linearization the effectiveness of controller has been improved. The tracking performance using steering with front wheel and braking at four wheels are presented to illustrate the effectiveness of the proposed method.

Assessment of Ethylene Vinyl-Acetato Copolymer (EVA) Samples Bombarded by Gamma Radiation via Linearity Analyses

NASA Astrophysics Data System (ADS)

de Oliveira, L. N.; do Nascimento, E. O.; Schimidt, F.; Antonio, P. L.; Caldas, L. V. E.

2018-03-01

Materials with the potential to become dosimeters are of interest in radiation physics. In this research, the materials were analyzed and compared in relation to their linearity ranges. Samples of ethylene vinyl-acetate copolymer (EVA) were irradiated with doses from 10 Gy to 10 kGy using a 60Co Gamma-Cell system 220 and evaluated with the FTIR technique. The linearity analyses were applied through two methodologies, searching for linear regions in their response. The results show that both applied analyses indicate linear regions in defined dose interval. The radiation detectors EVA can be useful for radiation dosimetry in intermediate and high doses.

Fast linear feature detection using multiple directional non-maximum suppression.

PubMed

Sun, C; Vallotton, P

2009-05-01

The capacity to detect linear features is central to image analysis, computer vision and pattern recognition and has practical applications in areas such as neurite outgrowth detection, retinal vessel extraction, skin hair removal, plant root analysis and road detection. Linear feature detection often represents the starting point for image segmentation and image interpretation. In this paper, we present a new algorithm for linear feature detection using multiple directional non-maximum suppression with symmetry checking and gap linking. Given its low computational complexity, the algorithm is very fast. We show in several examples that it performs very well in terms of both sensitivity and continuity of detected linear features.

Analysis of ERTS-1 linear features in New York State

NASA Technical Reports Server (NTRS)

Isachsen, Y. W. (Principal Investigator); Fakundiny, R. H.; Forster, S. W.

1974-01-01

The author has identified the following significant results. All ERTS-1 linears confirmed to date have topographic expression although they may appear as featureless tonal linears on the imagery. A bias is unavoidably introduced against any linears which may parallel raster lines, lithological trends, or the azimuth of solar illumination. Ground study of ERTS-1 topographic lineaments in the Adirondacks indicates: outcrops along linears are even more rare than expected, fault breccias are found along some NNE lineaments, chloritization and slickensiding without brecciation characterize one EW lineament whereas closely-spaced jointing plus a zone of plastic shear define another. Field work in the Catskills suggests that the prominent new NNE lineaments may be surface manifestations of normal faulting in the basement, and that it may become possible to map major joint sets over extensive plateau regions directly on the imagery. Fall and winter images each display some unique linears, and long linears on the fall image commonly appear as aligned segments on the winter scene. A computer-processed color composite image permitted the extraction or additional information on the shaded side of mountains.

Decentralization, stabilization, and estimation of large-scale linear systems

NASA Technical Reports Server (NTRS)

Siljak, D. D.; Vukcevic, M. B.

1976-01-01

In this short paper we consider three closely related aspects of large-scale systems: decentralization, stabilization, and estimation. A method is proposed to decompose a large linear system into a number of interconnected subsystems with decentralized (scalar) inputs or outputs. The procedure is preliminary to the hierarchic stabilization and estimation of linear systems and is performed on the subsystem level. A multilevel control scheme based upon the decomposition-aggregation method is developed for stabilization of input-decentralized linear systems Local linear feedback controllers are used to stabilize each decoupled subsystem, while global linear feedback controllers are utilized to minimize the coupling effect among the subsystems. Systems stabilized by the method have a tolerance to a wide class of nonlinearities in subsystem coupling and high reliability with respect to structural perturbations. The proposed output-decentralization and stabilization schemes can be used directly to construct asymptotic state estimators for large linear systems on the subsystem level. The problem of dimensionality is resolved by constructing a number of low-order estimators, thus avoiding a design of a single estimator for the overall system.

`Un-Darkening' the Cosmos: New laws of physics for an expanding universe

NASA Astrophysics Data System (ADS)

George, William

2017-11-01

Dark matter is believed to exist because Newton's Laws are inconsistent with the visible matter in galaxies. Dark energy is necessary to explain the universe expansion. (also available from www.turbulence-online.com) suggested that the equations themselves might be in error because they implicitly assume that time is measured in linear increments. This presentation couples the possible non-linearity of time with an expanding universe. Maxwell's equations for an expanding universe with constant speed of light are shown to be invariant only if time itself is non-linear. Both linear and exponential expansion rates are considered. A linearly expanding universe corresponds to logarithmic time, while exponential expansion corresponds to exponentially varying time. Revised Newton's laws using either leads to different definitions of mass and kinetic energy, both of which appear time-dependent if expressed in linear time. And provide the possibility of explaining the astronomical observations without either dark matter or dark energy. We would have never noticed the differences on earth, since the leading term in both expansions is linear in δ /to where to is the current age.

Sum-of-Squares-Based Region of Attraction Analysis for Gain-Scheduled Three-Loop Autopilot

NASA Astrophysics Data System (ADS)

Seo, Min-Won; Kwon, Hyuck-Hoon; Choi, Han-Lim

2018-04-01

A conventional method of designing a missile autopilot is to linearize the original nonlinear dynamics at several trim points, then to determine linear controllers for each linearized model, and finally implement gain-scheduling technique. The validation of such a controller is often based on linear system analysis for the linear closed-loop system at the trim conditions. Although this type of gain-scheduled linear autopilot works well in practice, validation based solely on linear analysis may not be sufficient to fully characterize the closed-loop system especially when the aerodynamic coefficients exhibit substantial nonlinearity with respect to the flight condition. The purpose of this paper is to present a methodology for analyzing the stability of a gain-scheduled controller in a setting close to the original nonlinear setting. The method is based on sum-of-squares (SOS) optimization that can be used to characterize the region of attraction of a polynomial system by solving convex optimization problems. The applicability of the proposed SOS-based methodology is verified on a short-period autopilot of a skid-to-turn missile.

Frequency Response of Synthetic Vocal Fold Models with Linear and Nonlinear Material Properties

PubMed Central

Shaw, Stephanie M.; Thomson, Scott L.; Dromey, Christopher; Smith, Simeon

2014-01-01

Purpose The purpose of this study was to create synthetic vocal fold models with nonlinear stress-strain properties and to investigate the effect of linear versus nonlinear material properties on fundamental frequency during anterior-posterior stretching. Method Three materially linear and three materially nonlinear models were created and stretched up to 10 mm in 1 mm increments. Phonation onset pressure (Pon) and fundamental frequency (F0) at Pon were recorded for each length. Measurements were repeated as the models were relaxed in 1 mm increments back to their resting lengths, and tensile tests were conducted to determine the stress-strain responses of linear versus nonlinear models. Results Nonlinear models demonstrated a more substantial frequency response than did linear models and a more predictable pattern of F0 increase with respect to increasing length (although range was inconsistent across models). Pon generally increased with increasing vocal fold length for nonlinear models, whereas for linear models, Pon decreased with increasing length. Conclusions Nonlinear synthetic models appear to more accurately represent the human vocal folds than linear models, especially with respect to F0 response. PMID:22271874

Is the local linearity of space-time inherited from the linearity of probabilities?

NASA Astrophysics Data System (ADS)

Müller, Markus P.; Carrozza, Sylvain; Höhn, Philipp A.

2017-02-01

The appearance of linear spaces, describing physical quantities by vectors and tensors, is ubiquitous in all of physics, from classical mechanics to the modern notion of local Lorentz invariance. However, as natural as this seems to the physicist, most computer scientists would argue that something like a ‘local linear tangent space’ is not very typical and in fact a quite surprising property of any conceivable world or algorithm. In this paper, we take the perspective of the computer scientist seriously, and ask whether there could be any inherently information-theoretic reason to expect this notion of linearity to appear in physics. We give a series of simple arguments, spanning quantum information theory, group representation theory, and renormalization in quantum gravity, that supports a surprising thesis: namely, that the local linearity of space-time might ultimately be a consequence of the linearity of probabilities. While our arguments involve a fair amount of speculation, they have the virtue of being independent of any detailed assumptions on quantum gravity, and they are in harmony with several independent recent ideas on emergent space-time in high-energy physics.

Linear monogamy of entanglement in three-qubit systems

NASA Astrophysics Data System (ADS)

Liu, Feng; Gao, Fei; Wen, Qiao-Yan

2015-11-01

For any three-qubit quantum systems ABC, Oliveira et al. numerically found that both the concurrence and the entanglement of formation (EoF) obey the linear monogamy relations in pure states. They also conjectured that the linear monogamy relations can be saturated when the focus qubit A is maximally entangled with the joint qubits BC. In this work, we prove analytically that both the concurrence and EoF obey linear monogamy relations in an arbitrary three-qubit state. Furthermore, we verify that all three-qubit pure states are maximally entangled in the bipartition A|BC when they saturate the linear monogamy relations. We also study the distribution of the concurrence and EoF. More specifically, when the amount of entanglement between A and B equals to that of A and C, we show that the sum of EoF itself saturates the linear monogamy relation, while the sum of the squared EoF is minimum. Different from EoF, the concurrence and the squared concurrence both saturate the linear monogamy relations when the entanglement between A and B equals to that of A and C.

A Technique of Fuzzy C-Mean in Multiple Linear Regression Model toward Paddy Yield

NASA Astrophysics Data System (ADS)

Syazwan Wahab, Nur; Saifullah Rusiman, Mohd; Mohamad, Mahathir; Amira Azmi, Nur; Che Him, Norziha; Ghazali Kamardan, M.; Ali, Maselan

2018-04-01

In this paper, we propose a hybrid model which is a combination of multiple linear regression model and fuzzy c-means method. This research involved a relationship between 20 variates of the top soil that are analyzed prior to planting of paddy yields at standard fertilizer rates. Data used were from the multi-location trials for rice carried out by MARDI at major paddy granary in Peninsular Malaysia during the period from 2009 to 2012. Missing observations were estimated using mean estimation techniques. The data were analyzed using multiple linear regression model and a combination of multiple linear regression model and fuzzy c-means method. Analysis of normality and multicollinearity indicate that the data is normally scattered without multicollinearity among independent variables. Analysis of fuzzy c-means cluster the yield of paddy into two clusters before the multiple linear regression model can be used. The comparison between two method indicate that the hybrid of multiple linear regression model and fuzzy c-means method outperform the multiple linear regression model with lower value of mean square error.

Object matching using a locally affine invariant and linear programming techniques.

PubMed

Li, Hongsheng; Huang, Xiaolei; He, Lei

2013-02-01

In this paper, we introduce a new matching method based on a novel locally affine-invariant geometric constraint and linear programming techniques. To model and solve the matching problem in a linear programming formulation, all geometric constraints should be able to be exactly or approximately reformulated into a linear form. This is a major difficulty for this kind of matching algorithm. We propose a novel locally affine-invariant constraint which can be exactly linearized and requires a lot fewer auxiliary variables than other linear programming-based methods do. The key idea behind it is that each point in the template point set can be exactly represented by an affine combination of its neighboring points, whose weights can be solved easily by least squares. Errors of reconstructing each matched point using such weights are used to penalize the disagreement of geometric relationships between the template points and the matched points. The resulting overall objective function can be solved efficiently by linear programming techniques. Our experimental results on both rigid and nonrigid object matching show the effectiveness of the proposed algorithm.

Real-time solution of linear computational problems using databases of parametric reduced-order models with arbitrary underlying meshes

NASA Astrophysics Data System (ADS)

Amsallem, David; Tezaur, Radek; Farhat, Charbel

2016-12-01

A comprehensive approach for real-time computations using a database of parametric, linear, projection-based reduced-order models (ROMs) based on arbitrary underlying meshes is proposed. In the offline phase of this approach, the parameter space is sampled and linear ROMs defined by linear reduced operators are pre-computed at the sampled parameter points and stored. Then, these operators and associated ROMs are transformed into counterparts that satisfy a certain notion of consistency. In the online phase of this approach, a linear ROM is constructed in real-time at a queried but unsampled parameter point by interpolating the pre-computed linear reduced operators on matrix manifolds and therefore computing an interpolated linear ROM. The proposed overall model reduction framework is illustrated with two applications: a parametric inverse acoustic scattering problem associated with a mockup submarine, and a parametric flutter prediction problem associated with a wing-tank system. The second application is implemented on a mobile device, illustrating the capability of the proposed computational framework to operate in real-time.

Pressure fluctuations and time scales in turbulent channel flow

NASA Astrophysics Data System (ADS)

Septham, Kamthon; Morrison, Jonathan; Diwan, Sourabh

2015-11-01

Pressure fluctuations in turbulent channel flow subjected to globally stabilising linear feedback control are investigated at Reτ = 400 . The passivity-based control is adopted and explained by the conservative characteristics of the nonlinear terms contributing to the Reynolds-Orr equation (Sharma et al. Phys. Fluids 2011). The linear control operates via vU' ; the maximum forcing is located at y+ ~ 20 , corresponding to the location of the maximum in the mean-square pressure gradient. The responses of the rapid (linear) and slow (nonlinear) pressure fluctuations to the linear control are investigated using the Green's function representations. It demonstrates that the linear control operates via the linear source terms of the Poisson equation for pressure fluctuations. Landahl's timescales of the minimal flow unit (MFU) in turbulent channel flow are examined at y+ = 20 . It shows that the timescales of MFU agree well with the theoretical values proposed by Landahl (1993). Therefore, the effectiveness of the linear control to attenuate wall turbulence is explained by Landahl's theory for timescales, in that the control proceeds via the shear interaction timescale which is significantly shorter than both the nonlinear and viscous timescales.

Amesos2 and Belos: Direct and Iterative Solvers for Large Sparse Linear Systems

DOE PAGES

Bavier, Eric; Hoemmen, Mark; Rajamanickam, Sivasankaran; ...

2012-01-01

Solvers for large sparse linear systems come in two categories: direct and iterative. Amesos2, a package in the Trilinos software project, provides direct methods, and Belos, another Trilinos package, provides iterative methods. Amesos2 offers a common interface to many different sparse matrix factorization codes, and can handle any implementation of sparse matrices and vectors, via an easy-to-extend C++ traits interface. It can also factor matrices whose entries have arbitrary “Scalar” type, enabling extended-precision and mixed-precision algorithms. Belos includes many different iterative methods for solving large sparse linear systems and least-squares problems. Unlike competing iterative solver libraries, Belos completely decouples themore » algorithms from the implementations of the underlying linear algebra objects. This lets Belos exploit the latest hardware without changes to the code. Belos favors algorithms that solve higher-level problems, such as multiple simultaneous linear systems and sequences of related linear systems, faster than standard algorithms. The package also supports extended-precision and mixed-precision algorithms. Together, Amesos2 and Belos form a complete suite of sparse linear solvers.« less

A simple linear regression method for quantitative trait loci linkage analysis with censored observations.

PubMed

Anderson, Carl A; McRae, Allan F; Visscher, Peter M

2006-07-01

Standard quantitative trait loci (QTL) mapping techniques commonly assume that the trait is both fully observed and normally distributed. When considering survival or age-at-onset traits these assumptions are often incorrect. Methods have been developed to map QTL for survival traits; however, they are both computationally intensive and not available in standard genome analysis software packages. We propose a grouped linear regression method for the analysis of continuous survival data. Using simulation we compare this method to both the Cox and Weibull proportional hazards models and a standard linear regression method that ignores censoring. The grouped linear regression method is of equivalent power to both the Cox and Weibull proportional hazards methods and is significantly better than the standard linear regression method when censored observations are present. The method is also robust to the proportion of censored individuals and the underlying distribution of the trait. On the basis of linear regression methodology, the grouped linear regression model is computationally simple and fast and can be implemented readily in freely available statistical software.

Frequency response of synthetic vocal fold models with linear and nonlinear material properties.

PubMed

Shaw, Stephanie M; Thomson, Scott L; Dromey, Christopher; Smith, Simeon

2012-10-01

The purpose of this study was to create synthetic vocal fold models with nonlinear stress-strain properties and to investigate the effect of linear versus nonlinear material properties on fundamental frequency (F0) during anterior-posterior stretching. Three materially linear and 3 materially nonlinear models were created and stretched up to 10 mm in 1-mm increments. Phonation onset pressure (Pon) and F0 at Pon were recorded for each length. Measurements were repeated as the models were relaxed in 1-mm increments back to their resting lengths, and tensile tests were conducted to determine the stress-strain responses of linear versus nonlinear models. Nonlinear models demonstrated a more substantial frequency response than did linear models and a more predictable pattern of F0 increase with respect to increasing length (although range was inconsistent across models). Pon generally increased with increasing vocal fold length for nonlinear models, whereas for linear models, Pon decreased with increasing length. Nonlinear synthetic models appear to more accurately represent the human vocal folds than do linear models, especially with respect to F0 response.

Linear monogamy of entanglement in three-qubit systems.

PubMed

Liu, Feng; Gao, Fei; Wen, Qiao-Yan

2015-11-16

For any three-qubit quantum systems ABC, Oliveira et al. numerically found that both the concurrence and the entanglement of formation (EoF) obey the linear monogamy relations in pure states. They also conjectured that the linear monogamy relations can be saturated when the focus qubit A is maximally entangled with the joint qubits BC. In this work, we prove analytically that both the concurrence and EoF obey linear monogamy relations in an arbitrary three-qubit state. Furthermore, we verify that all three-qubit pure states are maximally entangled in the bipartition A|BC when they saturate the linear monogamy relations. We also study the distribution of the concurrence and EoF. More specifically, when the amount of entanglement between A and B equals to that of A and C, we show that the sum of EoF itself saturates the linear monogamy relation, while the sum of the squared EoF is minimum. Different from EoF, the concurrence and the squared concurrence both saturate the linear monogamy relations when the entanglement between A and B equals to that of A and C.

Linear monogamy of entanglement in three-qubit systems

PubMed Central

Liu, Feng; Gao, Fei; Wen, Qiao-Yan

2015-01-01

For any three-qubit quantum systems ABC, Oliveira et al. numerically found that both the concurrence and the entanglement of formation (EoF) obey the linear monogamy relations in pure states. They also conjectured that the linear monogamy relations can be saturated when the focus qubit A is maximally entangled with the joint qubits BC. In this work, we prove analytically that both the concurrence and EoF obey linear monogamy relations in an arbitrary three-qubit state. Furthermore, we verify that all three-qubit pure states are maximally entangled in the bipartition A|BC when they saturate the linear monogamy relations. We also study the distribution of the concurrence and EoF. More specifically, when the amount of entanglement between A and B equals to that of A and C, we show that the sum of EoF itself saturates the linear monogamy relation, while the sum of the squared EoF is minimum. Different from EoF, the concurrence and the squared concurrence both saturate the linear monogamy relations when the entanglement between A and B equals to that of A and C. PMID:26568265

Dynamic constitutional frameworks for DNA biomimetic recognition.

PubMed

Catana, Romina; Barboiu, Mihail; Moleavin, Ioana; Clima, Lilia; Rotaru, Alexandru; Ursu, Elena-Laura; Pinteala, Mariana

2015-02-07

Linear and cross-linked dynamic constitutional frameworks generated from reversibly interacting linear PEG/core constituents and cationic sites shed light on the dominant coiling versus linear DNA binding behaviours, closer to the histone DNA binding wrapping mechanism.

Unsymmetrical squaraines for nonlinear optical materials

NASA Technical Reports Server (NTRS)

Marder, Seth R. (Inventor); Chen, Chin-Ti (Inventor); Cheng, Lap-Tak (Inventor)

1996-01-01

Compositions for use in non-linear optical devices. The compositions have first molecular electronic hyperpolarizability (.beta.) either positive or negative in sign and therefore display second order non-linear optical properties when incorporated into non-linear optical devices.

Linear regression crash prediction models : issues and proposed solutions.

DOT National Transportation Integrated Search

2010-05-01

The paper develops a linear regression model approach that can be applied to : crash data to predict vehicle crashes. The proposed approach involves novice data aggregation : to satisfy linear regression assumptions; namely error structure normality ...

Linear Motor With Air Slide

NASA Technical Reports Server (NTRS)

Johnson, Bruce G.; Gerver, Michael J.; Hawkey, Timothy J.; Fenn, Ralph C.

1993-01-01

Improved linear actuator comprises air slide and linear electric motor. Unit exhibits low friction, low backlash, and more nearly even acceleration. Used in machinery in which positions, velocities, and accelerations must be carefully controlled and/or vibrations must be suppressed.

Progress in linear optics, non-linear optics and surface alignment of liquid crystals

NASA Astrophysics Data System (ADS)

Ong, H. L.; Meyer, R. B.; Hurd, A. J.; Karn, A. J.; Arakelian, S. M.; Shen, Y. R.; Sanda, P. N.; Dove, D. B.; Jansen, S. A.; Hoffmann, R.

We first discuss the progress in linear optics, in particular, the formulation and application of geometrical-optics approximation and its generalization. We then discuss the progress in non-linear optics, in particular, the enhancement of a first-order Freedericksz transition and intrinsic optical bistability in homeotropic and parallel oriented nematic liquid crystal cells. Finally, we discuss the liquid crystal alignment and surface effects on field-induced Freedericksz transition.

The intelligence of dual simplex method to solve linear fractional fuzzy transportation problem.

PubMed

Narayanamoorthy, S; Kalyani, S

2015-01-01

An approach is presented to solve a fuzzy transportation problem with linear fractional fuzzy objective function. In this proposed approach the fractional fuzzy transportation problem is decomposed into two linear fuzzy transportation problems. The optimal solution of the two linear fuzzy transportations is solved by dual simplex method and the optimal solution of the fractional fuzzy transportation problem is obtained. The proposed method is explained in detail with an example.

Testing the Linearity of the Cosmic Origins Spectrograph FUV Channel Thermal Correction

NASA Astrophysics Data System (ADS)

Fix, Mees B.; De Rosa, Gisella; Sahnow, David

2018-05-01

The Far Ultraviolet Cross Delay Line (FUV XDL) detector on the Cosmic Origins Spectrograph (COS) is subject to temperature-dependent distortions. The correction performed by the COS calibration pipeline (CalCOS) assumes that these changes are linear across the detector. In this report we evaluate the accuracy of the linear approximations using data obtained on orbit. Our results show that the thermal distortions are consistent with our current linear model.

Restoring Low Sidelobe Antenna Patterns with Failed Elements in a Phased Array Antenna

DTIC Science & Technology

2016-02-01

optimum low sidelobes are demonstrated in several examples. Index Terms — Array signal processing, beams, linear algebra , phased arrays, shaped...represented by a linear combination of low sidelobe beamformers with no failed elements, ’s, in a neighborhood around under the constraint that the linear ...would expect that linear combinations of them in a neighborhood around would also have low sidelobes. The algorithms in this paper exploit this

Linear mass actuator

NASA Technical Reports Server (NTRS)

Holloway, Sidney E., III (Inventor); Crossley, Edward A., Jr. (Inventor); Jones, Irby W. (Inventor); Miller, James B. (Inventor); Davis, C. Calvin (Inventor); Behun, Vaughn D. (Inventor); Goodrich, Lewis R., Sr. (Inventor)

1992-01-01

A linear mass actuator includes an upper housing and a lower housing connectable to each other and having a central passageway passing axially through a mass that is linearly movable in the central passageway. Rollers mounted in the upper and lower housings in frictional engagement with the mass translate the mass linearly in the central passageway and drive motors operatively coupled to the roller means, for rotating the rollers and driving the mass axially in the central passageway.

Conical Lens for 5-Inch/54 Gun Launched Missile

DTIC Science & Technology

1981-06-01

Propagation, Interferenceand Diffraction of Light, 2nd ed. (revised), p. 121-124, Pergamon Press, 1964. 10. Anton , Howard, Elementary Linear Algebra , p. 1-21...equations is nonlinear in x, but is linear in the coefficients. Therefore, the techniques of linear algebra can be used on equation (F-13). The method...This thesis assumes the air to be homogenous, isotropic, linear , time indepen- dent (HILT) and free of shock waves in order to investigate the