Sample records for stacked macrocyclic molecular

  1. Creating molecular macrocycles for anion recognition

    Directory of Open Access Journals (Sweden)

    Amar H. Flood


    Full Text Available The creation and functionality of new classes of macrocycles that are shape persistent and can bind anions is described. The genesis of triazolophane macrocycles emerges out of activity surrounding 1,2,3-triazoles made using click chemistry; and the same triazoles are responsible for anion capture. Mistakes made and lessons learnt in anion recognition provide deeper understanding that, together with theory, now provides for computer-aided receptor design. The lessons are acted upon in the creation of two new macrocycles. First, cyanostars are larger and like to capture large anions. Second is tricarb, which also favors large anions but shows a propensity to self-assemble in an orderly and stable manner, laying a foundation for future designs of hierarchical nanostructures.

  2. Combined molecular and periodic DFT analysis of the adsorption of co macrocycles on graphene. (United States)

    Calborean, Adrian; Morari, Cristian; Maldivi, Pascale


    The molecular doping of graphene with π-stacked conjugated molecules has been widely studied during the last 10 years, both experimentally or using first-principle calculations, mainly with strongly acceptor or donor molecules. Macrocyclic metal complexes have been far less studied and their behavior on graphene is less clear-cut. The present density functional theory study of cobalt porphyrin and phthalocyanine adsorbed on monolayer or bilayer graphene allows to compare the outcomes of two models, either a finite-sized flake of graphene or an infinite 2D material using periodic calculations. The electronic structures yielded by both models are compared, with a focus on the density of states around the Fermi level. Apart from the crucial choice of calculation conditions, this investigation also shows that unlike strongly donating or accepting organic dopants, these macrocycles do not induce a significant doping of the graphene sheet and that a finite size model of graphene flake may be confidently used for most modeling purposes. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

  3. Supramolecular polymers constructed from macrocycle-based host-guest molecular recognition motifs. (United States)

    Dong, Shengyi; Zheng, Bo; Wang, Feng; Huang, Feihe


    CONSPECTUS: Supramolecular polymers, fabricated via the combination of supramolecular chemistry and polymer science, are polymeric arrays of repeating units held together by reversible, relatively weak noncovalent interactions. The introduction of noncovalent interactions, such as hydrogen bonding, aromatic stacking interactions, metal coordination, and host-guest interactions, endows supramolecular polymers with unique stimuli responsiveness and self-adjusting abilities. As a result, diverse monomer structures have been designed and synthesized to construct various types of supramolecular polymers. By changing the noncovalent interaction types, numbers, or chemical structures of functional groups in these monomers, supramolecular polymeric materials can be prepared with tailored chemical and physical properties. In recent years, the interest in supramolecular polymers has been extended from the preparation of intriguing topological structures to the discoveries of potential applications as functional materials. Compared with traditional polymers, supramolecular polymers show some advantages in the fabrication of reversible or responsive materials. The development of supramolecular polymers also offers a platform to construct complex and sophisticated materials with a bottom-up approach. Macrocylic hosts, including crown ethers, cyclodextrins, calixarenes, cucurbiturils, and pillararenes, are the most commonly used building blocks in the fabrication of host-guest interaction-based supramolecular polymers. With the introduction of complementary guest molecules, macrocylic hosts demonstrate selective and stimuli-responsive host-guest complexation behaviors. By elaborate molecular design, the resultant supramolecular polymers can exhibit diverse structures based on the self-selectivity of host-guest interactions. The introduction of reversible host-guest interactions can further endow these supramolecular polymers with interesting and fascinating chemical

  4. Site-selective guest inclusion in molecular networks of butadiyne-bridged pyridino and benzeno square macrocycles on a surface. (United States)

    Tahara, Kazukuni; Lei, Shengbin; Mamdouh, Wael; Yamaguchi, Yui; Ichikawa, Tomoyuki; Uji-I, Hiroshi; Sonoda, Motohiro; Hirose, Keiji; De Schryver, Frans C; De Feyter, Steven; Tobe, Yoshito


    We present here the formation of a modular 2D molecular network composed of two different types of square-shaped butadiyne-bridged macrocycles, having intrinsic molecular voids, aligned alternately at the solid-liquid interface. Site-selective inclusion of a guest cation took place at every other molecular void in the molecular network with two different recognition sites.

  5. Molecular Rearrangement of an Aza-Scorpiand Macrocycle Induced by pH: A Computational Study

    Directory of Open Access Journals (Sweden)

    Jesus Vicente De Julián-Ortiz


    Full Text Available Rearrangements and their control are a hot topic in supramolecular chemistry due to the possibilities that these phenomena open in the design of synthetic receptors and molecular machines. Macrocycle aza-scorpiands constitute an interesting system that can reorganize their spatial structure depending on pH variations or the presence of metal cations. In this study, the relative stabilities of these conformations were predicted computationally by semi-empirical and density functional theory approximations, and the reorganization from closed to open conformations was simulated by using the Monte Carlo multiple minimum method.

  6. Molecular Assemblies of Porphyrins and Macrocyclic Receptors: Recent Developments in Their Synthesis and Applications

    Directory of Open Access Journals (Sweden)

    Abdirahman A. Mohamod


    Full Text Available Metalloporphyrins which form the core of many bioenzymes and natural light harvesting or electron transport systems, exhibit a variety of selective functional properties depending on the state and surroundings with which they exist in biological systems. The specificity and ease with which they function in each of their bio-functions appear to be largely governed by the nature and disposition of the protein globule around the porphyrin reaction center. Synthetic porphyrin frameworks confined within or around a pre-organized molecular entity like the protein network in natural systems have attracted considerable attraction, especially in the field of biomimetic reactions. At the same time a large number of macrocyclic oligomers such as calixarenes, resorcinarenes, spherands, cyclodextrins and crown ethers have been investigated in detail as efficient molecular receptors. These molecular receptors are synthetic host molecules with enclosed interiors, which are designed three dimensionally to ensure strong and precise molecular encapsulation/recognition. Due to their complex structures, enclosed guest molecules reside in an environment isolated from the outside and as a consequence, physical properties and chemical reactions specific to that environment in these guest species can be identified. The facile incorporation of such molecular receptors into the highly photoactive and catalytically efficient porphyrin framework allows for convenient design of useful molecular systems with unique structural and functional properties. Such systems have provided over the years attractive model systems for the study of various biological and chemical processes, and the design of new materials and molecular devices. This review focuses on the recent developments in the synthesis of porphyrin assemblies associated with cyclodextrins, calixarenes and resorcinarenes and their potential applications in the fields of molecular encapsulation/recognition, and

  7. DNA binding affinity of a macrocyclic copper(II) complex: Spectroscopic and molecular docking studies. (United States)

    Shahabadi, Nahid; Hakimi, Mohammad; Morovati, Teimoor; Fatahi, Navid


    The interaction of a novel macrocyclic copper(II) complex, ([CuL(ClO 4 ) 2 ] that L is 1,3,6,10,12,15-hexaazatricyclo[ 6,10 ]eicosane) with calf thymus DNA (ct-DNA) was investigated by various physicochemical techniques and molecular docking at simulated physiological conditions (pH = 7.4). The absorption spectra of the Cu(II) complex with ct-DNA showed a marked hyperchroism with 10 nm blue shift. The intrinsic binding constant (K b ) was determined as 1.25 × 10 4 M -1 , which is more in keeping with the groove binding with DNA. Furthermore, competitive fluorimetric studies with Hoechst33258 have shown that Cu(II) complex exhibits the ability to displace the ct-DNA-bound Hoechst33258 indicating that it binds to ct-DNA in strong competition with Hoechst33258 for the groove binding. Also, no change in the relative viscosity of ct-DNA and fluorescence intensity of ct-DNA-MB complex in the present of Cu(II) complex is another evidence to groove binding. The thermodynamic parameters are calculated by van't Hoff equation, which demonstrated that hydrogen bonds and van der Waals interactions played major roles in the binding reaction. The experimental results were in agreement with the results obtained via molecular docking study.

  8. Synthesis, antimicrobial, antioxidant and molecular docking studies of thiophene based macrocyclic Schiff base complexes (United States)

    Rathi, Parveen; Singh, D. P.


    The macrocyclic complexes of pharmaceutical importance with trivalent transition metals have been synthesized by [1 + 1] condensation of succinyldihydrazide and thiophenedicarboxaldehyde, via template method, resulting in the formation of the complex [MLX] X2; where L is (C10H10N4O2S), a macrocyclic ligand, M = Cr (III) and Fe (III) and X = Cl-, CH3COO- or NO3- . These complexes have been characterized with the help of elemental analyses, molar conductance measurements, magnetic susceptibility measurements, ultraviolet, infrared, far infrared, electron spin resonance, mass spectral studies and powder x-ray diffraction analysis. On the basis of all these studies, mononuclear complexes having 1:2 electrolytic nature with a five coordinated square pyramidal geometry have been proposed. Powder diffraction XRD indicates the presence of triclinic crystal system with p bravais lattice for the representative complex. All the metal complexes have also been explored for their in vitro antimicrobial and antioxidant activities.

  9. Quantum chemical DFT study of the interaction between molecular oxygen and FeN₄ complexes, and effect of the macrocyclic ligand. (United States)

    Silva, Adilson Luís Pereira; de Almeida, Luciano Farias; Marques, Aldaléa Lopes Brandes; Costa, Hawbertt Rocha; Tanaka, Auro Atsushi; da Silva, Albérico Borges Ferreira; de Jesus Gomes Varela, Jaldyr


    Density functional theory (DFT) was used to examine the interaction between molecular oxygen (O₂) and macrocyclic iron complexes of the type FeN₄ during the formation of FeN₄--O₂ adducts. In order to understand how this interaction is affected by different macrocyclic ligands, O₂ was bonded to iron-tetraaza[14]annulene (FeTAA), iron-tetramethyl-tetraaza[14]annulene (FeTMTAA), iron-hexamethyl-tetraaza[14]annulene (FeHMTAA), iron dibenzotetraaza[14]annulene (FeDBTAA), and two iron-tetramethyl-dibenzotetraaza[14]annulene complexes (FeTMDBTAA1, FeTMDBTAA2). The ground state for FeN₄-O₂ adducts was the open-shell singlet. Analysis of the factors influencing the O₂ bonding process showed that different macrocyclic ligands yielded adducts with differences in O--O and Fe--O₂ bond lengths, total charge over the O₂ fragment, O--O vibrational frequency, and spin density in the O₂ fragment. A smaller energy gap between the α-HOMO of the FeN₄ complexes and the β-LUMO of O₂ increased the interaction between the complex and the O₂ molecule. The order of activity was FeDBTAA < FeTMDBTAA2 < FeTMDBTAA1 < FeTAA < FeTMTAA < FeHMTAA.

  10. Supramolecular macrocycles based on porphyrins- correlation of molecular structure and biological photoactivity

    International Nuclear Information System (INIS)

    Ion, R. M.; Oprea, F.; Bacinschi, Z.; Scarlat, F.; Scarlat, Fl.; Niculescu, V.I.R.


    Porphyrins and phthalocyanines are organic dyes which can be used as highly fluorescent species in laser technology, in photography, as radiation power indicators, as photosensitizers in photodynamic therapy of cancerous disease. Porphyrins constitute a class of the molecules which contain four pyrrole rings linked by the methane carbon bridges whereas the phthalocyanine molecules are composed of four indole units - pyrrole rings linked by nitrogen atoms conjugated with benzene rings. A large group of porphyrins and phthalocyanines can be chemically modified by introducing metal in the center of the pyrrole rings or by attaching the peripheral groups to the outer rings of the methane bridges or isoindole units, respectively. In this study five groups of tetraphenylporphyrins (TPP) and phthalocyanines (Pc) were investigated: - metal (Me)-free dyes without any substitutes, - non-substituted porphyrins and phthalocyanines but complexed with metal (Me) - Zn, Mg, Mn, Co, Cu, Pt, Pd, Pb and others, - metal-complexed dyes substituted with aromatic rings, - metal-complexed dyes substituted with fluorines, - metal-complexed dyes substituted with long organic chains (alkyl or alkyloxy). The difference in the TPP and Pc molecular structure, the kind of metal incorporated into the main molecular core or the variation in the peripheral groups attached to the molecular skeleton are expected to affect the effectiveness of dyes in photocurrent generation. Since there is a competition between the charge separation process and other deactivation processes in the molecule, in our study photochemical investigations (photodynamic action) are usually accompanied with the spectroscopic examinations (absorption, fluorescence- which give information on the (non-) radiative processes) of dyes. In the paper we have presented the review of our study on the correlation between the molecular structure of dyes and their photoactive properties. (authors)

  11. Multicomponent Syntheses of Macrocycles (United States)

    Masson, Géraldine; Neuville, Luc; Bughin, Carine; Fayol, Aude; Zhu, Jieping

    How to access efficiently the macrocyclic structure remained to be a challenging synthetic topic. Although many elegant approaches/reactions have been developed, construction of diverse collection of macrocycles is still elusive. This chapter summarized the recently emerged research area dealing with multicomponent synthesis of macrocycles, with particular emphasis on the approach named "multiple multicomponent reaction using two bifunctional building blocks".

  12. Comprehensive computational design of ordered peptide macrocycles

    Energy Technology Data Exchange (ETDEWEB)

    Hosseinzadeh, Parisa; Bhardwaj, Gaurav; Mulligan, Vikram K.; Shortridge, Matthew D.; Craven, Timothy W.; Pardo-Avila, Fatima; Rettie, Stephan A.; Kim, David E.; Silva, Daniel A.; Ibrahim, Yehia M.; Webb, Ian K.; Cort, John R.; Adkins, Joshua N.; Varani, Gabriele; Baker, David


    Mixed chirality peptide macrocycles such as cyclosporine are among the most potent therapeutics identified to-date, but there is currently no way to systematically search through the structural space spanned by such compounds for new drug candidates. Natural proteins do not provide a useful guide: peptide macrocycles lack regular secondary structures and hydrophobic cores and have different backbone torsional constraints. Hence the development of new peptide macrocycles has been approached by modifying natural products or using library selection methods; the former is limited by the small number of known structures, and the latter by the limited size and diversity accessible through library-based methods. To overcome these limitations, here we enumerate the stable structures that can be adopted by macrocyclic peptides composed of L and D amino acids. We identify more than 200 designs predicted to fold into single stable structures, many times more than the number of currently available unbound peptide macrocycle structures. We synthesize and characterize by NMR twelve 7-10 residue macrocycles, 9 of which have structures very close to the design models in solution. NMR structures of three 11-14 residue bicyclic designs are also very close to the computational models. Our results provide a nearly complete coverage of the rich space of structures possible for short peptide based macrocycles unparalleled for other molecular systems, and vastly increase the available starting scaffolds for both rational drug design and library selection methods.

  13. Macrocyclic fragrance materials

    DEFF Research Database (Denmark)

    Salvito, Daniel; Lapczynski, Aurelia; Sachse-Vasquez, Christen


    A screening-level aquatic environmental risk assessment for macrocyclic fragrance materials using a “group approach” is presented using data for 30 macrocyclic fragrance ingredients. In this group approach, conservative estimates of environmental exposure and ecotoxicological effects thresholds...... for compounds within two subgroups (15 macrocyclic ketones and 15 macrocyclic lactones/lactides) were used to estimate the aquatic ecological risk potential for these subgroups. It is reasonable to separate these fragrance materials into the two subgroups based on the likely metabolic pathway required....../L and for macrocyclic lactones/lactides is 2.7 μg/L. The results of this screening-level aquatic ecological risk assessment indicate that at their current tonnage, often referred to as volumes of use, macrocyclic fragrance materials in Europe and North America, pose a negligible risk to aquatic biota; with no PEC...

  14. New hexadentate macrocyclic ligand and their copper(II) and nickel(II) complexes: Spectral, magnetic, electrochemical, thermal, molecular modeling and antimicrobial studies (United States)

    Chandra, Sulekh; Ruchi; Qanungo, Kushal; Sharma, Saroj. K.

    Ni(II) and Cu(II) complexes were synthesized with a hexadentate macrocyclic ligand [3,4,8,9tetraoxo-2,5,7,10tetraaza-1,6dithio-(3,4,8,9) dipyridinedodecane(L)] and characterized by elemental analysis, molar conductance measurements, mass, NMR, IR, electronic, EPR spectral, thermal and molecular modeling studies. All the complexes are 1:2 electrolytes in nature and may be formulated as [M(L)]X2 [where, M = Ni(II) and Cu(II) and X = Cl-, NO3-, ½SO42-, CH3COO-]. On the basis of IR, electronic and EPR spectral studies an octahedral geometry has been assigned for Ni(II) complexes and tetragonal geometry for Cu(II) complexes. The antimicrobial activities and LD50 values of the ligand and its complexes, as growth inhibiting agents, have been screened in vitro against two different species of bacteria and plant pathogenic fungi.

  15. Chemistry of anthracene-acetylene oligomers XXV: on-surface chirality of a self-assembled molecular network of a fan-blade-shaped anthracene-acetylene macrocycle with a long alkyl chain. (United States)

    Tsuya, Takuya; Iritani, Kohei; Tahara, Kazukuni; Tobe, Yoshito; Iwanaga, Tetsuo; Toyota, Shinji


    An anthracene cyclic dimer with two different linkers and a dodecyl group was synthesized by means of coupling reactions. The calculated structure had a planar macrocyclic π core and a linear alkyl chain. Scanning tunneling microscopy observations at the 1-phenyloctane/graphite interface revealed that the molecules formed a self-assembled monolayer that consisted of linear striped bright and dark bands. In each domain, the molecular network consisted of either Re or Si molecules that differed in the two-dimensional chirality about the macrocyclic faces, which led to a unique conglomerate-type self-assembly. The molecular packing mode and the conformation of the alkyl chains are discussed in terms of the intermolecular interactions and the interactions between the molecules and the graphite surface with the aid of MM3 simulations of a model system. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Luminescent macrocyclic lanthanide complexes (United States)

    Raymond, Kenneth N; Corneillie, Todd M; Xu, Jide


    The present invention provides a novel class of macrocyclic compounds as well as complexes formed between a metal (e.g., lanthanide) ion and the compounds of the invention. Preferred complexes exhibit high stability as well as high quantum yields of lanthanide ion luminescence in aqueous media without the need for secondary activating agents. Preferred compounds incorporate hydroxy-isophthalamide moieties within their macrocyclic structure and are characterized by surprisingly low, non-specific binding to a variety of polypeptides such as antibodies and proteins as well as high kinetic stability. These characteristics distinguish them from known, open-structured ligands.

  17. Kinetic investigation of uranyl-uranophile complexation. 1. Macrocyclic kinetic effect and macrocyclic protection effect

    International Nuclear Information System (INIS)

    Tabushi, I.; Yoshizawa, A.


    Equilibria and rates of ligand-exchange reactions between uranyl tricarbonate and dithiocarbamates and between uranyl tris-(dithiocarbamates) and carbonate were studied under a variety of conditions. The dithiocarbamates used were acyclic diethyl-dithiocarbamate and macrocyclic tris(dithiocarbamate). The acyclic ligand showed a triphasic (successive three-step) equilibrium with three different equilibrium constants while the macrocyclic ligand showed a clear monophasic (one-step) equilibrium with a much larger stability constant for the dithiocarbamate-uranyl complex. The macrocyclic ligand showed the S/sub N/2-type ligand-exchange rate in the forward as well as reverse process, while the first step of the acyclic ligand-exchange reaction proceeded via the S/sub N/1-type mechanism. This kinetic macrocyclic effect on molecularity is interpreted as the result of a unique topological requirement of uranyl complexation. The macrocyclic ligand also exhibited a clear protection effect, leading to the large stability constant. 19 references, 10 figures, 2 tables

  18. Improving the leakage current of polyimide-based resistive memory by tuning the molecular chain stack of the polyimide film (United States)

    Wu, Chi-Chang; Hsiao, Yu-Ping; You, Hsin-Chiang; Lin, Guan-Wei; Kao, Min-Fang; Manga, Yankuba B.; Yang, Wen-Luh


    We have developed an organic-based resistive random access memory (ReRAM) by using spin-coated polyimide (PI) as the resistive layer. In this study, the chain distance and number of chain stacks of PI molecules are investigated. We employed different solid contents of polyamic acid (PAA) to synthesize various PI films, which served as the resistive layer of ReRAM, the electrical performance of which was evaluated. By tuning the PAA solid content, the intermolecular interaction energy of the PI films is changed without altering the molecular structure. Our results show that the leakage current in the high-resistance state and the memory window of the PI-based ReRAM can be substantially improved using this technique. The superior properties of the PI-based ReRAM are ascribed to fewer molecular chain stacks in the PI films when the PAA solid content is decreased, hence suppressing the leakage current. In addition, a device retention time of more than 107 s can be achieved using this technique. Finally, the conduction mechanism in the PI-based ReRAM was analyzed using hopping and conduction models.

  19. Note: A short-pulse high-intensity molecular beam valve based on a piezoelectric stack actuator

    Energy Technology Data Exchange (ETDEWEB)

    Abeysekera, Chamara; Joalland, Baptiste; Shi, Yuanyuan; Kamasah, Alexander; Oldham, James M.; Suits, Arthur G., E-mail: [Department of Chemistry, Wayne State University, Detroit, Michigan 48202 (United States)


    Solenoid and piezoelectric disk valves, which are widely used to generate molecular beam pulses, still suffer from significant restrictions, such as pulse durations typically >50 μs, low repetition rates, and limited gas flows and operational times. Much of this arises owing to the limited forces these actuators can achieve. To overcome these limitations, we have developed a new pulsed valve based on a high-force piezoelectric stack actuator. We show here that operation with pulse durations as low as 20 μs and repetition rates up to 100 Hz can be easily achieved by operating the valve in conjunction with a commercial fast high-voltage switch. We outline our design and demonstrate its performance with molecular beam characterization via velocity map ion imaging.

  20. Electrochemically assisted mechanically controllable break junction studies on the stacking configurations of oligo(phenylene ethynylene)s molecular junctions

    International Nuclear Information System (INIS)

    Zheng, Jue-Ting; Yan, Run-Wen; Tian, Jing-Hua; Liu, Jun-Yang; Pei, Lin-Qi; Wu, De-Yin; Dai, Ke; Yang, Yang; Jin, Shan


    Highlights: • I-V characteristics of a series of oligo(phenylene ethynylene)s molecular junctions were measured. • Conductance values were found to be dependent on molecular length and substituent group. • The measured low conductance values were explained by theoretical calculations. • EC-MCBJ is feasible to fabricate and characterize molecular junctions. - Abstract: We demonstrate an electrochemically assisted mechanically controllable break junction (EC-MCBJ) approach for current-voltage characteristic (I-V curve) measurements of metal/molecule/metal junctions. A series of oligo(phenylene ethynylene)s compounds (OPEs), including those involving electron withdrawing substituent group and different backbone lengths, had been successfully designed, synthesized, and placed onto the fabricated nanogap to form molecular junctions. The observed evolution in the measured conductances of OPEs indicates that there is a dependence of conductance on molecular length and substituent group. Compared with those extracted from conductance histogram construction, the conductances of OPEs measured from I-V curves are considerably lower. Based on the transmission spectra of OPEs that calculated by density functional theory (DFT) combined with non-equilibrium Green’s function (NEGF) method, this difference was attributed to our distinct experimental operation, which may give rise to a stacking configuration of two OPE molecules.

  1. Fourth symposium on macrocyclic compounds

    International Nuclear Information System (INIS)

    Christensen, J.J.; Izatt, R.M.


    Both theoretical and experimental aspects of the properties and behavior of synthetic and naturally occurring macrocyclic compounds are covered in this symposium. This document contains abstracts of the papers

  2. Third Symposium on Macrocyclic Compounds

    International Nuclear Information System (INIS)


    At the Third Symposium on Macrocyclic Compounds there were sessions on facilitated transport, analytical applications, organic synthesis and reactions, phase transfer catalysis, and metal complexation. Abstracts of the individual presentations are included

  3. Use of macrocycle- or hemisepulcrand-type poly(oxygen) compounds in nuclear hydrometallurgy. Study of the diluent effect: supra-molecular approach

    International Nuclear Information System (INIS)

    Bethmont, Valerie


    Liquid/liquid extraction has been used for many years to obtain high purity nuclear fuels (uranium salts and plutonium salts), notably with the Purex process which allows 99 per cent of uranium and plutonium contained by spent nuclear fuels to be recovered. This research thesis deals with the search for new and steadier extracting agents, and focuses on macro-cycle or hemisepulcrand type poly(oxygenated) compounds which have excellent properties in nuclear hydrometallurgy. The author thus first discusses the synthesis of oxygenated tripodands (bibliographical study and development of a catalytic method to synthesise ethers). Then, she reports the use of poly(oxygenated) compounds in liquid/liquid extraction, and the experimental study of the effect of the diluting agent by using a supramolecular approach [fr

  4. Towards further understanding of stacking fault tetrahedron absorption and defect-free channels – A molecular dynamics study

    International Nuclear Information System (INIS)

    Fan, Haidong; El-Awady, Jaafar A.; Wang, Qingyuan


    Highlights: • Stacking fault tetrahedron (SFT) is fully absorbed by screw dislocation. • Absorbed SFT becomes moveable with the aid of Lomer dislocations. • Finally SFT is removed from the specimen or from defect-free channels. • Two scenarios responsible for the formation of defect-free channels were proposed. - Abstract: The mechanisms leading to stacking fault tetrahedron (SFT) absorption via interactions with dislocations, and subsequent formation of plastic flow localization in defect-free channels, which were frequently observed in irradiated materials in transmission electron microscopy experiments, are still unclear. To address this, screw dislocation interactions with SFTs in copper were investigated using molecular dynamics (MD) simulations. The interaction details reveal that a screw dislocation can fully absorb an SFT through the thermally activated transformation of Lomer–Cottrell lock into Lomer dislocations. After absorption, almost all the vacancies in the SFT are transferred into Lomer dislocations, which are able to move transversely under complex loading conditions. As a result, SFTs can be removed from the material (for SFTs near surface) or from defect-free channels (for SFTs in the bulk) with the aid of Lomer dislocations. In addition, it was shown that this absorption process is favorable only at high temperature, low applied shear stress and/or high SFT density. These results are in good agreement with in situ TEM observations. The current simulations and analyses provide useful insights into the formation mechanisms of defect-free channels in irradiated materials

  5. Methods and intermediates for the synthesis of dipyrrin-substituted porphyrinic macrocycles (United States)

    Yu, Lianhe; Muthukumaran, Kannan; Sreedharan, Prathapan; Lindsey, Jonathan S.


    The present invention provides dipyrrin substituted porphyrinic macrocycles, intermediates useful for making the same, and methods of making the same. Such compounds may be used for purposes including the making of molecular memory devices, solar cells and light harvesting arrays.

  6. Surface enhanced second harmonic generation from macrocycle, catenane, and rotaxane thin films : Experiments and theory

    NARCIS (Netherlands)

    Arfaoui, I.; Bermudez, V.; Bottari, G.; De Nadai, C.; Jalkanen, J.P.; Kajzar, F.; Leigh, D.A.; Lubomska, M.; Mendoza, S.M.; Niziol, J.; Rudolf, Petra; Zerbetto, F.


    Surface enhanced second harmonic generation (SE SHG) experiments on molecular structures, macrocycles, catenanes, and rotaxanes, deposited as monolayers and multilayers by vacuum sublimation on silver, are reported. The measurements show that the molecules form ordered thin films, where the highest

  7. Macrocyclic ligands for uranium complexation

    Energy Technology Data Exchange (ETDEWEB)

    Potts, K.T.


    A highly preorganized 24-macrocycle containing biuret, thiobiuret and pyridine subunits has been prepared by high dilution ring-closure procedures. Intermediate products to this macrocycle have been utilized to extend this synthetic route to include further representatives where solubility and stability will be influenced by substituent variation. A 1:1 complex has been formed from uranyl acetate and a quinquepyridine derivative, this representing a new type of ligand for the uranyl ion. A very convenient synthetic procedure that will allow the incorporation of these macrocycles into polymeric systems has been developed for the introduction of a vinyl substituent into the 4-position of the pyridine ring. Using triflate, vinyltributyltin and Pd{sup 0} chemistry, this procedure should make a variety of substituted 4-vinylpyridines available for the first time. 3 refs.

  8. Macrocyclic ligands for uranium complexation

    International Nuclear Information System (INIS)

    Potts, K.T.


    A highly preorganized 24-macrocycle containing biuret, thiobiuret and pyridine subunits has been prepared by high dilution ring-closure procedures. Intermediate products to this macrocycle have been utilized to extend this synthetic route to include further representatives where solubility and stability will be influenced by substituent variation. A 1:1 complex has been formed from uranyl acetate and a quinquepyridine derivative, this representing a new type of ligand for the uranyl ion. A very convenient synthetic procedure that will allow the incorporation of these macrocycles into polymeric systems has been developed for the introduction of a vinyl substituent into the 4-position of the pyridine ring. Using triflate, vinyltributyltin and Pd 0 chemistry, this procedure should make a variety of substituted 4-vinylpyridines available for the first time. 3 refs

  9. Macrocyclic ligands for uranium complexation

    International Nuclear Information System (INIS)

    Potts, K.T.


    Macrocycles with cavity diameters in the region 4.5-5.2 Angstrom, based on computer modeling studies, have been prepared by high dilution cyclocondensation of 2-aminopyridyl substituted biurets and thiobiurets with appropriately substituted, reactive intermediates such as chlorocarbonyl isocyanate and malonyl dichloride. Detailed high field 1 H NMR studies have been used to identify all protons in these macrocycles for structural verification and in confromation studies, and by-products obtained in their synthesis as well as in complexation studies have been characterized and identified using these NMR techniques, as well as single crystal X-ray studies. 5 refs

  10. One-dimensional self-assembly of phenylacetylene macrocycles: effect of peripheral substituents. (United States)

    Li, Jie; Zhou, Wei; Yang, Jiping; Lang, Xiufeng; Huang, Pengcheng


    Tetra- and tri-substituted m-phenylacetylene macrocycles with diethylene glycol monoethyl ether (DEG) phenylether peripheral side chains (PAM 1 and PAM 1') were synthesized, and both of them could self-assemble into well-defined one-dimensional (1D) structures through two kinds of fabrication processing. The recrystallization approach led to similar microbelts for PAMs 1 and 1' with hundreds of microns in length, 2-4 μm in width, and 200-300 nm in thickness. But AFM, XRD, and spectrum characterizations indicated that the microbelts of PAM 1' had smaller intercolumnar distances and more favorable π-π stacking. Two different nanostructures were obtained through the other processing of solvent evaporation: nanobelts for PAM 1 and twisted nanorods for PAM 1'. The different molecular arrangement and nanostructures could be ascribed to the different molecular structures, especially the different positioning of the peripheral substituents. This research provides a potential control over the morphology and the structure of the 1D assembly by adjusting the molecular structure as well as the sample processing. Copyright © 2013 Elsevier Inc. All rights reserved.

  11. Novel macrocyclic carriers for proton-coupled liquid membrane transport. Final report

    Energy Technology Data Exchange (ETDEWEB)

    Lamb, J.D.; Izatt, R.M.; Bradshaw, J.S.; Shirts, R.B.


    The objective of this research program is to elucidate the chemical principles which are responsible for the cation selectivity and permeability of liquid membranes containing macrocyclic carriers. Several new macrocyclic carriers were synthesized during the last three year period. In addition, new, more convenient synthetic routes were achieved for several nitrogen-containing bicyclic and tricyclic macrocycles. The cation binding properties of these macrocycles were investigated by potentiometric titration, calorimetric titration, solvent extraction and NMR techniques. In addition, hydrophobic macrocycles were incorporated into dual hollow fiber and other membrane systems to investigate their membrane performance, especially in the proton-coupled transport mode. A study of the effect of methoxyalkyl macrocycle substituents on metal ion transport was completed. A new calorimeter was constructed which made it possible to study the thermodynamics of macrocycle-cation binding to very high temperatures. Measurements of thermodynamic data for the interaction of crown ethers with alkali and alkaline earth cations were achieved to 473 K. Molecular modeling work was begun for the first time on this project and fundamental principles were identified and developed for the establishment of working models in the future.

  12. Structure of fault stackings of molecular layers X-M-X in CdI2 polytypic crystals

    International Nuclear Information System (INIS)

    Palosz, B.; Przedmojski, J.


    The arrangements of molecular layers I-Cd-I, which may be regarded as 'faulted' for CdI 2 polytypic crystals, are analyzed. Tentative classification of faults into those which are intermediate structure between the basic polytypes 2H and 4H and faults occurring between different blocks of pure structure 4 H is proposed. The connection between some growth parameters and the structure of faults in CdI 2 crystals grown from solutions is discussed. It is shown that the geometrical classification of stacking faults used for layered inorganic crystals is not appropriate for the description of the faults existing in polytypic crystals of MX 2 type. The effect of weak external electric and magnetic fields on the polytypic structure of CdI 2 is analyzed. The experiments performed for several hundred of polytypes of CdI 2 showed that the external fields may, in some conditions, affect the organization of the polytypic structure of crystals very strongly. In particular, it was found that the external fields may change the period of polytype cells and that the relative number of hexagonal and rhombohedral polytypes differ very strongly for crystals grown in the absence and in the presence of external electric and magnetic fields. (author)

  13. Macrocyclic cyclodiphosphazane : synthesis of chalcogen ...

    Indian Academy of Sciences (India)



    Sep 6, 2017 ... 6. Calera S G and Wright D S 2010 Macrocyclic phosphaz- ane ligands Dalton Trans. 39 5055. 7. Gonzalez-Calera S, Eisler D J, Morey J V, McPartlin M, .... Silaghi-Dumitrescu I, Lara-Ochoa F and Haiduc I 1998. Edge or Verte Inversion at Phosphorus in the cis-trans. Isomerization of Diazadiphosphetidines ...

  14. Acetone-Linked Peptides: A Convergent Approach for Peptide Macrocyclization and Labeling. (United States)

    Assem, Naila; Ferreira, David J; Wolan, Dennis W; Dawson, Philip E


    Macrocyclization is a broadly applied approach for overcoming the intrinsically disordered nature of linear peptides. Herein, it is shown that dichloroacetone (DCA) enhances helical secondary structures when introduced between peptide nucleophiles, such as thiols, to yield an acetone-linked bridge (ACE). Aside from stabilizing helical structures, the ketone moiety embedded in the linker can be modified with diverse molecular tags by oxime ligation. Insights into the structure of the tether were obtained through co-crystallization of a constrained S-peptide in complex with RNAse S. The scope of the acetone-linked peptides was further explored through the generation of N-terminus to side chain macrocycles and a new approach for generating fused macrocycles (bicycles). Together, these studies suggest that acetone linking is generally applicable to peptide macrocycles with a specific utility in the synthesis of stabilized helices that incorporate functional tags. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Molecular marker assisted gene stacking for biotic and abiotic stress resistance genes in an elite rice cultivar (United States)

    Das, Gitishree; Rao, G. J. N.


    Severe yield loss due to various biotic stresses like bacterial blight (BB), gall midge (insect) and Blast (disease) and abiotic stresses like submergence and salinity are a serious constraint to the rice productivity throughout the world. The most effective and reliable method of management of the stresses is the enhancement of host resistance, through an economical and environmentally friendly approach. Through the application of marker assisted selection (MAS) technique, the present study reports a successful pyramidization of genes/QTLs to confer resistance/tolerance to blast (Pi2, Pi9), gall Midge (Gm1, Gm4), submergence (Sub1), and salinity (Saltol) in a released rice variety CRMAS2621-7-1 as Improved Lalat which had already incorporated with three BB resistance genes xa5, xa13, and Xa21 to supplement the Xa4 gene present in Improved Lalat. The molecular analysis revealed clear polymorphism between the donor and recipient parents for all the markers that are tagged to the target traits. The conventional backcross breeding approach was followed till BC3F1 generation and starting from BC1F1 onwards, marker assisted selection was employed at each step to monitor the transfer of the target alleles with molecular markers. The different BC3F1s having the target genes/QTLs were inter crossed to generate hybrids with all 10 stress resistance/tolerance genes/QTLs into a single plant/line. Homozygous plants for resistance/tolerance genes in different combinations were recovered. The BC3F3 lines were characterized for their agronomic and quality traits and promising progeny lines were selected. The SSR based background selection was done. Most of the gene pyramid lines showed a high degree of similarity to the recurrent parent for both morphological, grain quality traits and in SSR based background selection. Out of all the gene pyramids tested, two lines had all the 10 resistance/tolerance genes and showed adequate levels of resistance/tolerance against the five target

  16. Macrocyclic cyclodiphosphazane : synthesis of chalcogen ...

    Indian Academy of Sciences (India)



    Sep 6, 2017 ... Abstract. The synthesis of a Schiff base-appended macrocycle [{P(μ-tBuN)}2(O − m − C6H4CHNCH2)2]2. (1) containing cyclodiphosphazane moieties is described. Reactions of 1 with H2O2 and elemental selenium yielded derivatives tetrakis(oxide) [{P(O)(μ-tBuN)}2(O − m − C6H4CHNCH2)2]2 (2) and.

  17. Algebraic stacks

    Indian Academy of Sciences (India)

    generally, any fiber product) is not uniquely defined: it is only defined up to unique isomorphism. ..... Fiber product. Given two morphisms f1 : F1 ! G, f2 : F2 ! G, we define a new stack. F1 آG F2 (with projections to F1 and F2) as follows. The objects are triples ًX1; X2; ق ..... In fact, any Artin stack F can be defined in this fashion.

  18. Macrocyclic metal complexes for metalloenzyme mimicry and sensor development. (United States)

    Joshi, Tanmaya; Graham, Bim; Spiccia, Leone


    Examples of proteins that incorporate one or more metal ions within their structure are found within a broad range of classes, including oxidases, oxidoreductases, reductases, proteases, proton transport proteins, electron transfer/transport proteins, storage proteins, lyases, rusticyanins, metallochaperones, sporulation proteins, hydrolases, endopeptidases, luminescent proteins, iron transport proteins, oxygen storage/transport proteins, calcium binding proteins, and monooxygenases. The metal coordination environment therein is often generated from residues inherent to the protein, small exogenous molecules (e.g., aqua ligands) and/or macrocyclic porphyrin units found, for example, in hemoglobin, myoglobin, cytochrome C, cytochrome C oxidase, and vitamin B12. Thus, there continues to be considerable interest in employing macrocyclic metal complexes to construct low-molecular weight models for metallobiosites that mirror essential features of the coordination environment of a bound metal ion without inclusion of the surrounding protein framework. Herein, we review and appraise our research exploring the application of the metal complexes formed by two macrocyclic ligands, 1,4,7-triazacyclononane (tacn) and 1,4,7,10-tetraazacyclododecane (cyclen), and their derivatives in biological inorganic chemistry. Taking advantage of the kinetic inertness and thermodynamic stability of their metal complexes, these macrocyclic scaffolds have been employed in the development of models that aid the understanding of metal ion-binding natural systems, and complexes with potential applications in biomolecule sensing, diagnosis, and therapy. In particular, the focus has been on "coordinatively unsaturated" metal complexes that incorporate a kinetically inert and stable metal-ligand moiety, but which also contain one or more weakly bound ligands, allowing for the reversible binding of guest molecules via the formation and dissociation of coordinate bonds. With regards to mimicking

  19. Tetrathiafulvalene- (TTF-) Derived Oligopyrrolic Macrocycles

    DEFF Research Database (Denmark)

    Jana, Atanu; Ishida, Masatoshi; Park, Jung Su


    , organic field-effect transistors, and optical sensors. Modified TTF structures thus constitute promising candidates for the development of so-called “functional materials” that could see use in modern technological applications. The versatility of the TTF unit and the pioneering synthetic strategies...... that have been developed over the past few decades provide opportunities to tune the architecture and function for specific purposes. This review covers the “state of the art” associated with TTF-annulated oligopyrrolic macrocyclic compounds. Points of emphasis include synthesis, properties, and potential...

  20. Radical photocyclization route for macrocyclic lactone ring expansion and conversion to macrocyclic lactams and ketones. (United States)

    Nishikawa, Keisuke; Yoshimi, Yasuharu; Maeda, Kousuke; Morita, Toshio; Takahashi, Ichiro; Itou, Tatsuya; Inagaki, Sho; Hatanaka, Minoru


    A new method for the synthesis of macrocyclic lactones, lactams, and ketones, which utilizes photoinduced intramolecular radical cyclization reactions of substrates containing tethered carboxylic acids and α,β-unsaturated carbonyl moieties, has been uncovered. Photocyclization of the carboxylic acids tethered acrylate ester, which were prepared starting from the macrocyclic lactones, gave the two-carbon elongated macrocyclic lactones via decarboxylation. Similar photoreactions of carboxylic acid tethered acryl amide or α,β-unsaturated ketone moieties, which were also prepared starting from the macrocyclic lactones, produced macrocyclic lactams or ketones, respectively. The simple approach can be readily applied to the preparation of a variety of macrocyclic lactones, lactams, and ketones with tunable ring sizes.

  1. Algebraic stacks

    Indian Academy of Sciences (India)

    truct the 'moduli stack', that captures all the information that we would like in a fine moduli space. ..... the fine moduli space), it has the property that for any family W of vector bundles (i.e. W is a vector bundle over B ...... the etale topology is finer: V is a 'small enough open subset' because the square root can be defined on it.

  2. Comprehensive computational design of ordered peptide macrocycles (United States)

    Hosseinzadeh, Parisa; Bhardwaj, Gaurav; Mulligan, Vikram Khipple; Shortridge, Matthew D.; Craven, Timothy W.; Pardo-Avila, Fátima; Rettie, Stephen A.; Kim, David E.; Silva, Daniel-Adriano; Ibrahim, Yehia M.; Webb, Ian K.; Cort, John R.; Adkins, Joshua N.; Varani, Gabriele; Baker, David


    Mixed-chirality peptide macrocycles such as cyclosporine are among the most potent therapeutics identified to date, but there is currently no way to systematically search the structural space spanned by such compounds. Natural proteins do not provide a useful guide: Peptide macrocycles lack regular secondary structures and hydrophobic cores, and can contain local structures not accessible with L-amino acids. Here, we enumerate the stable structures that can be adopted by macrocyclic peptides composed of L- and D-amino acids by near-exhaustive backbone sampling followed by sequence design and energy landscape calculations. We identify more than 200 designs predicted to fold into single stable structures, many times more than the number of currently available unbound peptide macrocycle structures. Nuclear magnetic resonance structures of 9 of 12 designed 7- to 10-residue macrocycles, and three 11- to 14-residue bicyclic designs, are close to the computational models. Our results provide a nearly complete coverage of the rich space of structures possible for short peptide macrocycles and vastly increase the available starting scaffolds for both rational drug design and library selection methods. PMID:29242347

  3. 8th International Symposium on Supramolecular and Macrocyclic Chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Davis, Jeffery T. [Univ. of Maryland, College Park, MD (United States)


    This report summarizes the 8th International Conference on Supramolecular and Macrocyclic Chemistry (ISMSC-8). DOE funds were used to make it more affordable for students, post-docs and junior faculty to attend the conference by covering their registration costs. The conference was held in Crystal City, VA from July 7-11, 2013. See for the conference website. ISMSC-8 encompassed the broad scope and interdisciplinary nature of the field. We met our goal to bring together leading scientists in molecular recognition and supramolecular chemistry. New research directions and collaborations resulted this conference. The DOE funding was crucial for us achieving our primary goal.

  4. Macrocyclic extractants for separating Am(III)/Ln(III)

    International Nuclear Information System (INIS)

    Ludwig, R.; Nguyen, T.K.D.; Kunogi, K.; Tachimori, Shoichi


    The extraction of trivalent f-elements by calix(n)arene-type macrocyclic ligands increases in the order n=4, 8, 6 corresponding to the balance between cavity size, molecular flexibility, and number of donor atoms. Introduction of mixed functionalities into calix(6)arenes, e.g. carboxylic acid and amide groups, results in better extractability of actinides compared with lanthanides. For calix(4)arenes, such a different extractability could not be observed. Furthermore, the effects of solvent composition with respect to a modifier and of the aqueous phase composition were investigated. (author)

  5. Binding energies of the π-stacked anisole dimer: new molecular beam-laser spectroscopy experiments and CCSD(T) calculations. (United States)

    Řezáč, Jan; Nachtigallová, Dana; Mazzoni, Federico; Pasquini, Massimiliano; Pietraperzia, Giangaetano; Becucci, Maurizio; Müller-Dethlefs, Klaus; Hobza, Pavel


    Among noncovalent interactions, π-π stacking is a very important binding motif governed mainly by London dispersion. Despite its importance, for instance, for the structure of bio-macromolecules, the direct experimental measurement of binding energies in π-π stacked complexes has been elusive for a long time. Only recently, an experimental value for the binding energy of the anisole dimer was presented, determined by velocity mapping ion imaging in a two-photon resonant ionisation molecular beam experiment. However, in that paper, a discrepancy was already noted between the obtained experimental value and a theoretical estimate. Here, we present an accurate recalculation of the binding energy based on the combination of the CCSD(T)/CBS interaction energy and a DFT-D3 vibrational analysis. This proves unambiguously that the previously reported experimental value is too high and a new series of measurements with a different, more sensitive apparatus was performed. The new experimental value of 1800±100 cm(-1) (5.15±0.29 kcal mol(-1)) is close to the present theoretical prediction of 5.04±0.40 kcal mol(-1). Additional calculations of the properties of the cationic and excited states involved in the photodissociation of the dimer were used to identify and rationalise the difficulties encountered in the experimental work. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Donor-Acceptor Conjugated Macrocycles: Synthesis and Host-Guest Coassembly with Fullerene toward Photovoltaic Application. (United States)

    Zhang, Si-Qi; Liu, Zhen-Yu; Fu, Wei-Fei; Liu, Feng; Wang, Chuan-Ming; Sheng, Chun-Qi; Wang, Yi-Fei; Deng, Ke; Zeng, Qing-Dao; Shu, Li-Jin; Wan, Jun-Hua; Chen, Hong-Zheng; Russell, Thomas P


    Electron-rich (donor) and electron-deficient (acceptor) units to construct donor-acceptor (D-A) conjugated macrocycles were investigated to elucidate their interactions with electron-deficient fullerene. Triphenylamine and 4,7-bisthienyl-2,1,3-benzothiadiazole were alternately linked through acetylene, as the donor and acceptor units, respectively, for pentagonal 3B2A and hexagonal 4B2A macrocycles. As detected by scanning tunneling microscopy, both D-A macrocycles were found to form an interesting concentration-controlled nanoporous monolayer on highly oriented pyrolytic graphite, which could effectively capture fullerene. Significantly, the fullerene filling was cavity-size-dependent with only one C 70 or PC 71 BM molecule accommodated by 3B2A, while two were accommodated by 4B2A. Density functional theory calculations were also utilized to gain insight into the host-guest systems and indicted that the S···π contact is responsible for stabilizing these host-guest systems. Owing to the ellipsoidal shape of C 70 , C 70 molecules are standing or lying in molecular cavities depending on the energy optimization. For the 3B2A/PC 71 BM blended film, PC 71 BM was intercalated into the cavity formed by the macrocycle 3B2A and provided excellent power conversion efficiency despite the broad band gap (2.1 eV) of 3B2A. This study of D-A macrocycles incorporating fullerene provides insights into the interaction mechanism and electronic structure in the host-guest complexes. More importantly, this is a representative example using D-A macrocycles as a donor to match with the spherical fullerene acceptor for photovoltaic applications, which offer a good approach to achieve molecular scale p-n junctions for substantially enhanced efficiencies of organic solar cells through replacing linear polymer donors by cyclic conjugated oligomers.

  7. Design and synthesis of a new steroid-macrocyclic derivative with biological activity. (United States)

    López-Ramos, Maria; Figueroa-Valverde, Lauro; Herrera-Meza, Socorro; Rosas-Nexticapa, Marcela; Díaz-Cedillo, Francisco; García-Cervera, Elodia; Pool-Gómez, Eduardo; Cahuich-Carrillo, Regina


    The aims of this study were to evaluate the positive inotropic effect of a new macrocyclic derivative (compound 11 ) and characterize the molecular mechanism involved in its biological activity. The first step was achieved by synthesis of a macrocyclic derivative involving a series of reactions for the preparation of several steroid derivatives such as (a) steroid-pyrimidinone ( 3 and 4 ), (b) steroid-amino ( 5 ), (c) steroid-imino ( 6 ), (d) ester-steroid ( 7 and 8 ), and (e) amido-steroid ( 9 and 10 ). Finally, 11 was prepared by removing the tert -butyldimethylsilane fragment of 10 . The biological activity of compounds on perfusion pressure and vascular resistance was evaluated on isolated rat heart using the Langendorff model. The inotropic activity of 11 was evaluated in presence of prazosin, metoprolol, indomethacin, nifedipine, and flutamide to characterize its molecular mechanism. Theoretical experiments were carried out with a Docking model, to assess potential interactions of androgen receptor with 11 . The results showed that only this macrocyclic derivative exerts changes on perfusion pressure and vascular resistance translated as the positive inotropic effect, and this effect was blocked with flutamide; these data indicate that the positive inotropic activity induced by this macrocyclic derivative was via androgen receptor activation. The theoretical results indicated that the interaction of the macrocyclic derivative with the androgen receptor involves several amino acid residues such as Leu 704 , Asn 705 , Met 780 , Cys 784 , Met 749 , Leu 762 , Phe 764 , Ser 778 , and Met 787 . In conclusion, all these data suggest that the positive inotropic activity of the macrocyclic derivative may depend on its chemical structure.

  8. Phosphorus-containing macrocyclic compounds: synthesis and properties

    International Nuclear Information System (INIS)

    Knyazeva, I R; Burilov, Alexander R; Pudovik, Michael A; Habicher, Wolf D


    Main trends in the development of methods for the synthesis of phosphorus-containing macrocyclic compounds in the past 15 years are considered. Emphasis is given to reactions producing macrocyclic structures with the participation of a phosphorus atom and other functional groups involved in organophosphorus molecules and to modifications of macrocycles by phosphorus compounds in different valence states. Possibilities of the practical application of phosphorus-containing macrocyclic compounds in difference areas of science and engineering are discussed. The bibliography includes 205 references.

  9. Solar Thermal Energy Storage in a Photochromic Macrocycle. (United States)

    Vlasceanu, Alexandru; Broman, Søren L; Hansen, Anne S; Skov, Anders B; Cacciarini, Martina; Kadziola, Anders; Kjaergaard, Henrik G; Mikkelsen, Kurt V; Nielsen, Mogens Brøndsted


    The conversion and efficient storage of solar energy is recognized to hold significant potential with regard to future energy solutions. Molecular solar thermal batteries based on photochromic systems exemplify one possible technology able to harness and apply this potential. Herein is described the synthesis of a macrocycle based on a dimer of the dihydroazulene/vinylheptafulvene (DHA/VHF) photo/thermal couple. By taking advantage of conformational strain, this DHA-DHA macrocycle presents an improved ability to absorb and store incident light energy in chemical bonds (VHF-VHF). A stepwise energy release over two sequential ring-closing reactions (VHF→DHA) combines the advantages of an initially fast discharge, hypothetically addressing immediate energy consumption needs, followed by a slow process for consistent, long-term use. This exemplifies another step forward in the molecular engineering and design of functional organic materials towards solar thermal energy storage and release. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Interference between Coulombic and CT-mediated couplings in molecular aggregates: H- to J-aggregate transformation in perylene-based π-stacks

    International Nuclear Information System (INIS)

    Hestand, Nicholas J.; Spano, Frank C.


    The spectroscopic differences between J and H-aggregates are traditionally attributed to the spatial dependence of the Coulombic coupling, as originally proposed by Kasha. However, in tightly packed molecular aggregates wave functions on neighboring molecules overlap, leading to an additional charge transfer (CT) mediated exciton coupling with a vastly different spatial dependence. The latter is governed by the nodal patterns of the molecular LUMOs and HOMOs from which the electron (t e ) and hole (t h ) transfer integrals derive. The sign of the CT-mediated coupling depends on the sign of the product t e t h and is therefore highly sensitive to small (sub-Angstrom) transverse displacements or slips. Given that Coulombic and CT-mediated couplings exist simultaneously in tightly packed molecular systems, the interference between the two must be considered when defining J and H-aggregates. Generally, such π-stacked aggregates do not abide by the traditional classification scheme of Kasha: for example, even when the Coulomb coupling is strong the presence of a similarly strong but destructively interfering CT-mediated coupling results in “null-aggregates” which spectroscopically resemble uncoupled molecules. Based on a Frenkel/CT Holstein Hamiltonian that takes into account both sources of electronic coupling as well as intramolecular vibrations, vibronic spectral signatures are developed for integrated Frenkel/CT systems in both the perturbative and resonance regimes. In the perturbative regime, the sign of the lowest exciton band curvature, which rigorously defines J and H-aggregation, is directly tracked by the ratio of the first two vibronic peak intensities. Even in the resonance regime, the vibronic ratio remains a useful tool to evaluate the J or H nature of the system. The theory developed is applied to the reversible H to J-aggregate transformations recently observed in several perylene bisimide systems

  11. Pharmacologically significant tetraaza macrocyclic metal complexes ...

    Indian Academy of Sciences (India)



    Nov 22, 2017 ... along with medical sector (up to 60% of the total human infections are provoked by biofilms).24–26 The Candida biofilms formation has an important ..... 784.01 respectively, correspond to the nitrogen isotope. The mass spectra of Schiff base macrocyclic complexes of Co(II), (a) Ni, (b) Cu(II), (c) and Zn(II), ...

  12. Rapid synthesis of macrocycles from diol precursors

    DEFF Research Database (Denmark)

    Wingstrand, Magnus; Madsen, Charlotte Marie; Clausen, Mads Hartvig


    A method for the formation of synthetic macrocycles with different ring sizes from diols is presented. Reacting a simple diol precursor with electrophilic reagents leads to a cyclic carbonate, sulfite or phosphate in a single step in 25-60% yield. Converting the cyclization precursor to a bis-ele...

  13. Photoswitchable Dihydroazulene Macrocycles for Solar Energy Storage: The Effects of Ring Strain. (United States)

    Vlasceanu, Alexandru; Frandsen, Benjamin N; Skov, Anders B; Hansen, Anne Schou; Rasmussen, Mads Georg; Kjaergaard, Henrik G; Mikkelsen, Kurt V; Nielsen, Mogens Brøndsted


    Efficient energy storage and release are two major challenges of solar energy harvesting technologies. The development of molecular solar thermal systems presents one approach to address these issues by tuning the isomerization reactions of photo/thermoswitches. Here we show that the incorporation of photoswitches into macrocyclic structures is a particularly attractive solution for increasing the storage time. We present the synthesis and properties of a series of macrocycles incorporating two dihydroazulene (DHA) photoswitching subunits, bridged by linkers of varying chain length. Independent of ring size, all macrocycles exhibit stepwise, light-induced, ring-opening reactions (DHA-DHA to DHA-VHF to VHF-VHF; VHF = vinylheptafulvene) with the first DHA undergoing isomerization with a similar efficiency as the uncyclized parent system while the second (DHA-VHF to VHF-VHF) is significantly slower. The energy-releasing, VHF-to-DHA, ring closures also occur in a stepwise manner and are systematically found to proceed slower in the more strained (smaller) cycles, but in all cases with a remarkably slow conversion of the second VHF to DHA. We managed to increase the half-life of the second VHF-to-DHA conversion from 65 to 202 h at room temperature by simply decreasing the ring size. A computational study reveals the smallest macrocycle to have the most energetic VHF-VHF state and hence highest energy density.

  14. Relationship between molecular stacking and optical properties of 9,10-bis((4-N,N-dialkylamino)styryl) anthracene crystals: the cooperation of excitonic and dipolar coupling. (United States)

    Li, Feng; Gao, Na; Xu, Hai; Liu, Wei; Shang, Hui; Yang, Wenjun; Zhang, Ming


    Five 9,10-bis((4-N,N-dialkylamino)styryl) anthracene derivatives (DSA-C1-DSA-C7) with different length alkyl chains were synthesized. They showed the same color in dilute solutions but different colors in crystals. The absorption, photoluminescence, and fluorescence decay indicate that there exist both excitonic and dipolar coupling in crystals of DSA-C1-DSA-C7. X-ray crystallographic analysis revealed that all the crystals belong to the triclinic space group P1 with one molecule per unit cell and that the molecules in every crystal have the identical orientation. This offers ideal samples to investigate the impact of the molecular stacking on the optical properties of the crystals. For the first time, the cooperation of excitonic and dipolar coupling has been comprehensively studied, and the contribution to the spectral shift from the excitonic and dipolar couplings quantitatively obtained. The experiments of amplified spontaneous emission (ASE) together with measurements of the quantum efficiency further confirmed this interpretation. The results suggest that the excitonic and dipolar couplings between the adjacent molecules are both important and jointly induce the spectral shifts of the crystals. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Ab initio molecular dynamics simulation of the effects of stacking faults on the radiation response of 3C-SiC. (United States)

    Jiang, M; Peng, S M; Zhang, H B; Xu, C H; Xiao, H Y; Zhao, F A; Liu, Z J; Zu, X T


    In this study, an ab initio molecular dynamics method is employed to investigate how the existence of stacking faults (SFs) influences the response of SiC to low energy irradiation. It reveals that the C and Si atoms around the SFs are generally more difficult to be displaced than those in unfaulted SiC, and the corresponding threshold displacement energies for them are generally larger, indicative of enhanced radiation tolerance caused by the introduction of SFs, which agrees well with the recent experiment. As compared with the unfaulted state, more localized point defects are generated in faulted SiC. Also, the efficiency of damage production for Si recoils is generally higher than that of C recoils. The calculated potential energy increases for defect generation in SiC with intrinsic and extrinsic SFs are found to be higher than those in unfaulted SiC, due to the stronger screen-Coulomb interaction between the PKA and its neighbors. The presented results provide a fundamental insight into the underlying mechanism of displacement events in faulted SiC and will help to advance the understanding of the radiation response of SiC with and without SFs.

  16. Spectrophotometric method for determination of bifunctional macrocyclic ligands in macrocyclic ligand-protein conjugates

    International Nuclear Information System (INIS)

    Dadachova, E.; Chappell, L.L.; Brechbiel, M.W.


    A simple spectrophotometric assay for determination of bifunctional polyazacarboxylate-macrocyclic ligands of different sizes that are conjugated to proteins has been developed for: 12-membered macrocycle DOTA (2-[4-nitrobenzyl]-1, 4, 7, 10-tetraazacyclododecane-N,N',N'',N'''-tetraacetic acid) and analogs, the 15-membered PEPA macrocycle (2-[4-nitrobenzyl]-1,4,7,10,13-pentaazacyclopentadecane-N,N',N'',N''',N'''' -pentaacetic acid), and the large 18-membered macrocycle HEHA (1,4,7,10,13,16-hexaazacyclooctadecane-N,N',N'',N''',N''''-hexaacetic acid). The method is based on titration of the blue-colored 1:1 Pb(II)-Arsenazo III (AAIII) complex with the polyazacarboxylate macrocyclic ligand in the concentration range of 0-2.5 μM, wherein color change occurring upon transchelation of the Pb(II) from the AAIII to the polyazamacrocyclic ligand is monitored at 656 nm. The assay is performed at ambient temperature within 20 min without any interfering interaction between the protein and Pb(II)-AA(III) complex. Thus, this method also provides a ligand-to-protein ratio (L/P ratio) that reflects the effective number of ligands per protein molecule available to radiolabeling. The method is not suitable for 14-membered TETA macrocycle (2-[4-nitrobenzyl]-1, 4, 8, 11-tetraazacyclotetradecane N,N',N'',N'''-tetraacetic acid) because of low stability constant of Pb(II)-TETA complex. The method is rapid, simple and may be customized for other polyazacarboxylate macrocyclic ligands

  17. The unusual macrocycle forming thioesterase of mycolactone. (United States)

    Meier, Jordan L; Barrows-Yano, Tiffany; Foley, Timothy L; Wike, Candice L; Burkart, Michael D


    Mycolactone is a polyketide natural product secreted by Mycobacterium ulcerans, the organism responsible for the tropical skin disease Buruli ulcer. The finding that this small molecule virulence factor is sufficient to reconstitute the necrotic pathology associated with Buruli ulcer suggests that a better understanding of mycolactone biosynthesis, particularly the processes which are distinct from those in human metabolism, may provide a unique avenue for the development of selective therapeutics. In the present study we have cloned, expressed, and biochemically characterized the putative macrocycle forming thioesterase for mycolactone, MLSA2 TE. We have evaluated the enzyme both as the truncated thioesterase domain and as a carrier protein-linked didomain construct. The results of these analyses distinguish MLSA2 TE from traditional fatty acid and polyketide synthase TE-domains in terms of its sequence, kinetic parameters, and susceptibility to traditional active-site directed inhibitors. These findings suggest that MLSA2 TE utilizes a unique biochemical mechanism for macrocycle formation.

  18. Structural Interpretation of the Large Slowdown of Water Dynamics at Stacked Phospholipid Membranes for Decreasing Hydration Level: All-Atom Molecular Dynamics

    Directory of Open Access Journals (Sweden)

    Carles Calero


    Full Text Available Hydration water determines the stability and function of phospholipid membranes as well as the interaction of membranes with other molecules. Experiments and simulations have shown that water dynamics slows down dramatically as the hydration decreases, suggesting that the interfacial water that dominates the average dynamics at low hydration is slower than water away from the membrane. Here, based on all-atom molecular dynamics simulations, we provide an interpretation of the slowdown of interfacial water in terms of the structure and dynamics of water–water and water–lipid hydrogen bonds (HBs. We calculate the rotational and translational slowdown of the dynamics of water confined in stacked phospholipid membranes at different levels of hydration, from completely hydrated to poorly hydrated membranes. For all hydrations, we analyze the distribution of HBs and find that water–lipids HBs last longer than water–water HBs and that at low hydration most of the water is in the interior of the membrane. We also show that water–water HBs become more persistent as the hydration is lowered. We attribute this effect (i to HBs between water molecules that form, in turn, persistent HBs with lipids; (ii to the hindering of the H-bonding switching between water molecules due to the lower water density at the interface; and (iii to the higher probability of water–lipid HBs as the hydration decreases. Our interpretation of the large dynamic slowdown in water under dehydration is potentially relevant in understanding membrane biophysics at different hydration levels.

  19. Supramolecular Organocatalysis in Water Mediated by Macrocyclic Compounds

    Directory of Open Access Journals (Sweden)

    Margherita De Rosa


    Full Text Available In the last decades many efforts have been devoted to design supramolecular organocatalysts able to work in water as the reaction medium. The use of water as solvent provides promising benefits with respect to environmental impact. In this context, macrocyclic compounds played a role of primary importance thanks to their ease of synthesis and their molecular recognition abilities toward the reactants. The aim of this review is to give an overview of the recent advances in the field of supramolecular organocatalysis in water, focusing the attention on calixarene and cyclodextrins derivatives. Calixarenes and cyclodextrins, thanks to their hydrophobic cavities, are able to host selectively the substrates isolating they from the reaction environment. In addition, the synthetic versatilities of these macrocycles permits to introduce useful functional groups in close proximity of the hydrophobic binding sites. Regarding the cyclodextrins (CDs, we have here reviewed the their most recent uses as organocatalysts for the synthesis of heterocyclic compounds, in multi-component reactions and in carbon-carbon bond forming reactions. Examples have been reported in which CD catalysts are able to drive the regiochemistry of common organic reactions. In addition, cyclodextrins bearing catalytically active chiral groups, have shown excellent enantioselectivity in the catalysis of organic reactions. Recently reported results have shown that calixarene derivatives are able to accelerate organic reaction under “on-water” conditions with a significant selectivity toward the reactants. Under “on-water conditions” the hydrophobic effect, induced by insoluble calixarene derivatives, forces the reactants and the catalyst to aggregate and thus accelerating the reaction between them thanks to an amplification of weak secondary interactions. Regarding the use of water-soluble calixarene organocatalysts, we have here reviewed their role in the acceleration of

  20. Ring strain and total syntheses of modified macrocycles of the isoplagiochin type

    Directory of Open Access Journals (Sweden)

    Andreas Speicher


    Full Text Available Macrocycles of the bisbibenzyl-type are natural products that are found exclusively in bryophytes (liverworts. The molecular framework of the subtype “isoplagiochin” is of substantial structural interest because of the chirality of the entire molecule, which arises from two biaryl axes in combination with two helical two-carbon units in a cyclic arrangement. From a structural as well as a synthetic point of view we report on the total synthesis of compounds which possess more rigid two-carbon biaryl bridges like stilbene (E or Z or even tolane moieties which were introduced starting with a Sonogashira protocol. The McMurry method proved to be a powerful tool for the cyclization to these considerably ring-strained macrocycles.

  1. Kinetics of oxidation of nickel(II) aza macrocycles by ...

    Indian Academy of Sciences (India)

    Introduction. The chemical behaviour of transition-metal complexes often depends on their redox properties. This is true to a large extent for the natural and synthetic complexes involving macrocyclic ligands such as Ni(II) hexaaza and pentaaza macrocyclic derivatives which are known to display properties and reactivity ...

  2. Kinetics of oxidation of nickel(II) aza macrocycles by ...

    Indian Academy of Sciences (India)

    Almost all Ni(II) macrocyclic complexes investigated so far, display the typical macrocyclic inertness towards demetallation by strong acids 11. Most of the Ni(II) complexes have been isolated as perchlorate salts by the addition of concentrated perchloric acid to the reaction solution. These salts are water soluble and show ...

  3. Antibacterial and antioxidant properties of macrocyclic Schiff bases ...

    African Journals Online (AJOL)


    Also in-vitro antioxidant activity of all compounds was determined by nitric acid free radical scavanging assay. Keywords: Macrocyclic Schiff Bases; Vanadium complexes; Antibacterial; Antioxidant activities. 1. INTRODUCTION. The macrocyclic ligands are highly significant in bioinorganic chemistry, catalysis, extraction of ...

  4. Design, Properties and Recent Application of Macrocycles in Medicinal Chemistry. (United States)

    Ermert, Philipp


    Macrocyclic compounds have recently received increasing attention in drug discovery as these compounds offer the potential to modulate difficult targets and to access novel chemotypes. Approaches towards libraries of macrocyclic compounds based on modular organic synthesis and applications of these technology platforms to find and improve biologically active compounds are introduced in this minireview. Alternatively, lead compounds may be obtained by truncation and modification of macrocyclic natural products. Selected medicinal chemistry programs are discussed, illustrating a macrocyclization approach toward ligands with improved properties. The design of such ligands is often informed by X-ray crystal structures of protein-ligand complexes. Efforts to understand cellular permeability and oral bioavailability of cyclic peptides and non-peptidic macrocycles are summarized.

  5. Synthesis of New Macrocyclic Polyamides as Antimicrobial Agent Candidates

    Directory of Open Access Journals (Sweden)

    Osama I. Abd El-Salam


    Full Text Available A series of macrocyclic imides and Schiff-bases have been prepared via the cyclocondensation of pyridine-2,6-dicarbonyl dichloride (1 with L-ornithine methyl ester to give the corresponding macrocyclic bisester 2. Treatment of 2 with hydrazine hydrate gave macrocyclic bisacid hydrazide 3, which was used as starting material. Condensation of bishydrazide 3 with diacid anhydrides or aromatic aldehydes in refluxing acetic acid or ethanol gave the corresponding macrocyclic bisimides 4, 5a,b and macrocyclic bis- hydrazones 6a–j, respectively. The structure assignments of the new compounds were based on chemical and spectroscopic evidence. The antimicrobial screening showed that many of these newly synthesized compounds have good antimicrobial activities, comparable to ampicillin and ketaconazole used as reference drugs.

  6. Confined Synthesis of Organometallic Chains and Macrocycles by Cu-O Surface Templating. (United States)

    Fan, Qitang; Dai, Jingya; Wang, Tao; Kuttner, Julian; Hilt, Gerhard; Gottfried, J Michael; Zhu, Junfa


    The bottom-up construction of low-dimensional macromolecular nanostructures directly on a surface is a promising approach for future application in molecular electronics and integrated circuit production. However, challenges still remain in controlling the formation of these nanostructures with predetermined patterns (such as linear or cyclic) or dimensions (such as the length of one-dimensional (1D) chains). Here, we demonstrate that a high degree of structural control can be achieved by employing a Cu(110)-(2×1)O nanotemplate for the confined synthesis of organometallic chains and macrocycles. This template contains ordered arrays of alternating stripes of Cu-O chains and bare Cu, the widths of which are controllable. Using scanning tunneling microscopy and low-energy electron diffraction, we show that well-defined, ordered 1D zigzag organometallic oligomeric chains with uniform lengths can be fabricated on the Cu stripes (width >5.6 nm) of the Cu(110)-(2×1)O surface. In addition, the lengths of the meta-terphenyl (MTP)-based chains can be adjusted by controlling the widths of the Cu stripes within a certain range. When reducing the widths of Cu stripes to a range of 2.6 to 5.6 nm, organometallic macrocycles including tetramer (MTP-Cu)4, hexamer (MTP-Cu)6, and octamer (MTP-Cu)8 species are formed due to the spatial confinement effect and attraction to the Cu-O chains. An overview of all formed organometallic macrocycles on the Cu stripes with different widths reveals that the origin of the formation of these macrocycles is the cis-configured organometallic dimer (MTP)2Cu3, which was observed on the extremely narrow Cu stripe with a width of 1.5 nm.

  7. Deploying OpenStack

    CERN Document Server

    Pepple, Ken


    OpenStack was created with the audacious goal of being the ubiquitous software choice for building public and private cloud infrastructures. In just over a year, it's become the most talked-about project in open source. This concise book introduces OpenStack's general design and primary software components in detail, and shows you how to start using it to build cloud infrastructures. If you're a developer, technologist, or system administrator familiar with cloud offerings such as Rackspace Cloud or Amazon Web Services, Deploying OpenStack shows you how to obtain and deploy OpenStack softwar

  8. Binding Energies of the pi-Stacked Anisole Dimer: New Molecular Beam-Laser Spectroscopy Experiments and CCSD(T) Calculations

    Czech Academy of Sciences Publication Activity Database

    Řezáč, Jan; Nachtigallová, Dana; Mazzoni, F.; Pasquini, M.; Pietraperzia, G.; Becucci, M.; Müller-Dethlefs, K.; Hobza, Pavel


    Roč. 21, č. 18 (2015), s. 6740-6746 ISSN 0947-6539 R&D Projects: GA ČR GBP208/12/G016 Grant - others:GA MŠk(CZ) ED2.1.00/03.0058 Program:ED Institutional support: RVO:61388963 Keywords : binding energy * noncovalent interactions * pi stacking * laser spectroscopy * CCSD(T) calculations Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 5.771, year: 2015

  9. A room-temperature phosphorescent polymer film containing a molecular web based on one-dimensional chiral stacking of a simple luminophore. (United States)

    Yoshida, Kyohei; Kuwahara, Yutaka; Miyamoto, Koji; Nakashima, Seiya; Jintoku, Hirokuni; Takafuji, Makoto; Ihara, Hirotaka


    We propose a new approach for a totally organic, room-temperature phosphorescent system with a lifetime on the order of milliseconds, which is achieved by promotion of the one-dimensional chiral stacking of a simple, small fluorophore in a solution state. The versatility of this system is highlighted by its good applicability to the fabrication of a phosphorescent polymer film. This paper demonstrates the first example of a room-temperature phosphorescent polymer film prepared with our methodology.

  10. OpenStack essentials

    CERN Document Server

    Radez, Dan


    If you need to get started with OpenStack or want to learn more, then this book is your perfect companion. If you're comfortable with the Linux command line, you'll gain confidence in using OpenStack.

  11. Mastering OpenStack

    CERN Document Server

    Khedher, Omar


    This book is intended for system administrators, cloud engineers, and system architects who want to deploy a cloud based on OpenStack in a mid- to large-sized IT infrastructure. If you have a fundamental understanding of cloud computing and OpenStack and want to expand your knowledge, then this book is an excellent checkpoint to move forward.

  12. Design and Synthesis of Novel Macrocyclic Mer Tyrosine Kinase Inhibitors. (United States)

    Wang, Xiaodong; Liu, Jing; Zhang, Weihe; Stashko, Michael A; Nichols, James; Miley, Michael J; Norris-Drouin, Jacqueline; Chen, Zhilong; Machius, Mischa; DeRyckere, Deborah; Wood, Edgar; Graham, Douglas K; Earp, H Shelton; Kireev, Dmitri; Frye, Stephen V


    Mer tyrosine kinase (MerTK) is aberrantly elevated in various tumor cells and has a normal anti-inflammatory role in the innate immune system. Inhibition of MerTK may provide dual effects against these MerTK-expressing tumors through reducing cancer cell survival and redirecting the innate immune response. Recently, we have designed novel and potent macrocyclic pyrrolopyrimidines as MerTK inhibitors using a structure-based approach. The most active macrocycles had an EC 50 below 40 nM in a cell-based MerTK phosphor-protein ELISA assay. The X-ray structure of macrocyclic analogue 3 complexed with MerTK was also resolved and demonstrated macrocycles binding in the ATP binding pocket of the MerTK protein as anticipated. In addition, the lead compound 16 (UNC3133) had a 1.6 h half-life and 16% oral bioavailability in a mouse PK study.

  13. Guanine base stacking in G-quadruplex nucleic acids (United States)

    Lech, Christopher Jacques; Heddi, Brahim; Phan, Anh Tuân


    G-quadruplexes constitute a class of nucleic acid structures defined by stacked guanine tetrads (or G-tetrads) with guanine bases from neighboring tetrads stacking with one another within the G-tetrad core. Individual G-quadruplexes can also stack with one another at their G-tetrad interface leading to higher-order structures as observed in telomeric repeat-containing DNA and RNA. In this study, we investigate how guanine base stacking influences the stability of G-quadruplexes and their stacked higher-order structures. A structural survey of the Protein Data Bank is conducted to characterize experimentally observed guanine base stacking geometries within the core of G-quadruplexes and at the interface between stacked G-quadruplex structures. We couple this survey with a systematic computational examination of stacked G-tetrad energy landscapes using quantum mechanical computations. Energy calculations of stacked G-tetrads reveal large energy differences of up to 12 kcal/mol between experimentally observed geometries at the interface of stacked G-quadruplexes. Energy landscapes are also computed using an AMBER molecular mechanics description of stacking energy and are shown to agree quite well with quantum mechanical calculated landscapes. Molecular dynamics simulations provide a structural explanation for the experimentally observed preference of parallel G-quadruplexes to stack in a 5′–5′ manner based on different accessible tetrad stacking modes at the stacking interfaces of 5′–5′ and 3′–3′ stacked G-quadruplexes. PMID:23268444

  14. Synthesis and Characterisation of Macrocyclic Diamino Chiral Crown Ethers

    Directory of Open Access Journals (Sweden)

    Janet L. Scott


    Full Text Available A benign and efficient synthesis of chiral macrocyclic ‘aza-crown’ ethers of varying ring size is reported. The synthesis involves a Schiff base condensation of ether linked dialdehydes of varying chain length and (1R,2R-(–-1,2-diaminocyclohexane under mild conditions to yield the macrocycles, which are subsequently reduced to yield the diamino analogues.


    NARCIS (Netherlands)



    A chemically modified field-effect transistor (CHEMFET) with satisfactory Ag+ selectivity is described. The potentiometric Ag+ selectivities of CHEMFETs with plasticized PVC membranes based on macrocyclic thioethers have been determined. All the macrocyclic thioethers tested showed silver response

  16. Macrocyclic Assembly: A Dive into the Pecking Order and Applied Aspects of Multitalented Metallomacrocycles

    Directory of Open Access Journals (Sweden)

    Ashu Chaudhary


    Full Text Available To aid in knowledge of macrocyclic complexes and biomedical scientists, we are presenting here a review article with compilation of work done so far along in relation to macrocyclic ligands and their metal complexes. The metal ion chemistry of macrocyclic ligands has now become a major subdivision of coordination chemistry. This overview focuses on developments in design, synthesis, and self-assembly of metal-based architectures and ligands related to macrocyclic chemistry.

  17. Design and synthesis of binucleating macrocyclic clefts derived from Schiff-base calixpyrroles. (United States)

    Givaja, Gonzalo; Volpe, Manuel; Leeland, James W; Edwards, Michael A; Young, Thomas K; Darby, S Barnie; Reid, Stuart D; Blake, Alexander J; Wilson, Claire; Wolowska, Joanna; McInnes, Eric J L; Schröder, Martin; Love, Jason B


    The syntheses, characterisation and complexation reactions of a series of binucleating Schiff-base calixpyrrole macrocycles are described. The acid-templated [2+2] condensations between meso-disubstituted diformyldipyrromethanes and o-phenylenediamines generate the Schiff-base pyrrolic macrocycles H(4)L(1) to H(4)L(6) upon basic workup. The single-crystal X-ray structures of both H(4)L(3).2 EtOH and H(4)L(6).H2O confirm that [2+2] cyclisation has occurred, with either EtOH or H2O hydrogen-bonded within the macrocyclic cleft. A series of complexation reactions generate the dipalladium [Pd2(L)] (L=L(1) to L(5)), dinickel [Ni2(L(1))] and dicopper [Cu2(L)] (L=L(1) to L(3)) complexes. All of these complexes have been structurally characterised in the solid state and are found to adopt wedged structures that are enforced by the rigidity of the aryl backbone to give a cleft reminiscent of the structures of Pacman porphyrins. The binuclear nickel complexes [Ni2(mu-OMe)2Cl2(HOMe)2(H(4)L(1))] and [Ni2(mu-OH)2Cl2(HOMe)(H(4)L(5))] have also been prepared, although in these cases the solid-state structures show that the macrocyclic ligand remains protonated at the pyrrolic nitrogen atoms, and the Ni(II) cations are therefore co-ordinated by the imine nitrogen atoms only to give an open conformation for the complex. The dicopper complex [Cu2(L(3))] was crystallised in the presence of pyridine to form the adduct [Cu2(py)(L(3))], in which, in the solid state, the pyridine ligand is bound within the binuclear molecular cleft. Reaction between H(4)L(1) and [Mn(thf){N(SiMe(3))2}2] results in clean formation of the dimanganese complex [Mn2(L(1))], which, upon crystallisation, formed the mixed-valent complex [Mn2(mu-OH)(L(1))] in which the hydroxo ligand bridges the metal centres within the molecular cleft.

  18. Discovery of Macrocyclic Pyrimidines as MerTK-Specific Inhibitors. (United States)

    McIver, Andrew L; Zhang, Weihe; Liu, Qingyang; Jiang, Xinpeng; Stashko, Michael A; Nichols, James; Miley, Michael J; Norris-Drouin, Jacqueline; Machius, Mischa; DeRyckere, Deborah; Wood, Edgar; Graham, Douglas K; Earp, H Shelton; Kireev, Dmitri; Frye, Stephen V; Wang, Xiaodong


    Macrocycles have attracted significant attention in drug discovery recently. In fact, a few de novo designed macrocyclic kinase inhibitors are currently in clinical trials with good potency and selectivity for their intended target. In this study, we successfully engaged a structure-based drug design approach to discover macrocyclic pyrimidines as potent Mer tyrosine kinase (MerTK)-specific inhibitors. An enzyme-linked immunosorbent assay (ELISA) in 384-well format was employed to evaluate the inhibitory activity of macrocycles in a cell-based assay assessing tyrosine phosphorylation of MerTK. Through structure-activity relationship (SAR) studies, analogue 11 [UNC2541; (S)-7-amino-N-(4-fluorobenzyl)-8-oxo-2,9,16-triaza-1(2,4)-pyrimidinacyclohexadecaphane-1-carboxamide] was identified as a potent and MerTK-specific inhibitor that exhibits sub-micromolar inhibitory activity in the cell-based ELISA. In addition, an X-ray structure of MerTK protein in complex with 11 was resolved to show that these macrocycles bind in the MerTK ATP pocket. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Columnar Liquid Crystals from a Giant Macrocycle Mesogen. (United States)

    Kawano, Shin-Ichiro; Kato, Masahiro; Soumiya, Shinya; Nakaya, Masato; Onoe, Jun; Tanaka, Kentaro


    Columnar liquid crystals composed of a giant macrocyclic mesogen were prepared. The giant macrocyclic mesogen has a square hollow with a 2.5 nm diagonal, which was bounded by diindolo[3,2-b:2',3'-h]carbazole (diindolocarbazole) moieties as the edges and bis(salicylidene)-o-phenylenediamine (salphen) moieties as the corners. The shape and size of the macrocycle were directly observed by scanning tunneling microscopy (STM). Each side of the bright square in the STM image corresponds to a diindolocarbazole moiety, and the length of the sides was consistent with the result of the single crystal analysis of diindolocarbazole. Finally, we successfully obtained a giant macrocycle with long and branched side chains, which exhibited a rectangular columnar LC phase over a wide temperature range. To the best of our knowledge, it contained the largest discrete inner space of any thermotropic columnar liquid crystal composed of macrocyclic mesogens. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Control of olefin geometry in macrocyclic ring-closing metathesis using a removable silyl group. (United States)

    Wang, Yikai; Jimenez, Miguel; Hansen, Anders S; Raiber, Eun-Ang; Schreiber, Stuart L; Young, Damian W


    Introducing a silyl group at one of the internal olefin positions in diolefinic substrates results in E-selective olefin formation in macrocyclic ring-forming metathesis. The application of this method to a range of macrocyclic (E)-alkenylsiloxanes is described. Protodesilylation of alkenylsiloxane products yields novel Z-configured macrocycles.

  1. Biologically Active Macrocyclic Compounds – from Natural Products to Diversity‐Oriented Synthesis

    DEFF Research Database (Denmark)

    Madsen, Charlotte Marie; Clausen, Mads Hartvig


    Macrocyclic compounds are attractive targets when searching for molecules with biological activity. The interest in this compound class is increasing, which has led to a variety of methods for tackling the difficult macrocyclization step in their synthesis. This microreview highlights some recent...... developments in the synthesis of macrocycles, with an emphasis on chemistry developed to generate libraries of putative biologically active compounds....

  2. Stack filter classifiers

    Energy Technology Data Exchange (ETDEWEB)

    Porter, Reid B [Los Alamos National Laboratory; Hush, Don [Los Alamos National Laboratory


    Just as linear models generalize the sample mean and weighted average, weighted order statistic models generalize the sample median and weighted median. This analogy can be continued informally to generalized additive modeels in the case of the mean, and Stack Filters in the case of the median. Both of these model classes have been extensively studied for signal and image processing but it is surprising to find that for pattern classification, their treatment has been significantly one sided. Generalized additive models are now a major tool in pattern classification and many different learning algorithms have been developed to fit model parameters to finite data. However Stack Filters remain largely confined to signal and image processing and learning algorithms for classification are yet to be seen. This paper is a step towards Stack Filter Classifiers and it shows that the approach is interesting from both a theoretical and a practical perspective.

  3. On Stack Reconstruction Problem

    Directory of Open Access Journals (Sweden)

    V. D. Аkeliev


    Full Text Available The paper describes analytical investigations that study relation of fuel combustion regimes with concentration values of sulphur anhydride in flue gases and acid dew point. Coefficients of convective heat transfer at internal and external surfaces of stacks have been determined in the paper. The paper reveals the possibility to reconstruct stacks while using gas discharging channel made of composite material on the basis of glass-reinforced plastic which permits to reduce thermo-stressed actions on reinforced concrete and increase volume of released gases due to practically two-fold reduction of gas-dynamic pressure losses along the pipe length.

  4. Laser pulse stacking method (United States)

    Moses, E.I.


    A laser pulse stacking method is disclosed. A problem with the prior art has been the generation of a series of laser beam pulses where the outer and inner regions of the beams are generated so as to form radially non-synchronous pulses. Such pulses thus have a non-uniform cross-sectional area with respect to the outer and inner edges of the pulses. The present invention provides a solution by combining the temporally non-uniform pulses in a stacking effect to thus provide a more uniform temporal synchronism over the beam diameter. 2 figs.

  5. Rigid Organization of Fluorescence-Active Ligands by Artificial Macrocyclic Receptor to Achieve the Thioflavin T-Amyloid Fibril Level Association. (United States)

    Zhang, Ying-Ming; Zhang, Xu-Jie; Xu, Xiufang; Fu, Xiao-Ning; Hou, Hong-Biao; Liu, Yu


    The push-pull molecules with an intramolecular charge transfer from donor to acceptor sides upon excitation exhibit a wide variety of biological and electronic activities, as exemplified by the in vivo fluorescence imaging probes for amyloid fibrils in the diagnosis and treatment of amyloid diseases. Interestingly, the structurally much simpler bis(4,8-disulfonato-1,5-naphtho)-32-crown-8 (DNC), in keen contrast to the conventional macrocyclic receptors, was found to dramatically enhance the fluorescence of twisted intramolecular charge-transfer molecules possessing various benzothiazolium and stilbazolium fluorophores upon complexation. Spectroscopic and microcalorimetric titrations jointly demonstrated the complex structures and the interactions that promote the extremely strong complexation, revealing that the binding affinity in these artificial host-guest pairs could reach up to a nearly 10(7) M(-1) order of magnitude in water, and the sandwich-type complexation is driven by electrostatic, hydrophobic, π-stacking, and hydrogen-bonding interactions. Quantum chemical calculations on free molecules and their DNC-bound species in both the ground and excited states elucidated that the encapsulation by DNC could greatly deter the central single and double chemical bonds from free intramolecular rotation in the singlet excited state, thus leading to the unique and unprecedented fluorescence enhancement upon sandwich-type complexation. This complexation-induced structural reorganization mechanism may also apply to the binding of other small-molecule ligands by functional receptors and contribute to the molecular-level understanding of the receptor-ligand interactions in many biology-related systems.

  6. Macrocyclic polyether complexes of amino acids and amino acid salts

    International Nuclear Information System (INIS)

    Bidzilya, V.A.; Oleksenko, LP.


    This paper deals with the isolation of the complexes formed between various types of amino acid derivatives and macrocyclic polyethers, and the characterisation of their physical and chemical properties. The study shows that macrocyclic polyethers form 1:1 complexes with amino acids and amino acid derivatives, and that these complexes can be isolated in pure form. Amino acids can be bound to these complexes in their anionic forms, in switterionic forms, as well as in their protonated forms. These types of complexes may be useful for the transport of amino acids or their derivatives across both synthetic and natural membranes

  7. Biosynthesis of macrocyclic diterpenoids in Euphorbia lathyris L

    DEFF Research Database (Denmark)

    Luo, Dan

    documents the investigation of the biosynthetic pathways of macrocyclic diterpenoids known as Euphorbia factors in Euphorbia lathyris L. (caper spurge). These macrocyclic diterpenoids are the current industrial source of ingenol mebutate, which is approved for the treatment of actinic keratosis......, a precancerous skin condition. Metabolite profiling of various tissues of E. lathyris L. revealed that the mature seeds constituted a highly specialized tissue for the biosynthesis of lathyrane and ingenane diterpenoids. RNA–seq and transcriptome analysis of E. lathyris L. mature seeds followed by functional...

  8. Dysprosium complexes with the tetraphenylporphyrin macrocyclic ligand

    International Nuclear Information System (INIS)

    Martinez M, V.; Padilla, J.; Ramirez, F.M.


    In this report, the results obtained on the synthesis, characterization and study of the chemical behavior of dysprosium complex with the acetylacetone chelating agent (Hacac) and the tetraphenylporphyrin macrocyclic ligand (H 2 TFP) are given. Based on the literature but according to our necessities and interest, the appropriate methodology settled down from the synthesis of prime matters until the obtaining and characterization of the products. The acetyl acetonate complex was obtained of mono hydrated dysprosium [Dy(acac) 3 . H 2 0] and trihydrated [Dy(acac) 3 .3 H 2 0], the mono tetra phenyl porphyrinate [Dy(TFP)(acac). 2 ac] the double sandwich of the dysprosium porphyrinate [Dy(TFP) 2 ] and the triple sandwich of the dysprosium porphyrinate [Dy(TFP) 3 . 2 TCB] (TCB = trichlorobenzene). Its were characterized by their melting points, solubility, IR, UV, TGA and DTA both first and besides the techniques already mentioned for NMR'H, RPE and Magnetic susceptibility the three last complexes. From the spectroscopic point of view, IR and RPE its suggested the existence of a complex of inverse mixed valence [Dy(TFP) 2- (TFP) 1- ] for the Dy(TFP) 2 as a result of the existence of the free radical (TFP' 1- and that it was not in none of the other porphyrin compounds. In the NMR'H spectra of the compounds were not observed signals in the region from 0 to 10 ppm that which shows that the dysprosium complexes in special those of the porphyrin type are highly paramagnetic and its could be used as displacement reagents, creators of images and contrast agents of great utility in these days in studies of NMR, technique today by today used in medical diagnoses. (Author)

  9. Macrocyclic olefin metathesis at high concentrations by using a phase-separation strategy. (United States)

    Raymond, Michaël; Holtz-Mulholland, Michael; Collins, Shawn K


    Macrocyclic olefin metathesis has seen advances in the areas of stereochemistry, chemoselectivity, and catalyst stability, but strategies aimed at controlling dilution effects in macrocyclizations are rare. Herein, a protocol to promote macrocyclic olefin metathesis, one of the most common synthetic tools used to prepare macrocycles, at relatively high concentrations (up to 60 mM) is described by exploitation of a phase-separation strategy. A variety of macrocyclic skeletons could be prepared having either different alkyl, aryl, or amino acids spacers. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. One novel 1D coordination polymer with parallel dinuclear copper(II) macrocyclic platforms bridged by trans dimeric half-water molecules and two dinuclear copper(II) macrocyclic complexes with different coordination geometry obtained from different solvents (United States)

    Chu, Zhaolian; You, Wei; Huang, Wei


    Three dinuclear copper(II) macrocyclic complexes, formulated as [Cu 2L(N 3) 2(0.5H 2O) 2] n ( 1), [Cu 2L(ClO 4) 2(CH 3CH 2OH)] ( 2) and [Cu 2L(CH 3OH) 2](ClO 4) 2 ( 3) (LH 2 = [2+2] Schiff base macrocyclic ligand condensed from 4-chloro-2,6-diformylphenol and 1,3-diaminopropane), have been prepared and determined by X-ray single-crystal diffraction. Complex 1 shows two six-coordinate Cu(II) centers in which two monodentate N3- anions and two half-water molecules are bonded at the apical positions in the trans configuration. Furthermore, the dimeric half-water molecules serve as a μ2-bridge linking adjacent macrocyclic units together with the multiple O sbnd H…N hydrogen bonds with azide anions, forming a novel 1D chain-like coordination polymer. Complexes 2 and 3 are obtained from different solvents (ethanol and methanol) and they can be converted into each other. The molecular structures and packing mode of 2 and 3 are different where six-coordinate and five-coordinate copper(II) centers are present, respectively.

  11. po_stack_movie

    DEFF Research Database (Denmark)


    po_stack® er et reolsystem, hvis enkle elementer giver stor flexibilitet, variation og skulpturel virkning. Elementerne stables og forskydes frit, så reolens rum kan vendes til begge sider, være åbne eller lukkede og farvekombineres ubegrænset. Reolen kan let ombygges, udvides eller opdeles, når ...

  12. Learning SaltStack

    CERN Document Server

    Myers, Colton


    If you are a system administrator who manages multiple servers, then you know how difficult it is to keep your infrastructure in line. If you've been searching for an easier way, this book is for you. No prior experience with SaltStack is required.

  13. Kinetics of oxidation of nickel(II) aza macrocycles by ...

    Indian Academy of Sciences (India)

    The kinetics of the oxidation of nickel (II) hexaaza and nickel (II) pentaaza macrocycles by the peroxydisulphate anion, S2O8 2-, were studied in aqueous media. Effect of H on reaction rate was also studied. The rate increases with increase of S2OO8 2- concentration. Rates are almost independent of acid between H 4 ...

  14. Study of behaviour of Ni (III) macrocyclic complexes in acidic ...

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences; Volume 129; Issue 2. Study of behaviour of Ni(III) macrocyclic complexes in acidic aqueous medium through kinetic measurement involving hydrogen peroxide oxidation and DFT calculations. ANURADHA SANKARAN E J PADMA MALAR VENKATAPURAM RAMANUJAM ...

  15. Flexible macrocycles as versatile supports for catalytically active metal clusters

    Energy Technology Data Exchange (ETDEWEB)

    Ryan, JD; Gagnon, KJ; Teat, SJ; McIntosh, RD


    Here we present three structurally diverse clusters stabilised by the same macrocyclic polyphenol; t-butylcalix[8]arene. This work demonstrates the range of conformations the flexible ligand is capable of adopting, highlighting its versatility in metal coordination. In addition, a Ti complex displays activity for the ring-opening polymerisation of lactide

  16. Kinetics of oxidation of nickel (II) aza macrocycles by ...

    Indian Academy of Sciences (India)

    The kinetics of the oxidation of nickel (II) hexaaza and nickel (II) pentaaza macrocycles by the peroxydisulphate anion, S2O8 2-, were studied in aqueous media. Effect of H on reaction rate was also studied. The rate increases with increase of S2OO8 2- concentration. Rates are almost independent of acid between H 4 ...

  17. A novel complexity-to-diversity strategy for the diversity-oriented synthesis of structurally diverse and complex macrocycles from quinine. (United States)

    Ciardiello, J J; Stewart, H L; Sore, H F; Galloway, W R J D; Spring, D R


    Recent years have witnessed a global decline in the productivity and advancement of the pharmaceutical industry. A major contributing factor to this is the downturn in drug discovery successes. This can be attributed to the lack of structural (particularly scaffold) diversity and structural complexity exhibited by current small molecule screening collections. Macrocycles have been shown to exhibit a diverse range of biological properties, with over 100 natural product-derived examples currently marketed as FDA-approved drugs. Despite this, synthetic macrocycles are widely considered to be a poorly explored structural class within drug discovery, which can be attributed to their synthetic intractability. Herein we describe a novel complexity-to-diversity strategy for the diversity-oriented synthesis of novel, structurally complex and diverse macrocyclic scaffolds from natural product starting materials. This approach exploits the inherent structural (including functional) and stereochemical complexity of natural products in order to rapidly generate diversity and complexity. Readily-accessible natural product-derived intermediates serve as structural templates which can be divergently functionalized with different building blocks to generate a diverse range of acyclic precursors. Subsequent macrocyclisation then furnishes compounds that are each based around a distinct molecular scaffold. Thus, high levels of library scaffold diversity can be rapidly achieved. In this proof-of-concept study, the natural product quinine was used as the foundation for library synthesis, and six novel structurally diverse, highly complex and functionalized macrocycles were generated. Copyright © 2017 Elsevier Ltd. All rights reserved.

  18. Reversible adaptation to photoinduced shape switching by oligomer-macrocycle interconversion with component selection in a three-state constitutional dynamic system. (United States)

    Vantomme, Ghislaine; Lehn, Jean-Marie


    Light irradiation of the molecular photoswitch 1-E causes isomerization into the 1-Z configuration stabilized by an internal hydrogen bond. 1-E bears aldehyde groups allowing for dynamic covalent reaction with linear diamines. On photoinduced E/Z shape switching of 1 in presence of diamines, the system undergoes interconversion between two states, a non-cyclic oligomeric one and a macrocyclic one, corresponding respectively to the E and Z configurations of 1. With a mixture of linear α,ω-diamines, 1-E yields non-selective dynamic oligomers by random incorporation of diamine components. Photoswitching to the 1-Z form leads to constitutional adaptation with preferential formation of the macrocycle incorporating the best suited diamine, H2 N(CH2 )7 NH2 . In presence of metal cations, the E form switches from its unbound W shape to its coordinated U shape and yields the macrocycle resulting from the selective incorporation of the diamine H2 NCH2 CH2 OCH2 CH2 NH2 that contains an additional O coordination site. Taken together, the results obtained describe constitutional adaptation in a triple state system: an oligomeric one and two different macrocyclic ones generated in response to two orthogonal agents, a physical stimulus, light, or a chemical effector, metal cations. These three states present, towards the incorporation of diamine components, respectively no selection, photoselection and metalloselection. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Energy Expenditure of Sport Stacking (United States)

    Murray, Steven R.; Udermann, Brian E.; Reineke, David M.; Battista, Rebecca A.


    Sport stacking is an activity taught in many physical education programs. The activity, although very popular, has been studied minimally, and the energy expenditure for sport stacking is unknown. Therefore, the purposes of this study were to determine the energy expenditure of sport stacking in elementary school children and to compare that value…

  20. OpenStack cloud security

    CERN Document Server

    Locati, Fabio Alessandro


    If you are an OpenStack administrator or developer, or wish to build solutions to protect your OpenStack environment, then this book is for you. Experience of Linux administration and familiarity with different OpenStack components is assumed.

  1. Stacking InAs quantum dots over ErAs semimetal nanoparticles on GaAs (0 0 1) using molecular beam epitaxy (United States)

    Zhang, Yuanchang; Eyink, Kurt G.; Grazulis, Lawrence; Hill, Madelyn; Peoples, Joseph; Mahalingam, Krishnamurthy


    Hybrid nanostructures are known to elicit an enhanced optical response. We study the directed alignment of ErAs metal nanoparticle (NP) and InAs quantum dot (QD) using molecular beam eptaxy (MBE) in a GaAs matrix. Due to high surface free energy caused by the crystal structure difference, overgrowth of an ErAs NP with GaAs forms a depression that condenses subsequent InAs adatoms to form an inverted QD self-aligned to the underlying ErAs NP. The ErAs NP growth, GaAs overgrowth, and InAs QD deposition were carefully controlled and studied with transmission electron microscopy (TEM) and atomic force microscopy (AFM) to investigate their effects on the QD-NP alignment.

  2. Stack Caching Using Split Data Caches

    DEFF Research Database (Denmark)

    Nielsen, Carsten; Schoeberl, Martin


    In most embedded and general purpose architectures, stack data and non-stack data is cached together, meaning that writing to or loading from the stack may expel non-stack data from the data cache. Manipulation of the stack has a different memory access pattern than that of non-stack data, showing...... higher temporal and spatial locality. We propose caching stack and non-stack data separately and develop four different stack caches that allow this separation without requiring compiler support. These are the simple, window, and prefilling with and without tag stack caches. The performance of the stack...

  3. Tunable photophysical processes of porphyrin macrocycles on the surface of ZnO nanoparticles

    KAUST Repository

    Parida, Manas R.


    We investigated the impact of the molecular structure of cationic porphyrins on the degree of electrostatic interactions with zinc oxide nanoparticles (ZnO NPs) using steady-state and time-resolved fluorescence and transient absorption spectroscopy. Our results demonstrate that the number of cationic pyridinium units has a crucial impact on the photophysics of the porphyrin macrocycle. Fluorescence enhancement, relative to initial free porphyrin fluorescence, was found to be tuned from 3.4 to 1.3 times higher by reducing the number of cationic substituents on the porphyrin from 4 to 2. The resulting enhancement of the intensity of the fluorescence is attributed to the decrease in the intramolecular charge transfer (ICT) character between the porphyrin cavity and its meso substituent. The novel findings reported in this work provide an understanding of the key variables involved in nanoassembly, paving the way toward optimizing the interfacial chemistry of porphyrin-ZnO NP assembly for photodynamic therapy and energy conversion.

  4. A new spermidine macrocyclic alkaloid isolated from Gymnosporia arenicola leaf. (United States)

    da Silva, Gustavo; Martinho, Ana; Soengas, Raquel González; Duarte, Ana Paula; Serrano, Rita; Gomes, Elsa Teixeira; Silva, Olga


    The isolation and structural elucidation of a macrocyclic alkaloid, characterized by the presence of a 13-membered macrolactam ring containing a spermidine unit N-linked to a benzoyl group is hereby reported. The structure of this previously unknown spermidine alkaloid isolated from Gymnosporia arenicola (Celastraceae) leaves has been elucidated by (1)H and (13)C NMR spectroscopy (including bidimensional analysis) and further characterized by high-resolution mass spectrometry and polarimetry. A route for the biosynthesis of this new bioactive macrocycle is proposed and the cytotoxicity of the compound was evaluated against two ATCC cell lines - one normal-derived (MCF10A) and one cancer-derived cell line (MCF7) - using the MTT assay. The alkaloid revealed to be non-cytotoxic against both cell lines. The IC50 values from the cells were also determined. Copyright © 2015 Elsevier B.V. All rights reserved.

  5. Passive stack ventilation

    Energy Technology Data Exchange (ETDEWEB)

    Palmer, J.; Parkins, L.; Shaw, P.; Watkins, R. [Databuild, Birmingham (United Kingdom)


    The adequate ventilation of houses is essential for both the occupants and the building fabric. As air-tightness standards increase, background infiltration levels decrease and extra ventilation has to be designed into the building. Passive stack ventilation has many advantages - particularly when employed in low cost housing schemes -but it is essential that it performs satisfactorily. This paper give the results from monitoring two passive stack ventilation schemes. One scheme was a retrofit into refurbished local authority houses in which a package of energy efficiency measures had been taken and condensation had been a problem. The other series of tests were conducted on a new installation in a Housing Association development. Nine houses were monitored each of which had at least two passive vents. The results show air flow rates by the passive ducts equivalent to approximately 1 room air change per hour. The air flow in the ducts was influenced by both, internal to external temperature difference and wind speed and direction. (author)

  6. Asymmetric Flexible Supercapacitor Stack

    Directory of Open Access Journals (Sweden)

    Leela Mohana Reddy A


    Full Text Available AbstractElectrical double layer supercapacitor is very significant in the field of electrical energy storage which can be the solution for the current revolution in the electronic devices like mobile phones, camera flashes which needs flexible and miniaturized energy storage device with all non-aqueous components. The multiwalled carbon nanotubes (MWNTs have been synthesized by catalytic chemical vapor deposition technique over hydrogen decrepitated Mischmetal (Mm based AB3alloy hydride. The polymer dispersed MWNTs have been obtained by insitu polymerization and the metal oxide/MWNTs were synthesized by sol-gel method. Morphological characterizations of polymer dispersed MWNTs have been carried out using scanning electron microscopy (SEM, transmission electron microscopy (TEM and HRTEM. An assymetric double supercapacitor stack has been fabricated using polymer/MWNTs and metal oxide/MWNTs coated over flexible carbon fabric as electrodes and nafion®membrane as a solid electrolyte. Electrochemical performance of the supercapacitor stack has been investigated using cyclic voltammetry, galvanostatic charge-discharge, and electrochemical impedance spectroscopy.

  7. Mixed Mechanism of Lubrication by Lipid Bilayer Stacks. (United States)

    Boţan, Alexandru; Joly, Laurent; Fillot, Nicolas; Loison, Claire


    Although the key role of lipid bilayer stacks in biological lubrication is generally accepted, the mechanisms underlying their extreme efficiency remain elusive. In this article, we report molecular dynamics simulations of lipid bilayer stacks undergoing load and shear. When the hydration level is reduced, the velocity accommodation mechanism changes from viscous shear in hydration water to interlayer sliding in the bilayers. This enables stacks of hydrated lipid bilayers to act as efficient boundary lubricants for various hydration conditions, structures, and mechanical loads. We also propose an estimation for the friction coefficient; thanks to the strong hydration forces between lipid bilayers, the high local viscosity is not in contradiction with low friction coefficients.

  8. Macrocyclic ligands for uranium complexation: Progress report, August 15, 1987-present

    International Nuclear Information System (INIS)

    Potts, K.T.


    The synthesis of several macrocyclic ligands, designed by a computer modeling approach for the complexation of the uranyl ion, has now been completed and their structures established. Preliminary indicate that these macrocycles successfully complex the uranyl ion. Other synthetic efforts have led to a variety of intermediates suitable for final ring closure to the desired macrocycles, providing appreciable potential for variation of the macrocyclic peripheral atoms. A 1:1-uranyl ion complex of one of these precursor products has been shown to undergo a DMSO-induced rearrangement to a 2:1 uranyl ion to ligand complex, both structures having been established by single crystal x-ray data. 10 refs

  9. Field-induced stacking transition of biofunctionalized trilayer graphene

    Energy Technology Data Exchange (ETDEWEB)

    Masato Nakano, C. [Flintridge Preparatory School, La Canada, California 91011 (United States); Sajib, Md Symon Jahan; Samieegohar, Mohammadreza; Wei, Tao [Dan F. Smith Department of Chemical Engineering, Lamar University, Beaumont, Texas 77710 (United States)


    Trilayer graphene (TLG) is attracting a lot of attention as their stacking structures (i.e., rhombohedral vs. Bernal) drastically affect electronic and optical properties. Based on full-atom molecular dynamics simulations, we here predict electric field-induced rhombohedral-to-Bernal transition of TLG tethered with proteins. Furthermore, our simulations show that protein's electrophoretic mobility and diffusivity are enhanced on TLG surface. This phenomenon of controllable TLG stacking transition will contribute to various applications including biosensing.

  10. Recent Advances in Macrocyclic Fluorescent Probes for Ion Sensing

    Directory of Open Access Journals (Sweden)

    Joseph K.-H. Wong


    Full Text Available Small-molecule fluorescent probes play a myriad of important roles in chemical sensing. Many such systems incorporating a receptor component designed to recognise and bind a specific analyte, and a reporter or transducer component which signals the binding event with a change in fluorescence output have been developed. Fluorescent probes use a variety of mechanisms to transmit the binding event to the reporter unit, including photoinduced electron transfer (PET, charge transfer (CT, Förster resonance energy transfer (FRET, excimer formation, and aggregation induced emission (AIE or aggregation caused quenching (ACQ. These systems respond to a wide array of potential analytes including protons, metal cations, anions, carbohydrates, and other biomolecules. This review surveys important new fluorescence-based probes for these and other analytes that have been reported over the past five years, focusing on the most widely exploited macrocyclic recognition components, those based on cyclam, calixarenes, cyclodextrins and crown ethers; other macrocyclic and non-macrocyclic receptors are also discussed.

  11. Fluorescence Resonance Energy Transfer Systems in Supramolecular Macrocyclic Chemistry

    Directory of Open Access Journals (Sweden)

    Xin-Yue Lou


    Full Text Available The fabrication of smart materials is gradually becoming a research focus in nanotechnology and materials science. An important criterion of smart materials is the capacity of stimuli-responsiveness, while another lies in selective recognition. Accordingly, supramolecular host-guest chemistry has proven a promising support for building intelligent, responsive systems; hence, synthetic macrocyclic hosts, such as calixarenes, cucurbiturils, cyclodextrins, and pillararenes, have been used as ideal building blocks. Meanwhile, manipulating and harnessing light artificially is always an intensive attempt for scientists in order to meet the urgent demands of technological developments. Fluorescence resonance energy transfer (FRET, known as a well-studied luminescent activity and also a powerful tool in spectroscopic area, has been investigated from various facets, of which the application range has been broadly expanded. In this review, the innovative collaboration between FRET and supramolecular macrocyclic chemistry will be presented and depicted with typical examples. Facilitated by the dynamic features of supramolecular macrocyclic motifs, a large variety of FRET systems have been designed and organized, resulting in promising optical materials with potential for applications in protein assembly, enzyme assays, diagnosis, drug delivery monitoring, sensing, photosynthesis mimicking and chemical encryption.

  12. Engineering macrocyclic figure–eight motif

    Indian Academy of Sciences (India)


    acceptance of Albert Einstein's 1905 proposal that the speed of light is a universal constant. This may proba- bly have made Physicists and Chemists to loose in- terest in knots for some time, but mathematicians are intrigued by the beauty and mathematics of such structures. Recently, knotted molecular structures at-.

  13. Instant BlueStacks

    CERN Document Server

    Judge, Gary


    Get to grips with a new technology, understand what it is and what it can do for you, and then get to work with the most important features and tasks. A fast-paced, example-based approach guide for learning BlueStacks.This book is for anyone with a Mac or PC who wants to run Android apps on their computer. Whether you want to play games that are freely available for Android but not your computer, or you want to try apps before you install them on a physical device or use it as a development tool, this book will show you how. No previous experience is needed as this is written in plain English

  14. Kinetically E-selective macrocyclic ring-closing metathesis (United States)

    Shen, Xiao; Nguyen, Thach T.; Koh, Ming Joo; Xu, Dongmin; Speed, Alexander W. H.; Schrock, Richard R.; Hoveyda, Amir H.


    Macrocyclic compounds are central to the development of new drugs, but preparing them can be challenging because of the energy barrier that must be surmounted in order to bring together and fuse the two ends of an acyclic precursor such as an alkene (also known as an olefin). To this end, the catalytic process known as ring-closing metathesis (RCM) has allowed access to countless biologically active macrocyclic organic molecules, even for large-scale production. Stereoselectivity is often critical in such cases: the potency of a macrocyclic compound can depend on the stereochemistry of its alkene; alternatively, one isomer of the compound can be subjected to stereoselective modification (such as dihydroxylation). Kinetically controlled Z-selective RCM reactions have been reported, but the only available metathesis approach for accessing macrocyclic E-olefins entails selective removal of the Z-component of a stereoisomeric mixture by ethenolysis, sacrificing substantial quantities of material if E/Z ratios are near unity. Use of ethylene can also cause adventitious olefin isomerization—a particularly serious problem when the E-alkene is energetically less favoured. Here, we show that dienes containing an E-alkenyl-B(pinacolato) group, widely used in catalytic cross-coupling, possess the requisite electronic and steric attributes to allow them to be converted stereoselectively to E-macrocyclic alkenes. The reaction is promoted by a molybdenum monoaryloxide pyrrolide complex and affords products at a yield of up to 73 per cent and an E/Z ratio greater than 98/2. We highlight the utility of the approach by preparing recifeiolide (a 12-membered-ring antibiotic) and pacritinib (an 18-membered-ring enzyme inhibitor), the Z-isomer of which is less potent than the E-isomer. Notably, the 18-membered-ring moiety of pacritinib—a potent anti-cancer agent that is in advanced clinical trials for treating lymphoma and myelofibrosis—was prepared by RCM carried out at a

  15. Metal Organic Framework: Crystalline Stacked Molecular Containers

    Indian Academy of Sciences (India)

    Home; Journals; Resonance – Journal of Science Education; Volume 19; Issue 12. Metal Organic Framework: ... Ramanathan Vaidhyanathan. General Article Volume 19 Issue 12 December 2014 pp 1147-1157 ... Vaidhyanathan1. Department of Chemistry Indian Institute of Science Education and Research Pune, India.

  16. Co-N-macrocyclic modified graphene with excellent electrocatalytic activity for lithium-thionyl chloride batteries

    International Nuclear Information System (INIS)

    Li, Bimei; Yuan, Zhongzhi; Xu, Ying; Liu, Jincheng


    Highlights: • A Co-N-graphene catalyst composed of CoN 4 -macrocyclic-like (CoN x ) structure is synthesized. • Co-N x -Graphene has effective electrocatalytic activity for Li/SOCl 2 batteries. • The storage stability of the catalyst is attributed to its insolubility in electrolyte. - Abstract: A mixture of cobalt phthalocyanine (CoPc) and graphene is thermally decomposed at 800 °C to synthesize a novel catalyst. Scanning electron microscopy (SEM) and transmission electron microscope (TEM) show that the catalyst retains the lamellar structure of graphene. X-ray diffraction (XRD) reveals that the catalyst is no longer composed of CoPc and high-resolution TEM (HRTEM), X-ray photoelectron spectra (XPS) prove that Co and N elements have entered the graphene molecular structure, thus forming a Co-N x -graphene (Co-N x -G) catalyst composed of a CoN 4 -macrocyclic-like structure. This catalyst serves as an excellent catalyst of thionyl chloride (SOCl 2 ) reduction. Cyclic voltammetry and battery discharge tests reveal that Co-N x -G-800 substantially increases the discharge voltage and capacity of a Li/SOCl 2 battery. Moreover, Co-N x -G-800 exhibits stable catalytic activity during battery storage. Ultraviolet–visible spectroscopy shows that CoPc is soluble in a SOCl 2 electrolyte solution, whereas Co-N x -G-800 is not, this characteristic contributes to the stable catalytic property of Co-N x -G.

  17. Assessing Elementary Algebra with STACK (United States)

    Sangwin, Christopher J.


    This paper concerns computer aided assessment (CAA) of mathematics in which a computer algebra system (CAS) is used to help assess students' responses to elementary algebra questions. Using a methodology of documentary analysis, we examine what is taught in elementary algebra. The STACK CAA system,, which uses the CAS…

  18. HPC Software Stack Testing Framework

    Energy Technology Data Exchange (ETDEWEB)


    The HPC Software stack testing framework (hpcswtest) is used in the INL Scientific Computing Department to test the basic sanity and integrity of the HPC Software stack (Compilers, MPI, Numerical libraries and Applications) and to quickly discover hard failures, and as a by-product it will indirectly check the HPC infrastructure (network, PBS and licensing servers).

  19. Zinc, copper and nickel complexes of a macrocycle synthesized from pyridinedicarboxylic acid: A spectroscopic, thermal and theoretical study

    Directory of Open Access Journals (Sweden)

    Soleimani Esmaiel


    Full Text Available The metal(II ion complexes of a pentadentate macrocycle 1, namely 3,12-dioxa-6,9,18-triazabicyclo[12.3.1]octadeca-1(18,14,16-triene-2,13-dione are synthesized. This macrocycle is prepared from the reaction of dipotassium salt of 2,6-pyridinedicarboxylic acid with ethylenediamine and 1,2-dibromoethane. The reaction of 1 (L in methanol with MCl2.xH2O gave complexes with the general formula [M(LCl2] (where M= Ni(II 2, Cu(II 3 and Zn(II 4, respectively. The analysis of IR, 1H- and 13C-NMR spectral data of all complexes propose that 1 is bonded to metal(II ions through a nitrogen atom of pyridine ring, two nitrogen atoms of amine groups and two oxygen atoms of ester moieties. The thermal analysis indicated that there are no water molecules of hydration or coordinated in the structure of the complexes. Among these complexes, the Cu(II 3 complex demonstrated good antibacterial and antifungal activities. The molecular geometry, AIM atomic charge and frontier molecular orbitals of the compounds are investigated theoretically using DFT method. Based on the theoretical data of these complexes represented, a bipyramidal pentagonal arrangement can be envisaged in such a way that the N3O2 pentadentate donor sites form the planar pentagonal base of the bipyramid and the two Cl atoms occupy the vertexes.

  20. Hydrogen bond templated 1:1 macrocyclization through an olefin metathesis/hydrogenation sequence. (United States)

    Trita, Andrada Stefania; Roisnel, Thierry; Mongin, Florence; Chevallier, Floris


    The construction of pyridine-containing macrocyclic architectures using a nonmetallic template is described. 4,6-Dichlororesorcinol was used as an exotemplate to self-organize two aza-heterocyclic units by OH···N hydrogen bonds. Subsequent sequential double olefin metathesis/hydrogenation reactions employing a single ruthenium-alkylidene precatalyst open access to macrocyclic molecules.

  1. Camelliin B and nobotanin I, macrocyclic ellagitannin dimers and related dimers, and their antitumor activity. (United States)

    Yoshida, T; Chou, T; Haba, K; Okano, Y; Shingu, T; Miyamoto, K; Koshiura, R; Okuda, T


    Camelliin B and nobotanin I, dimeric hydrolyzable tannins of a new class having macrocyclic structures, were isolated from Camellia japonica and Heterocentron roseum, respectively. Nobotanin G and H of the structures related to nobotanin I, were also obtained from H. roseum. Camelliin B and also woodfordin C, a macrocyclic dimer from Woodfordia fruticosa, exhibited marked host-mediated antitumor activities.

  2. Toward understanding macrocycle specificity of iron on the dioxygen-binding ability: a theoretical study. (United States)

    Sun, Yong; Chen, Kexian; Jia, Lu; Li, Haoran


    In an effort to examine the interaction between dioxygen and iron-macrocyclic complexes, and to understand how this interaction was affected by those different macrocyclic ligands, dioxygen binding with iron-porphyrin, iron-phthalocyanine, iron-dibenzotetraaza[14]annulene, and iron-salen complexes is investigated by means of quantum chemical calculations utilizing Density Functional Theory (DFT). Based on the analysis of factors influencing the corresponding dioxygen binding process, it showed that different macrocyclic ligands possess different O-O bond distances, and different electronic configurations for the bound O(2) and non-aromatic macrocyclic ligands favor dioxygen activation. Furthermore, the smaller the energy gap between the HOMO of iron-macrocyclic complexes and the LUMO of dioxygen, the more active the bound O(2) becomes, with a longer O-O bond distance and a shorter Fe-O bond length.

  3. Environmental assessment of phosphogypsum stacks

    International Nuclear Information System (INIS)

    Odat, M.; Al-Attar, L.; Raja, G.; Abdul Ghany, B.


    Phosphogypsum is one of the most important by-products of phosphate fertilizer industry. It is kept in large stacks to the west of Homs city. Storing Phosphogypsum as open stacks exposed to various environmental effects, wind and rain, may cause pollution of the surrounding ecosystem (soil, plant, water and air). This study was carried out in order to assess the environmental impact of Phosphogypsum stacks on the surrounding ecosystem. The obtained results show that Phosphogypsum stacks did not increase the concentration of radionuclides, i.e. Radon-222 and Radium-226, the external exposed dose of gamma rays, as well as the concentration of heavy metals in the components of the ecosystem, soil, plant, water and air, as their concentrations did not exceed the permissible limits. However, the concentration of fluorine in the upper layer of soil, located to the east of the Phosphogypsum stacks, increased sufficiently, especially in the dry period of the year. Also, the concentration of fluoride in plants growing up near-by the Phosphogypsum stacks was too high, exceeded the permissible levels. This was reflected in poising plants and animals, feeding on the plants. Consequently, increasing the concentration of fluoride in soil and plants is the main impact of Phosphogypsum stacks on the surrounding ecosystem. Minimising this effect could be achieved by establishing a 50 meter wide protection zone surrounding the Phosphogypsum stacks, which has to be planted with non palatable trees, such as pine and cypress, forming wind barriers. Increasing the concentrations of heavy metals and fluoride in infiltrated water around the stacks was high; hence cautions must be taken to prevent its usage in any application or disposal in adjacent rivers and leaks.(author)

  4. PieceStack: Toward Better Understanding of Stacked Graphs. (United States)

    Wu, Tongshuang; Wu, Yingcai; Shi, Conglei; Qu, Huamin; Cui, Weiwei


    Stacked graphs have been widely adopted in various fields, because they are capable of hierarchically visualizing a set of temporal sequences as well as their aggregation. However, because of visual illusion issues, connections between overly-detailed individual layers and overly-generalized aggregation are intercepted. Consequently, information in this area has yet to be fully excavated. Thus, we present PieceStack in this paper, to reveal the relevance of stacked graphs in understanding intrinsic details of their displayed shapes. This new visual analytic design interprets the ways through which aggregations are generated with individual layers by interactively splitting and re-constructing the stacked graphs. A clustering algorithm is designed to partition stacked graphs into sub-aggregated pieces based on trend similarities of layers. We then visualize the pieces with augmented encoding to help analysts decompose and explore the graphs with respect to their interests. Case studies and a user study are conducted to demonstrate the usefulness of our technique in understanding the formation of stacked graphs.

  5. Novel archaeal macrocyclic diether core membrane lipids in a methane-derived carbonate crust from a mud volcano in the Sorokin Trough, NE Black Sea

    Directory of Open Access Journals (Sweden)

    Alina Stadnitskaia


    Full Text Available A methane-derived carbonate crust was collected from the recently discovered NIOZ mud volcano in the Sorokin Trough, NE Black Sea during the 11th Training-through-Research cruise of the R/V Professor Logachev. Among several specific bacterial and archaeal membrane lipids present in this crust, two novel macrocyclic diphytanyl glycerol diethers, containing one or two cyclopentane rings, were detected. Their structures were tentatively identified based on the interpretation of mass spectra, comparison with previously reported mass spectral data, and a hydrogenation experiment. This macrocyclic type of archaeal core membrane diether lipid has so far been identified only in the deep-sea hydrothermal vent methanogen Methanococcus jannaschii. Here, we provide the first evidence that these macrocyclic diethers can also contain internal cyclopentane rings. The molecular structure of the novel diethers resembles that of dibiphytanyl tetraethers in which biphytane chains, containing one and two pentacyclic rings, also occur. Such tetraethers were abundant in the crust. Compound-specific isotope measurements revealed δ13C values of –104 to –111‰ for these new archaeal lipids, indicating that they are derived from methanotrophic archaea acting within anaerobic methane-oxidizing consortia, which subsequently induce authigenic carbonate formation.

  6. Photoresponsive Amphiphilic Macrocycles Containing Main-Chain Azobenzene Polymers. (United States)

    Sun, Yadong; Wang, Zhao; Li, Yiwen; Zhang, Zhengbiao; Zhang, Wei; Pan, Xiangqiang; Zhou, Nianchen; Zhu, Xiulin


    Herein, the first example of photosensitive cyclic amphiphilic homopolymers consisting of multiple biphenyl azobenzene chromophores in the cyclic main chain tethered with hydrophilic tetraethylene glycol monomethyl ether units is presented. The synthetic approach involves sequentially performed thermal catalyzed "click" step-growth polymerization in bulk, and Cu(I)-catalyzed azide-alkyne cycloaddition (CuAAC) intramolecular cyclization from α-alkyne/ω-azide linear precursors. It is observed that such amphiphilic macrocycles exhibit increased glass transition temperatures (Tg ), slightly faster trans-cis-trans photoisomerization, and enhanced fluorescence emission intensity compared with the corresponding linear polymers. In addition, the cyclic amphiphilic homopolymers self-assemble into spherical nanoparticles with smaller sizes which possess slower photoresponsive behaviors in a tetrahydrofuran/water mixture compared with those of the linear ones. All these interesting observations suggest that the cyclic topology has a great influence on the physical properties and self-assembly behavior of these photoresponsive amphiphilic macrocycles in general. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Macrocyclic ligands and their use in chemical separations

    International Nuclear Information System (INIS)

    Izatt, R.M.; Bradshaw, J.S.; Bruening, R.L.; Krakowiak, K.E.; Tarbet, B.J.


    Macrocyclic chemistry has had a phenomenal growth curve during the past three decades (Izatt et al.). Interest in this field was catalyzed by Pedersen's report of the synthesis and partial characterization of a large number of novel cyclic polyethers. The unusual affinity of these new compounds for and selectivity among alkali metal cations was noted (Pedersen) and quantitated (Izatt et al.). A 1987 National Academy of Science publication on separations listed three high priority needs in the separations field (King). These were to develop highly selective reagents capable of discriminating among similar chemical species, reagents capable of concentrating trace amounts of solutes even in the presence of large excesses of matrix solutes, and reagents capable of removing solutes from large quantities of solvent. Certain macrocycles offer the promise of being successful in achieving all three of these goals. This promise arises from their high selectivity for particular cations in various series of closely related cations, their large affinities for particular cations, and the ease with which they can be modified to meet particular needs inherent to chemical separations

  8. Enantioseparation and chiral recognition mechanism of new chiral derivatives of xanthones on macrocyclic antibiotic stationary phases. (United States)

    Fernandes, Carla; Tiritan, Maria Elizabeth; Cass, Quezia; Kairys, Visvaldas; Fernandes, Miguel Xavier; Pinto, Madalena


    A chiral HPLC method using four macrocyclic antibiotic chiral stationary phases (CSPs) has been investigated for determination of the enantiomeric purity of fourteen new chiral derivatives of xanthones (CDXs). The separations were performed with the CSPs Chirobiotic T, Chirobiotic TAG, Chirobiotic V and Chirobiotic R under multimodal elution conditions (normal-phase, reversed-phase and polar ionic mode). The analyses were performed at room temperature in isocratic mode and UV and CD detection at a wavelength of 254 nm. The best enantioselectivity and resolution were achieved on Chirobiotic R and Chirobiotic T CSPs, under normal elution conditions, with R(S) ranging from 1.25 to 2.50 and from 0.78 to 2.06, respectively. The optimized chromatographic conditions allowed the determination of the enantiomeric ratio of eight CDXs, always higher than 99%. In order to better understand the chromatographic behavior at a molecular level, and the structural features associated with the chiral recognition mechanism, computational studies by molecular docking were carried out using VDock. These studies shed light on the mechanisms involved in the enantioseparation for this important class of chiral compounds. Copyright © 2012 Elsevier B.V. All rights reserved.

  9. Standoff Stack Emissions Monitoring Using Short Range Lidar (United States)

    Gravel, Jean-Francois Y.; Babin, Francois; Allard, Martin


    There are well documented methods for stack emissions monitoring. These are all based on stack sampling through sampling ports in well defined conditions. Once sampled, the molecules are quantified in instruments that often use optical techniques. Unfortunately sampling ports are not found on all stacks/ducts or the use of the sampling ports cannot be planned efficiently because of operational constraints or the emissions monitoring equipment cannot be driven to a remote stack/duct. Emissions monitoring using many of the same optical techniques, but at a standoff distance, through the atmosphere, using short range high spatial resolution lidar techniques was thus attempted. Standoff absorption and Raman will be discussed and results from a field campaign will be presented along with short descriptions of the apparatus. In the first phase of these tests, the molecules that were targeted were NO and O2. Spatially resolved optical measurements allow for standoff identification and quantification of molecules, much like the standardized methods, except for the fact that it is not done in the stack, but in the plume formed by the emissions from the stack. The pros and cons will also be discussed, and in particular the problem of mass emission estimates that require the knowledge of the flow rate and the distribution of molecular concentration in the plane of measurement.

  10. Standoff Stack Emissions Monitoring Using Short Range Lidar

    Directory of Open Access Journals (Sweden)

    Gravel Jean-Francois Y.


    Full Text Available There are well documented methods for stack emissions monitoring. These are all based on stack sampling through sampling ports in well defined conditions. Once sampled, the molecules are quantified in instruments that often use optical techniques. Unfortunately sampling ports are not found on all stacks/ducts or the use of the sampling ports cannot be planned efficiently because of operational constraints or the emissions monitoring equipment cannot be driven to a remote stack/duct. Emissions monitoring using many of the same optical techniques, but at a standoff distance, through the atmosphere, using short range high spatial resolution lidar techniques was thus attempted. Standoff absorption and Raman will be discussed and results from a field campaign will be presented along with short descriptions of the apparatus. In the first phase of these tests, the molecules that were targeted were NO and O2. Spatially resolved optical measurements allow for standoff identification and quantification of molecules, much like the standardized methods, except for the fact that it is not done in the stack, but in the plume formed by the emissions from the stack. The pros and cons will also be discussed, and in particular the problem of mass emission estimates that require the knowledge of the flow rate and the distribution of molecular concentration in the plane of measurement.

  11. Time-predictable Stack Caching

    DEFF Research Database (Denmark)

    Abbaspourseyedi, Sahar

    completely. Thus, in systems with hard deadlines the worst-case execution time (WCET) of the real-time software running on them needs to be bounded. Modern architectures use features such as pipelining and caches for improving the average performance. These features, however, make the WCET analysis more...... addresses, provides an opportunity to predict and tighten the WCET of accesses to data in caches. In this thesis, we introduce the time-predictable stack cache design and implementation within a time-predictable processor. We introduce several optimizations to our design for tightening the WCET while...... keeping the timepredictability of the design intact. Moreover, we provide a solution for reducing the cost of context switching in a system using the stack cache. In design of these caches, we use custom hardware and compiler support for delivering time-predictable stack data accesses. Furthermore...

  12. Glassy carbon based supercapacitor stacks

    Energy Technology Data Exchange (ETDEWEB)

    Baertsch, M.; Braun, A.; Koetz, R.; Haas, O. [Paul Scherrer Inst. (PSI), Villigen (Switzerland)


    Considerable effort is being made to develop electrochemical double layer capacitors (EDLC) that store relatively large quantities of electrical energy and possess at the same time a high power density. Our previous work has shown that glassy carbon is suitable as a material for capacitor electrodes concerning low resistance and high capacity requirements. We present the development of bipolar electrochemical glassy carbon capacitor stacks of up to 3 V. Bipolar stacks are an efficient way to meet the high voltage and high power density requirements for traction applications. Impedance and cyclic voltammogram measurements are reported here and show the frequency response of a 1, 2, and 3 V stack. (author) 3 figs., 1 ref..

  13. Surface enhanced SHG from macrocycle, catenane and rotaxane thin films : experiments and theory.

    NARCIS (Netherlands)

    Arfaoui, I.; Bermudez, V.; De Nadai, C.; Jalkanen, J.-P.; Kajzar, F.; Leigh, D.A.; Lubomska, M.; Mendoza, S.M.; Niziol, J.; Rudolf, Petra; Zerbetto, F.; Grote, JG; Kaino, T; Kajzar, F


    Surface enhanced second harmonic generation experiments on supramolecules: macrocycles, catenanes and rotaxanes, monolayers and multilayers deposited by vacuum evaporation on silver layers are reported and described. The measurements show that the molecules are ordered in thin films. The highest

  14. Convergent Synthesis of Rigid Macrocycles Containing One and Two Tetrathiafulvalene Units

    DEFF Research Database (Denmark)

    Simonsen, Klaus B.; Thorup, Niels; Becher, Jan


    The synthesis of rigid tetrathiafulvalenophanes containing one or two tetrathiafulvalene units is presented, together with a stepwise convergent synthesis of macrocyclic bis-tetrathiafulvalenes via several open dimeric tetrathiafulvalenes. These systems were investigated by cyclic voltammetry...

  15. Solvent extraction of europium trifluoromethanesulfonate into nitrobenzene by using some electroneutral macrocyclic lactam receptors

    Czech Academy of Sciences Publication Activity Database

    Makrlík, E.; Sedláková, Zdeňka; Selucký, P.; Vaňura, P.


    Roč. 293, č. 2 (2012), s. 699-702 ISSN 0236-5731 Institutional support: RVO:61389013 Keywords : europium * macrocyclic lactam receptors * extraction and stability constants Subject RIV: CD - Macromolecular Chemistry Impact factor: 1.467, year: 2012

  16. Complexation of the strontium cation with a macrocyclic lactam receptor: Experimental and theoretical study

    Czech Academy of Sciences Publication Activity Database

    Makrlík, E.; Záliš, Stanislav; Vaňura, P.


    Roč. 214, FEB 2016 (2016), s. 171-174 ISSN 0167-7322 Institutional support: RVO:61388955 Keywords : strontium cation * macrocyclic lactam receptor Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.648, year: 2016

  17. Macrocyclic bis-quinolizidine alkaloids from Xestospongia muta. (United States)

    Dung, Duong Thi; Hang, Dan Thi Thuy; Yen, Pham Hai; Quang, Tran Hong; Nhiem, Nguyen Xuan; Tai, Bui Huu; Minh, Chau Van; Kim, Youn-Chul; Kim, Dong Cheol; Oh, Hyuncheol; Kiem, Phan Van


    A new stereoisomer Meso-araguspongine C together with nine reported macrocyclic bis-quinolizidine alkaloids araguspongines A, C, E, L, N-P, petrosin, and petrosin A were isolated from marine sponge Xestospongia muta. Stereochemistry of meso-araguspongine C (2) and araguspongines N-P (3-5) were established by their NMR data and conformational analyses. Both araguspongine C (1) and meso-araguspongine C (2) exhibited great cytotoxic activity towards HepG-2, HL-60, LU-1, MCF-7, and SK-Mel-2 human cancer cells (IC 50 in the range of 0.43-1.02 μM). At a concentration of 20 μM, isolated compounds (1-10) also showed modest inhibitory effects (from 7.6 to 40.8%) on the NO production in LPS activated RAW264.7 macrophages.

  18. Multiple Segmentation of Image Stacks

    DEFF Research Database (Denmark)

    Smets, Jonathan; Jaeger, Manfred


    We propose a method for the simultaneous construction of multiple image segmentations by combining a recently proposed “convolution of mixtures of Gaussians” model with a multi-layer hidden Markov random field structure. The resulting method constructs for a single image several, alternative...... segmentations that capture different structural elements of the image. We also apply the method to collections of images with identical pixel dimensions, which we call image stacks. Here it turns out that the method is able to both identify groups of similar images in the stack, and to provide segmentations...

  19. Simulating Small-Scale Object Stacking Using Stack Stability

    DEFF Research Database (Denmark)

    Kronborg Thomsen, Kasper; Kraus, Martin


    This paper presents an extension system to a closed-source, real-time physics engine for improving structured stacking behavior with small-scale objects such as wooden toy bricks. The proposed system was implemented and evaluated. The tests showed that the system is able to simulate several common...

  20. 1H NMR study on the intermolecular interactions of macrocyclic and single α-amino acids (United States)

    Quevedo, Rodolfo; Pabón, Laura; Quevedo-Acosta, Yovanny


    Through analysis of 1H NMR spectra, evidence was found for intermolecular interactions between macrocyclic amino acid derivatives from L-tyrosine and their importance in the formation of aggregates in solution. It was also shown that both macrocyclic and simple amino acids are capable of retaining alcohol molecules through hydrogen bonding, where the alcohol molecule acts as a proton donor and the amino group acts as an acceptor.

  1. Macrocyclic Gd(3+) complexes with pendant crown ethers designed for binding zwitterionic neurotransmitters. (United States)

    Oukhatar, Fatima; Meudal, Hervé; Landon, Céline; Logothetis, Nikos K; Platas-Iglesias, Carlos; Angelovski, Goran; Tóth, Éva


    A series of Gd(3+) complexes exhibiting a relaxometric response to zwitterionic amino acid neurotransmitters was synthesized. The design concept involves ditopic interactions 1) between a positively charged and coordinatively unsaturated Gd(3+) chelate and the carboxylate group of the neurotransmitters and 2) between an azacrown ether appended to the chelate and the amino group of the neurotransmitters. The chelates differ in the nature and length of the linker connecting the cyclen-type macrocycle that binds the Ln(3+) ion and the crown ether. The complexes are monohydrated, but they exhibit high proton relaxivities (up to 7.7 mM(-1)  s(-1) at 60 MHz, 310 K) due to slow molecular tumbling. The formation of ternary complexes with neurotransmitters was monitored by (1) H relaxometric titrations of the Gd(3+) complexes and by luminescence measurements on the Eu(3+) and Tb(3+) analogues at pH 7.4. The remarkable relaxivity decrease (≈80 %) observed on neurotransmitter binding is related to the decrease in the hydration number, as evidenced by luminescence lifetime measurements on the Eu(3+) complexes. These complexes show affinity for amino acid neurotransmitters in the millimolar range, which can be suited to imaging concentrations of synaptically released neurotransmitters. They display good selectivity over non-amino acid neurotransmitters (acetylcholine, serotonin, and noradrenaline) and hydrogenphosphate, but selectivity over hydrogencarbonate was not achieved. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Structural, spectral, DFT and biological studies on macrocyclic mononuclear ruthenium (II) complexes (United States)

    Muthukkumar, M.; Kamal, C.; Venkatesh, G.; Kaya, C.; Kaya, S.; Enoch, Israel V. M. V.; Vennila, P.; Rajavel, R.


    Macrocyclic mononuclear ruthenium (II) complexes have been synthesized by condensation method [Ru (L1, L2, L3) Cl2] L1 = (C36 H31 N9), L2= (C42H36N8), L3= (C32H32 N8)]. These ruthenium complexes have been established by elemental analyses and spectroscopic techniques (Fourier transform infrared spectroscopy (FT-IR), 1H- nuclear magnetic resonance (NMR), 13C- NMR and Electrospray ionization mass spectrometry (ESI-MS)). The coordination mode of the ligand has been confirmed and the octahedral geometry around the ruthenium ion has been revealed. Binding affinity and binding mode of ruthenium (II) complexes with Bovine serum Albumin (BSA) have been characterized by Emission spectra analysis. UV-Visible and fluorescence spectroscopic techniques have also been utilized to examine the interaction between ligand and its complexes L1, L2, & L3 with BSA. Chemical parameters and molecular structure of Ru (II) complexes L1H, L2H, & L3H have been determined by DFT coupled with B3LYP/6-311G** functional in both the gaseous and aqueous phases.

  3. Pressurized electrolysis stack with thermal expansion capability (United States)

    Bourgeois, Richard Scott


    The present techniques provide systems and methods for mounting an electrolyzer stack in an outer shell so as to allow for differential thermal expansion of the electrolyzer stack and shell. Generally, an electrolyzer stack may be formed from a material with a high coefficient of thermal expansion, while the shell may be formed from a material having a lower coefficient of thermal expansion. The differences between the coefficients of thermal expansion may lead to damage to the electrolyzer stack as the shell may restrain the thermal expansion of the electrolyzer stack. To allow for the differences in thermal expansion, the electrolyzer stack may be mounted within the shell leaving a space between the electrolyzer stack and shell. The space between the electrolyzer stack and the shell may be filled with a non-conductive fluid to further equalize pressure inside and outside of the electrolyzer stack.

  4. Stereoselective synthesis of macrocyclic peptides via a dual olefin metathesis and ethenolysis approach. (United States)

    Mangold, Shane L; Grubbs, Robert H


    Macrocyclic compounds occupy an important chemical space between small molecules and biologics and are prevalent in many natural products and pharmaceuticals. The growing interest in macrocycles has been fueled, in part, by the design of novel synthetic methods to these compounds. One appealing strategy is ring-closing metathesis (RCM) that seeks to construct macrocycles from acyclic diene precursors using defined transition-metal alkylidene catalysts. Despite its broad utility, RCM generally gives rise to a mixture of E - and Z- olefin isomers that can hinder efforts for the large-scale production and isolation of such complex molecules. To address this issue, we aimed to develop methods that can selectively enrich macrocycles in E - or Z -olefin isomers using an RCM/ethenolysis strategy. The utility of this methodology was demonstrated in the stereoselective formation of macrocyclic peptides, a class of compounds that have gained prominence as therapeutics in drug discovery. Herein, we report an assessment of various factors that promote catalyst-directed RCM and ethenolysis on a variety of peptide substrates by varying the olefin type, peptide sequence, and placement of the olefin in macrocycle formation. These methods allow for control over olefin geometry in peptides, facilitating their isolation and characterization. The studies outlined in this report seek to expand the scope of stereoselective olefin metathesis in general RCM.

  5. The Direct FuelCell™ stack engineering (United States)

    Doyon, J.; Farooque, M.; Maru, H.

    FuelCell Energy (FCE) has developed power plants in the size range of 300 kW to 3 MW for distributed power generation. Field-testing of the sub-megawatt plants is underway. The FCE power plants are based on its Direct FuelCell™ (DFC) technology. This is so named because of its ability to generate electricity directly from a hydrocarbon fuel, such as natural gas, by reforming it inside the fuel cell stack itself. All FCE products use identical 8000 cm 2 cell design, approximately 350-400 cells per stack, external gas manifolds, and similar stack compression systems. The difference lies in the packaging of the stacks inside the stack module. The sub-megawatt system stack module contains a single horizontal stack whereas the MW-class stack module houses four identical vertical stacks. The commonality of the design, internal reforming features, and atmospheric operation simplify the system design, reduce cost, improve efficiency, increase reliability and maintainability. The product building-block stack design has been advanced through three full-size stack operations at company's headquarters in Danbury, CT. The initial proof-of-concept of the full-size stack design was verified in 1999, followed by a 1.5 year of endurance verification in 2000-2001, and currently a value-engineered stack version is in operation. This paper discusses the design features, important engineering solutions implemented, and test results of FCE's full-size DFC stacks.

  6. Potent Inhibitors of the Hepatitis C Virus NS3 Protease: Design and Synthesis of Macrocyclic Substrate-Based [beta]-Strand Mimics

    Energy Technology Data Exchange (ETDEWEB)

    Goudreau, Nathalie; Brochu, Christian; Cameron, Dale R.; Duceppe, Jean-Simon; Faucher, Anne-Marie; Ferland, Jean-Marie; Grand-Maître, Chantal; Poirier, Martin; Simoneau, Bruno; Tsantrizos, Youla S. (Boehringer)


    The virally encoded NS3 protease is essential to the life cycle of the hepatitis C virus (HCV), an important human pathogen causing chronic hepatitis, cirrhosis of the liver, and hepatocellular carcinoma. The design and synthesis of 15-membered ring {beta}-strand mimics which are capable of inhibiting the interactions between the HCV NS3 protease enzyme and its polyprotein substrate will be described. The binding interactions between a macrocyclic ligand and the enzyme were explored by NMR and molecular dynamics, and a model of the ligand/enzyme complex was developed.

  7. Stack semantics of type theory

    DEFF Research Database (Denmark)

    Coquand, Thierry; Mannaa, Bassel; Ruch, Fabian


    We give a model of dependent type theory with one univalent universe and propositional truncation interpreting a type as a stack, generalizing the groupoid model of type theory. As an application, we show that countable choice cannot be proved in dependent type theory with one univalent universe...

  8. Multilayer Piezoelectric Stack Actuator Characterization (United States)

    Sherrit, Stewart; Jones, Christopher M.; Aldrich, Jack B.; Blodget, Chad; Bao, Xioaqi; Badescu, Mircea; Bar-Cohen, Yoseph


    Future NASA missions are increasingly seeking to use actuators for precision positioning to accuracies of the order of fractions of a nanometer. For this purpose, multilayer piezoelectric stacks are being considered as actuators for driving these precision mechanisms. In this study, sets of commercial PZT stacks were tested in various AC and DC conditions at both nominal and extreme temperatures and voltages. AC signal testing included impedance, capacitance and dielectric loss factor of each actuator as a function of the small-signal driving sinusoidal frequency, and the ambient temperature. DC signal testing includes leakage current and displacement as a function of the applied DC voltage. The applied DC voltage was increased to over eight times the manufacturers' specifications to investigate the correlation between leakage current and breakdown voltage. Resonance characterization as a function of temperature was done over a temperature range of -180C to +200C which generally exceeded the manufacturers' specifications. In order to study the lifetime performance of these stacks, five actuators from one manufacturer were driven by a 60volt, 2 kHz sine-wave for ten billion cycles. The tests were performed using a Lab-View controlled automated data acquisition system that monitored the waveform of the stack electrical current and voltage. The measurements included the displacement, impedance, capacitance and leakage current and the analysis of the experimental results will be presented.

  9. Open stack thermal battery tests

    Energy Technology Data Exchange (ETDEWEB)

    Long, Kevin N. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Roberts, Christine C. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Grillet, Anne M. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Headley, Alexander J. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Fenton, Kyle [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Wong, Dennis [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Ingersoll, David [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)


    We present selected results from a series of Open Stack thermal battery tests performed in FY14 and FY15 and discuss our findings. These tests were meant to provide validation data for the comprehensive thermal battery simulation tools currently under development in Sierra/Aria under known conditions compared with as-manufactured batteries. We are able to satisfy this original objective in the present study for some test conditions. Measurements from each test include: nominal stack pressure (axial stress) vs. time in the cold state and during battery ignition, battery voltage vs. time against a prescribed current draw with periodic pulses, and images transverse to the battery axis from which cell displacements are computed. Six battery configurations were evaluated: 3, 5, and 10 cell stacks sandwiched between 4 layers of the materials used for axial thermal insulation, either Fiberfrax Board or MinK. In addition to the results from 3, 5, and 10 cell stacks with either in-line Fiberfrax Board or MinK insulation, a series of cell-free “control” tests were performed that show the inherent settling and stress relaxation based on the interaction between the insulation and heat pellets alone.

  10. Adding large EM stack support

    KAUST Repository

    Holst, Glendon


    Serial section electron microscopy (SSEM) image stacks generated using high throughput microscopy techniques are an integral tool for investigating brain connectivity and cell morphology. FIB or 3View scanning electron microscopes easily generate gigabytes of data. In order to produce analyzable 3D dataset from the imaged volumes, efficient and reliable image segmentation is crucial. Classical manual approaches to segmentation are time consuming and labour intensive. Semiautomatic seeded watershed segmentation algorithms, such as those implemented by ilastik image processing software, are a very powerful alternative, substantially speeding up segmentation times. We have used ilastik effectively for small EM stacks – on a laptop, no less; however, ilastik was unable to carve the large EM stacks we needed to segment because its memory requirements grew too large – even for the biggest workstations we had available. For this reason, we refactored the carving module of ilastik to scale it up to large EM stacks on large workstations, and tested its efficiency. We modified the carving module, building on existing blockwise processing functionality to process data in manageable chunks that can fit within RAM (main memory). We review this refactoring work, highlighting the software architecture, design choices, modifications, and issues encountered.

  11. High yielding synthesis of 2,2′-bipyridine macrocycles, versatile intermediates in the synthesis of rotaxanes


    Lewis, J. E. M.; Bordoli, R. J.; Denis, M.; Fletcher, C. J.; Galli, M.; Neal, E. A.; Rochette, E. M.; Goldup, S. M.


    We present an operationally simple approach to 2,2?-bipyridine macrocycles. Our method uses simple starting materials to produce these previously hard to access rotaxane precursors in remarkable yields (typically >65%) across a range of scales (0.1–5 mmol). All of the macrocycles reported are efficiently converted (>90%) to rotaxanes under AT-CuAAC conditions. With the requisite macrocycles finally available in sufficient quantities, we further demonstrate their long term utility throug...

  12. Metal ion sequestration: An exciting dimension for molecularly ...

    African Journals Online (AJOL)

    Metal ion sequestration: An exciting dimension for molecularly imprinted polymer technology. DMS Mosha, LL Mkayula. Abstract. The use of a tight binding macrocyclic ligand to complex a metal ion so that this serves as receptee on the Molecularly Imprinted Polymer (MIP) receptor as described here affords a sequestration ...

  13. Development and durability of SOFC stacks

    Energy Technology Data Exchange (ETDEWEB)

    Beeaff, D.; Dinesen, A.R.; Mikkelsen, Lars; Nielsen, Karsten A.; Solvang, M.; Hendriksen, Peter V.


    The present project is a part of the Danish SOFC programme, which has the overall aim of establishing a Danish production of SOFC - cells, stacks and systems for economical and environmentally friendly power production. The aim of the present project was to develop and demonstrate (on a small scale, few cells, few thousand hours) a durable, thermally cyclable stack with high performance at 750 deg. C. Good progress towards this target has been made and demonstrated at the level of stack-elements (one cell between two interconnects) or small stacks (3 5 cells). Three different stacks or stack-elements have been operated for periods exceeding 3000 hr. The work has covered development of stack-components (seals, interconnects, coatings, contact layers), establishment of procedures for stack assembly and initiation, and detailed electrical characterisation with the aims of identifying performance limiting factors as well as long term durability. Further, post test investigations have been carried out to identify possible degradation mechanisms. (BA)


    Directory of Open Access Journals (Sweden)



    Full Text Available The authors present a comparative analysis of the number of repetitions in two training macro-cycles of the weightlifting Olympic team. We have considered that the differences between the number of reps in each training stage of the macro-cycles no. 1 and 2 will influence the performances achieved in competition. This approach has led to the organization of a study group in the weightlifting Olympic team of Romania. The scientific argument is the presentation of the number of reps during the preparation of the weightlifting Olympic team in different mezzo and micro-cycles of training, that, by decreasing the number of reps and increasing the intensity of the effort up to the maximum level from a training micro-cycle to another,contributes to reaching the fitness peak in competitive period within the macro-cycle no.1; also, an optimum number of reps during the training macro-cycle no.2 will make possible to keep the fitness necessary for their turning into good account in the next competition.The study was conducted over a period of two training macro-cycles (04.01-16.08.2008, with a group of 6 athletes, of 17 to 31 years old, whose target of performance was the participation in the EuropeanChampionships (E. C. for Seniors, Lignano – Sabbiadoro, Italy 2008 and the Olympic Games (J.O. in Beijing in 2008. The athletes’ progresses during the training stages and competitions were recorded by means of the statistical-mathematical and plotting methods.The study highlights the number of reps within two training macro-cycles of the weightlifting Olympic team. At the end of the paper we are able to confirm that the differences between the number of reps at each stage of training in the macro-cycles no. 1 and 2 have influenced the performances achieved in competition

  15. Metal Complexes with a Hexadentate Macrocyclic Diamine-Tetracarbene Ligand. (United States)

    Lu, Taotao; Yang, Chu-Fan; Zhang, Li-Yi; Fei, Fan; Chen, Xue-Tai; Xue, Zi-Ling


    A hexadentate macrocyclic N-heterocyclic carbene (NHC) ligand precursor (H 4 L)(PF 6 ) 4 containing four benzimidazolium and two secondary amine groups, has been synthesized and characterized. Coordination chemistry of this new macrocyclic diamine-tetracarbene ligand has been studied by the synthesis of its Ag(I), Au(I), Ni(II), and Pd(II) complexes. Reactions of (H 4 L)(PF 6 ) 4 with different equiv of Ag 2 O result in Ag(I) complexes [Ag(H 2 L)](PF 6 ) 3 (1) and [Ag 2 (H 2 L)](PF 6 ) 4 (2). A mononuclear Au(I) complex [Au(H 2 L)](PF 6 ) 3 (3) and a trinuclear Au(I) complex [Au 3 (H 2 L)(Cl) 2 ](PF 6 ) (4) are obtained by transmetalation of 1 and 2 with AuCl(SMe 2 ), respectively. Reactions of (H 4 L)(PF 6 ) 4 with Ni(OAc) 2 and Pd(OAc) 2 in the presence of NaOAc yield [Ni(L)](PF 6 ) 2 (5) and [Pd(L)](PF 6 ) 2 (6), respectively, containing one Ni(II) and Pd(II) ion with distorted square-planar geometry. Using more NaOAc results in the formation of unusual dinuclear complexes [Ni 2 (L-2H)](PF 6 ) 2 (7) and [Pd 2 (L-2H)](PF 6 ) 2 (8) (L-2H = deprotonated ligand after removing two H + ions from two secondary amine groups in L), respectively, featuring a rare M 2 N 2 core formed by two bridging amides. 7 is also formed by the reaction of 5 with 1.0 equiv of Ni(OAc) 2 ·4H 2 O in the presence of NaOAc. Transmetalation of 2 with 2.0 equiv of Ni(PPh 3 ) 2 Cl 2 gives [Ni 2 (L)(μ-O)](PF 6 ) 2 (9), the first example of a dinuclear Ni(II) complex with a singly bridging oxo group. 9 is converted to 7 in good yield through the treatment with NaOAc.

  16. Electron transfer reactions of macrocyclic compounds of cobalt

    Energy Technology Data Exchange (ETDEWEB)

    Heckman, R.A.


    The kinetics and mechanisms of reduction of H/sub 2/O/sub 2/, Br/sub 2/, and I/sub 2/ by various macrocyclic tetraaza complexes of cobalt(II), including Vitamin B/sub 12r/, were studied. The synthetic macrocycles studied were all 14-membered rings which varied in the degree of unsaturation,substitution of methyl groups on the periphery of the ring, and substitution within the ring itself. Scavenging experiments demonstrated that the reductions of H/sub 2/O/sub 2/ produce free hydroxyl radicals only in the case of Co((14)ane)/sup 2 +/ but with none of the others. In the latter instances apparently H/sub 2/O/sub 2/ simultaneously oxidizes the metal center and the ligand. The reductions of Br/sub 2/ and I/sub 2/ produce an aquohalocobalt(III) product for all reductants (except B/sub 12r/ + Br/sub 2/, which was complicated by bromination of the corrin ring). The mechanism of halogen reduction was found to involve rate-limiting inner-sphere electron transfer from cobalt to halogen to produce a dihalide anion coordinated to the cobalt center. This intermediate subsequently decomposes in rapid reactions to halocobalt(III) and halogen atom species or reacts with another cobalt(II) center to give two molecules of halocobalt(III). The reductions of halomethylcobaloximes and related compounds and diamminecobaloxime by Cr/sup 2 +/ were also studied. The reaction was found to be biphasic in all cases with the reaction products being halomethane (for the halomethylcobaloximes), Co/sup 2 +/ (in less than 100 percent yield), a Cr(III)-dimethylglyoxime species, a small amount of free dmgH/sub 2/, and a highly-charged species containing both cobalt and chromium. The first-stage reaction occurs with a stoichiometry of 1:1 producing an intermediate with an absorption maximum at 460 nm for all starting reagents. The results were interpreted in terms of inner-sphere coordination of the cobaloxime to the Cr(II) and electron transfer through the oxime N-O bond.

  17. Dermatobia hominis: Potencial risk of resistance to macrocyclic lactones. (United States)

    das Neves, José Henrique; Carvalho, Nadino; Amarante, Alessandro F T


    Dermatobia hominis is an ectoparasite that infests various species of mammals, including cattle, impairing the quality of cowhides and leather. After observing natural infestation with D. hominis larvae in cattle on two farms in the state of São Paulo, Brazil, we evaluated the efficacy of two macrocyclic lactones, ivermectin and moxidectin, against this parasite. The drugs were administered to 10 animals in each group, following the manufacturer's instructions. The groups were: Group 1-treated with ivermectin (0.2mg/kg of body weight (BW)); Group 2-treated with moxidectin (0.2mg/kg BW); and Group 3-control (untreated). On the farm in Pardinho, a total of 12 and 16 live larvae were found in 6 and in 8 animals 10 days after the treatment with ivermectin and moxidectin, respectively, while in the control group 4 bovines had a total of 7 live larvae. On the farm in Anhembi, 2, 4 and 6 live larvae were extracted from ivermectin, moxidectin and control groups, respectively, after the treatment. This is the first report of the presence of live D. hominis larvae after the treatment of cattle with ivermectin and moxidectin in Brazil. Copyright © 2015 Elsevier B.V. All rights reserved.

  18. Unsaturated 15 and 16 Membered Appended Naphthalene Macrocyclic Molecules for The Development of Fluorometric Chemosensors (United States)

    Hasan, S.; Salleh, S.; Hamdan, S.; Yamin, B.


    Unsaturated macrocyclic molecules have got an interest due to their potential in catalysis, ion exchange and electron transfer. Salicaldehyde derivatives macrocyclic molecules have a broad range in synthesis. In this study, two unsaturated macrocyclic molecules (L1 and L2) have been synthesized. The preparation of unsaturated macrocyclic ligands involve two steps; the reaction of salicylaldehyde with 1,2-dibromoethane or 1,4-dibromobutane to produce precursor, then cyclisation were completed using schiff base technique by adding diamines (naphthalene diamine). The ligands were characterized spectroscopically. In FT-IR spectrums, the form of the ligands mainly can be observed on the disappearance of the carbonyl group of aldehyde at approximately 1650cm-1 that was readily assigned to C=O group of salicylaldehyde with the replacement of C=N peak at 1684.13cm-1. The success in producing macrocyclic ligands have been further characterized using fluorescence emission spectroscopy (FES) and revealed the typical emission of naphthalene at ∼430nm. Fluorescence changes of L1 and L2 showed high selectivity for Fe3+ and Cu2+ respectively in the presence of other common metal ions, such as Zn2+, Ni2+ and Co2+. Besides, the ligand was sensitive enough to detect the concentration of ferric ion with the detection limit down to 1.08 x 10-6 M and fluorescence change that was unaffected by the presence of other common coexisting metal ions. Complexation with Co(II) was also attempted.

  19. ConfBuster: Open-Source Tools for Macrocycle Conformational Search and Analysis

    Directory of Open Access Journals (Sweden)

    Xavier Barbeau


    Full Text Available Macrocycles are cyclic macromolecules that have gained an increased interest in drug development. To our knowledge, the current bioinformatics tools that are available to investigate and predict macrocycles 3D conformations are limited in their availability. In this paper, we introduce ConfBuster, a suite of tools written in Python with the goal of sampling the lower energy conformations of macrocycles. The suite also includes tools for the analysis and visualisation of the conformational search results. Coordinate sets of single molecules in MOL2 or PDB format are required as input, and a set of lower energy conformation coordinates is returned as output, as well as PyMOL script and graphics for results analysis. In addition to Python and the optional R programming languages with freely available packages, the tools require Open Babel and PyMOL to work properly. For several examples, ConfBuster found macrocycle conformations that are within few tenths of Å of the experimental structures in minutes. To our knowledge, this is the only open-source tools for macrocycle conformational search available to the scientific community

  20. Theoretical studies on the possible sensitizers of DSSC: Nanocomposites of graphene quantum dot hybrid phthalocyanine/tetrabenzoporphyrin/tetrabenzotriazaporphyrins/cis-tetrabenzodiazaporphyrins/tetrabenzomonoazaporphyrins and their Cu-metallated macrocycles (United States)

    Gao, Feng; Yang, Chuan-Lu; Wang, Mei-Shan; Ma, Xiao-Guang; Liu, Wen-Wang


    The feasibility of nanocomposites of cir-coronene graphene quantum dot (GQD) with phthalocyanine, tetrabenzoporphyrin, tetrabenzotriazaporphyrins, cis-tetrabenzodiazaporphyrins, tetrabenzomonoazaporphyrins and their Cu-metallated macrocycles as a sensitizer of dye-sensitized solar cells (DSSC) are investigated. Based on the first principles density functional theory (DFT), the geometrical structures of the separate GQD and 10 macrocycles, and their hybridized nanocomposites are fully optimized. The energy stabilities of the obtained structures are confirmed by harmonic frequency analysis. The optical absorptions of the optimized structures are calculated with time-dependent DFT. The feasibility of the nanocomposites as the sensitizer of DSSC is examined by the charge spatial separation, the electron transfer, the molecular orbital energy levels of the nanocomposites and the electrolyte, and the conduction band minimum of TiO2 electrode. The results demonstrate that all the nanocomposites have enhanced absorptions in the visible light range, and their molecular orbital energies satisfy the requirement of sensitizers. However, only two of the ten considered nanocomposites demonstrate significantly charge spatial separation. The GQD-Cu-TBP is identified as the most favorable candidate sensitizer of DSSC by the most enhanced in optical absorption, obvious charge spatial separation, suitable LUMO energy levels and driving force for electron transfer, and low recombination rate of electron and hole.

  1. Lightweight Stacks of Direct Methanol Fuel Cells (United States)

    Narayanan, Sekharipuram; Valdez, Thomas


    An improved design concept for direct methanol fuel cells makes it possible to construct fuel-cell stacks that can weigh as little as one-third as much as do conventional bipolar fuel-cell stacks of equal power. The structural-support components of the improved cells and stacks can be made of relatively inexpensive plastics. Moreover, in comparison with conventional bipolar fuel-cell stacks, the improved fuel-cell stacks can be assembled, disassembled, and diagnosed for malfunctions more easily. These improvements are expected to bring portable direct methanol fuel cells and stacks closer to commercialization. In a conventional bipolar fuel-cell stack, the cells are interspersed with bipolar plates (also called biplates), which are structural components that serve to interconnect the cells and distribute the reactants (methanol and air). The cells and biplates are sandwiched between metal end plates. Usually, the stack is held together under pressure by tie rods that clamp the end plates. The bipolar stack configuration offers the advantage of very low internal electrical resistance. However, when the power output of a stack is only a few watts, the very low internal resistance of a bipolar stack is not absolutely necessary for keeping the internal power loss acceptably low.

  2. Solid Oxide Fuel Cell Stack Diagnostics

    DEFF Research Database (Denmark)

    Mosbæk, Rasmus Rode; Barfod, Rasmus Gottrup

    . An operating stack is subject to compositional gradients in the gaseous reactant streams, and temperature gradients across each cell and across the stack, which complicates detailed analysis. Several experimental stacks from Topsoe Fuel Cell A/S were characterized using Electrochemical Impedance Spectroscopy...... (EIS). The stack measurement geometry was optimized for EIS by careful selection of the placement of current feeds and voltage probes in order to minimize measurement errors. It was demonstrated that with the improved placement of current feeds and voltage probes it is possible to separate the loss...... in the hydrogen fuel gas supplied to the stack. EIS was used to examine the long-term behavior and monitor the evolution of the impedance of each of the repeating units and the whole stack. The observed impedance was analyzed in detail for one of the repeating units and the whole stack and the losses reported...

  3. Self-assembled monolayers of shape-persistent macrocycles on graphite: interior design and conformational polymorphism

    Directory of Open Access Journals (Sweden)

    Joscha Vollmeyer


    Full Text Available Three shape-persistent naphthylene–phenylene–acetylene macrocycles of identical backbone structures and extraannular substitution patterns but different (empty, apolar, polar nanopore fillings are self-assembled at the solid/liquid interface of highly oriented pyrolytic graphite and 1,2,4-trichlorobenzene. Submolecularly resolved images of the resulting two-dimensional (2D crystalline monolayer patterns are obtained by in situ scanning tunneling microscopy. A concentration-dependent conformational polymorphism is found, and open and more dense packing motifs are observed. For all three compounds alike lattice parameters are found, therefore the intermolecular macrocycle distances are mainly determined by their size and symmetry. This is an excellent example that the graphite acts as a template for the macrocycle organization independent from their specific interior.

  4. Self-assembled monolayers of shape-persistent macrocycles on graphite: interior design and conformational polymorphism. (United States)

    Vollmeyer, Joscha; Eberhagen, Friederike; Höger, Sigurd; Jester, Stefan-S


    Three shape-persistent naphthylene-phenylene-acetylene macrocycles of identical backbone structures and extraannular substitution patterns but different (empty, apolar, polar) nanopore fillings are self-assembled at the solid/liquid interface of highly oriented pyrolytic graphite and 1,2,4-trichlorobenzene. Submolecularly resolved images of the resulting two-dimensional (2D) crystalline monolayer patterns are obtained by in situ scanning tunneling microscopy. A concentration-dependent conformational polymorphism is found, and open and more dense packing motifs are observed. For all three compounds alike lattice parameters are found, therefore the intermolecular macrocycle distances are mainly determined by their size and symmetry. This is an excellent example that the graphite acts as a template for the macrocycle organization independent from their specific interior.

  5. Heterogeneous and Homogeneous Routes in Water Oxidation Catalysis Starting from Cu(II) Complexes with Tetraaza Macrocyclic Ligands. (United States)

    Prevedello, Andrea; Bazzan, Irene; Dalle Carbonare, Nicola; Giuliani, Angela; Bhardwaj, Sunil; Africh, Cristina; Cepek, Cinzia; Argazzi, Roberto; Bonchio, Marcella; Caramori, Stefano; Robert, Marc; Sartorel, Andrea


    Since the first report in 2012, molecular copper complexes have been proposed as efficient electrocatalysts for water oxidation reactions, carried out in alkaline/neutral aqueous media. However, in some cases the copper species have been recognized as precursors of an active copper oxide layer, electrodeposited onto the working electrode. Therefore, the question whether copper catalysis is molecular or not is particularly relevant in the field of water oxidation. In this study, we investigate the electrochemical activity of copper(II) complexes with two tetraaza macrocyclic ligands, distinguishing heterogeneous or homogeneous processes depending on the reaction media. In an alkaline aqueous solution, and upon application of an anodic bias to working electrodes, an active copper oxide layer is observed to electrodeposit at the electrode surface. Conversely, water oxidation in neutral aqueous buffers is not associated to formation of the copper oxide layer, and could be exploited to evaluate and optimize a molecular, homogeneous catalysis. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Macrocyclic ligands for uranium complexation. Final report, August 1, 1986--March 31, 1993

    International Nuclear Information System (INIS)

    Potts, K.T.


    Macrocycles, designed for complexation of the uranyl ion by computer modeling studies and utilizing six ligating atoms in the equatorial plane of the uranyl ions, have been prepared and their complexation of the uranyl ions evaluated. The ligating atoms, either oxygen or sulfur, were part of acylurea, biuret or thiobiuret subunits with alkane chains or pyridine units completing the macrocyclic periphery. These macrocycles with only partial preorganization formed uranyl complexes in solution but no crystalline complexes were isolated. Refinement of the cavity diameter by variation of the peripheral functional groups is currently studied to achieve an optimized cavity diameter of 4.7--5.2 angstrom. Acyclic ligands containing the same ligating atoms in equivalent functional entities were found to form a crystalline 1:1 uranyl-ligand complex (stability constant log K = 10.7) whose structure was established by X-ray data. This complex underwent a facile, DMSO-induced rearrangement to a 2:1 uranyl-ligand complex whose structure was also established by X-ray data. The intermediates to the macrocycles all behaved as excellent ligands for the complexation of transition metals. Acylthiourea complexes of copper and nickel as well as intermolecular, binuclear copper and nickel complexes of bidentate carbonyl thioureas formed readily and their structures were established in several representative instances by X-ray structural determinations. Tetradentate bis(carbonylthioureas) were found to be very efficient selective reagents for the complexation of copper in the presence of nickel ions. Several preorganized macrocycles were also prepared but in most instances these macrocycles underwent ring-opening under complexation conditions

  7. Macrocyclic ligands for uranium complexation. Final report, August 1, 1986--March 31, 1993

    Energy Technology Data Exchange (ETDEWEB)

    Potts, K.T.


    Macrocycles, designed for complexation of the uranyl ion by computer modeling studies and utilizing six ligating atoms in the equatorial plane of the uranyl ions, have been prepared and their complexation of the uranyl ions evaluated. The ligating atoms, either oxygen or sulfur, were part of acylurea, biuret or thiobiuret subunits with alkane chains or pyridine units completing the macrocyclic periphery. These macrocycles with only partial preorganization formed uranyl complexes in solution but no crystalline complexes were isolated. Refinement of the cavity diameter by variation of the peripheral functional groups is currently studied to achieve an optimized cavity diameter of 4.7--5.2 {angstrom}. Acyclic ligands containing the same ligating atoms in equivalent functional entities were found to form a crystalline 1:1 uranyl-ligand complex (stability constant log K = 10.7) whose structure was established by X-ray data. This complex underwent a facile, DMSO-induced rearrangement to a 2:1 uranyl-ligand complex whose structure was also established by X-ray data. The intermediates to the macrocycles all behaved as excellent ligands for the complexation of transition metals. Acylthiourea complexes of copper and nickel as well as intermolecular, binuclear copper and nickel complexes of bidentate carbonyl thioureas formed readily and their structures were established in several representative instances by X-ray structural determinations. Tetradentate bis(carbonylthioureas) were found to be very efficient selective reagents for the complexation of copper in the presence of nickel ions. Several preorganized macrocycles were also prepared but in most instances these macrocycles underwent ring-opening under complexation conditions.

  8. BINOL Macrocycle Derivatives: Synthesis of New Dinaphthyl Sulfide Aza Oxa Thia Crowns (Lariats

    Directory of Open Access Journals (Sweden)

    Abbas Shockravi


    Full Text Available In this research work, dinaphthyl sulfide diester was prepared from the reaction of 1,1′-thiobis (2-hydroxy naphthalene and methylchloroacetate. Its aza-macrocyclic derivative was synthesized from the reaction of dinaphthyl sulfide diester and diethylenetriamine. Lariats were prepared from the reaction of chloroamides (four derivatives and initial macrocycle. Chloroamides were synthesized from the reaction of amines (aniline, benzylamine, 8-amino quinoline and 4-amino azobenzene and chloroacetyl chloride. All the materials were identified by IR, 1H NMR, 13C NMR, and mass spectroscopies, and elemental analysis.





    The authors present a comparative analysis of the number of repetitions in two training macro-cycles of the weightlifting Olympic team. We have considered that the differences between the number of reps in each training stage of the macro-cycles no. 1 and 2 will influence the performances achieved in competition. This approach has led to the organization of a study group in the weightlifting Olympic team of Romania. The scientific argument is the presentation of the number of reps during the ...

  10. Macrocyclic prolinyl acyl guanidines as inhibitors of β-secretase (BACE). (United States)

    Boy, Kenneth M; Guernon, Jason M; Wu, Yong-Jin; Zhang, Yunhui; Shi, Joe; Zhai, Weixu; Zhu, Shirong; Gerritz, Samuel W; Toyn, Jeremy H; Meredith, Jere E; Barten, Donna M; Burton, Catherine R; Albright, Charles F; Good, Andrew C; Grace, James E; Lentz, Kimberley A; Olson, Richard E; Macor, John E; Thompson, Lorin A


    The synthesis, evaluation, and structure-activity relationships of a class of acyl guanidines which inhibit the BACE-1 enzyme are presented. The prolinyl acyl guanidine chemotype (7c), unlike compounds of the parent isothiazole chemotype (1), yielded compounds with good agreement between their enzymatic and cellular potency as well as a reduced susceptibility to P-gp efflux. Further improvements in potency and P-gp ratio were realized via a macrocyclization strategy. The in vivo profile in wild-type mice and P-gp effects for the macrocyclic analog 21c is presented. Copyright © 2015 Elsevier Ltd. All rights reserved.

  11. Short communication: Macrocyclic lactone residues in butter from Brazilian markets. (United States)

    Macedo, Fabio; Marsico, Eliane Teixeira; Conte-Júnior, Carlos Adam; de Almeida Furtado, Leonardo; Brasil, Taila Figueredo; Pereira Netto, Annibal Duarte


    Macrocyclic lactones (ML) are commonly used in drug formulations for the treatment of parasites in cattle. In Brazil, except for drugs (or formulations) with long-term (half-life) effects, ML are registered for use in bovines. Indiscriminate use of ML may result in the presence of residues in milk and dairy products due to their lipophilic properties and thermal stability. This study applied a method of liquid chromatography with fluorimetric detection, recently developed and validated for the determination of residues of abamectin, doramectin, ivermectin, and moxidectin in butter. The method was applied to 38 samples of commercial butter purchased in the metropolitan area of Rio de Janeiro, Brazil, between June and September 2013, analyzed in triplicate. Ivermectin was detected in 89.5% of the samples, with concentrations between 0.3 and 119.4 µg/kg; 76.3% of the samples contained doramectin (0.6 to 64.7 µg/kg) and 55.2% contained abamectin (0.7 to 4.5 µg/kg). Most butter samples (76.3%) contained residues of more than 1 ML; however, no residues of moxidectin were detected. The results showed a high incidence of the presence of avermectins in butter samples. Butter is not included in the Brazilian National Plan for Control of Residues and Contaminants in Animal Products. As ML residues concentrate in lipophilic compounds, butter and other fatty dairy products should be screened for the presence of ML residues. Copyright © 2015 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

  12. The Porphobilinogen Conundrum in Prebiotic Routes to Tetrapyrrole Macrocycles (United States)

    Taniguchi, Masahiko; Ptaszek, Marcin; Chandrashaker, Vanampally; Lindsey, Jonathan S.


    Attempts to develop a credible prebiotic route to tetrapyrroles have relied on enzyme-free recapitulation of the extant biosynthesis, but this process has foundered from the inability to form the pyrrole porphobilinogen ( PBG) in good yield by self-condensation of the precursor δ-aminolevulinic acid ( ALA). PBG undergoes robust oligomerization in aqueous solution to give uroporphyrinogen (4 isomers) in good yield. ALA, PBG, and uroporphyrinogen III are universal precursors to all known tetrapyrrole macrocycles. The enzymic formation of PBG entails carbon-carbon bond formation between the less stable enolate/enamine of one ALA molecule (3-position) and the carbonyl/imine (4-position) of the second ALA molecule; without enzymes, the first ALA reacts at the more stable enolate/enamine (5-position) and gives the pyrrole pseudo-PBG. pseudo-PBG cannot self-condense, yet has one open α-pyrrole position and is proposed to be a terminator of oligopyrromethane chain-growth from PBG. Here, 23 analogues of ALA have been subjected to density functional theoretical (DFT) calculations, but no motif has been identified that directs reaction at the 3-position. Deuteriation experiments suggested 5-(phosphonooxy)levulinic acid would react preferentially at the 3- versus 5-position, but a hybrid condensation with ALA gave no observable uroporphyrin. The results suggest efforts toward a biomimetic, enzyme-free route to tetrapyrroles from ALA should turn away from structure-directed reactions and focus on catalysts that orient the two aminoketones to form PBG in a kinetically controlled process, thereby avoiding formation of pseudo-PBG.

  13. Synthesis of novel macrocycles carrying pincer-type ligands as future candidates for potential applications in size-selective, stereochemical and recyclable catalysts (United States)

    Khan, Burhan; Shah, Muhammad Raza; Rabnawaz, Muhammad


    Macrocycles with ultra dense functionalities are very useful but are difficult to synthesize. In this study, we report six novel macrocycles bearing a pincer ligand alone or a combination of pincer-calixarenes, and pincer-fluorene moieties. Click chemistry was utilized to synthesize the desired macrocycles in good yields. These macrocycles were fully characterized using mass spectrometry (EI-MS, ESI-MS, and MALDI-TOF MS), and NMR spectroscopy. These macrocycles are under investigations as size-selective and recyclable catalysts for various chemical transformations.

  14. Vertically stacked nanocellulose tactile sensor. (United States)

    Jung, Minhyun; Kim, Kyungkwan; Kim, Bumjin; Lee, Kwang-Jae; Kang, Jae-Wook; Jeon, Sanghun


    Paper-based electronic devices are attracting considerable attention, because the paper platform has unique attributes such as flexibility and eco-friendliness. Here we report on what is claimed to be the firstly fully integrated vertically-stacked nanocellulose-based tactile sensor, which is capable of simultaneously sensing temperature and pressure. The pressure and temperature sensors are operated using different principles and are stacked vertically, thereby minimizing the interference effect. For the pressure sensor, which utilizes the piezoresistance principle under pressure, the conducting electrode was inkjet printed on the TEMPO-oxidized-nanocellulose patterned with micro-sized pyramids, and the counter electrode was placed on the nanocellulose film. The pressure sensor has a high sensitivity over a wide range (500 Pa-3 kPa) and a high durability of 10 4 loading/unloading cycles. The temperature sensor combines various materials such as poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT:PSS), silver nanoparticles (AgNPs) and carbon nanotubes (CNTs) to form a thermocouple on the upper nanocellulose layer. The thermoelectric-based temperature sensors generate a thermoelectric voltage output of 1.7 mV for a temperature difference of 125 K. Our 5 × 5 tactile sensor arrays show a fast response, negligible interference, and durable sensing performance.

  15. Generalized data stacking programming model with applications

    Directory of Open Access Journals (Sweden)

    Hala Samir Elhadidy


    Full Text Available Recent researches have shown that, everywhere in various sciences the systems are following stacked-based stored change behavior when subjected to events or varying environments “on and above” their normal situations. This paper presents a generalized data stack programming (GDSP model which is developed to describe the system changes under varying environment. These changes which are captured with different ways such as sensor reading are stored in matrices. Extraction algorithm and identification technique are proposed to extract the different layers between images and identify the stack class the object follows; respectively. The general multi-stacking network is presented including the interaction between various stack-based layering of some applications. The experiments prove that the concept of stack matrix gives average accuracy of 99.45%.

  16. Flexural characteristics of a stack leg

    International Nuclear Information System (INIS)

    Cook, J.


    A 30 MV tandem Van de Graaff accelerator is at present under construction at Daresbury Laboratory. The insulating stack of the machine is of modular construction, each module being 860 mm in length. Each live section stack module contains 8 insulating legs mounted between bulkhead rings. The design, fabrication (from glass discs bonded to stainless steel discs using an epoxy film adhesive) and testing of the stack legs is described. (U.K.)

  17. Hydrogen Embrittlement And Stacking-Fault Energies (United States)

    Parr, R. A.; Johnson, M. H.; Davis, J. H.; Oh, T. K.


    Embrittlement in Ni/Cu alloys appears related to stacking-fault porbabilities. Report describes attempt to show a correlation between stacking-fault energy of different Ni/Cu alloys and susceptibility to hydrogen embrittlement. Correlation could lead to more fundamental understanding and method of predicting susceptibility of given Ni/Cu alloy form stacking-fault energies calculated from X-ray diffraction measurements.

  18. Toward a small molecule, biomimetic carbonic anhydrase model: theoretical and experimental investigations of a panel of zinc(II) aza-macrocyclic catalysts. (United States)

    Koziol, Lucas; Valdez, Carlos A; Baker, Sarah E; Lau, Edmond Y; Floyd, William C; Wong, Sergio E; Satcher, Joe H; Lightstone, Felice C; Aines, Roger D


    A panel of five zinc-chelated aza-macrocycle ligands and their ability to catalyze the hydration of carbon dioxide to bicarbonate, H(2)O + CO(2) → H(+) + HCO(3)(–), was investigated using quantum-mechanical methods and stopped-flow experiments. The key intermediates in the reaction coordinate were optimized using the M06-2X density functional with aug-cc-pVTZ basis set. Activation energies for the first step in the catalytic cycle, nucleophilic CO(2) addition, were calculated from gas-phase optimized transition-state geometries. The computationally derived trend in activation energies was found to not correspond with the experimentally observed rates. However, activation energies for the second, bicarbonate release step, which were estimated using calculated bond dissociation energies, provided good agreement with the observed trend in rate constants. Thus, the joint theoretical and experimental results provide evidence that bicarbonate release, not CO(2) addition, may be the rate-limiting step in CO(2) hydration by zinc complexes of aza-macrocyclic ligands. pH-independent rate constants were found to increase with decreasing Lewis acidity of the ligand-Zn complex, and the trend in rate constants was correlated with molecular properties of the ligands. It is suggested that tuning catalytic efficiency through the first coordination shell of Zn(2+) ligands is predominantly a balance between increasing charge-donating character of the ligand and maintaining the catalytically relevant pK(a) below the operating pH.

  19. Grafting of aza-macrocyclic ligands onto organic fibres for the sequestering of radioelements and cadmium: application to industrial waste water treatment

    International Nuclear Information System (INIS)

    Rascalou, Frederic


    Within the frame of a preparation to the industrial transfer of a decontamination process for the processing of low-activity radioactive effluents of the Valduc nuclear centre, this research thesis reports research works which aimed at developing a new support for macrocyclic molecules in replacement of silica, in order to obtain a material which is steady in process conditions, can be incinerated at the end of the process, and could result in a higher production capacity. It also aimed at elaborating a sequestering material specific to cadmium. After a general presentation of challenges related to waste management and a presentation of the specific case of Valduc, the author gives an overview of earlier works, and discusses the validation of the selective solid-liquid extraction as additional technique to those provided by the existing processing plant. He justifies the selection of organic fibres as a new support. He reports the study of the grafting of macrocyclic molecules on viscose and polypropylene fibres, and describes ways of modification of these supports and the synthesis of the different molecular entities. The last part addresses the study of the performance of these new materials: results in static mode, performance in dynamic mode on pilot installations [fr

  20. Nuclear Magnetic Shieldings of Stacked Aromatic and Antiaromatic Molecules. (United States)

    Sundholm, Dage; Rauhalahti, Markus; Özcan, Nergiz; Mera-Adasme, Raúl; Kussmann, Jörg; Luenser, Arne; Ochsenfeld, Christian


    Nuclear magnetic shieldings have been calculated at the density functional theory (DFT) level for stacks of benzene, hexadehydro[12]annulene, dodecadehydro[18]annulene, and hexabenzocoronene. The magnetic shieldings due to the ring currents in the adjacent molecules have been estimated by calculating nucleus independent molecular shieldings for the monomer in the atomic positions of neighbor molecules. The calculations show that the independent shielding model works reasonably well for the 1 H NMR shieldings of benzene and hexadehydro[12]annulene, whereas for the larger molecules and for the 13 C NMR shieldings the interaction between the molecules leads to shielding effects that are at least of the same size as the ring current contributions from the adjacent molecules. A better agreement is obtained when the nearest neighbors are also considered at full quantum mechanical (QM) level. The calculations suggest that the nearest solvent molecules must be included in the quantum mechanical system, at least when estimating solvent shifts at the molecular mechanics (MM) level. Current density calculations show that the stacking does not significantly affect the ring current strengths of the individual molecules, whereas the shape of the ring current for a single molecule differs from that of the stacked molecules.

  1. Stacks of SPS Dipole Magnets

    CERN Multimedia


    Stacks of SPS Dipole Magnets ready for installation in the tunnel. The SPS uses a separated function lattice with dipoles for bending and quadrupoles for focusing. The 6.2 m long normal conducting dipoles are of H-type with coils that are bent-up at the ends. There are two types, B1 (total of 360) and B2 (384). Both are for a maximum field of 1.8 Tesla and have the same outer dimensions (450x800 mm2 vxh) but with different gaps (B1: 39x129 mm2, B2: 52x92 mm2) tailored to the beam size. The yoke, made of 1.5 mm thick laminations, consists of an upper and a lower half joined together in the median plane once the coils have been inserted.

  2. California dreaming?[PEM stacks

    Energy Technology Data Exchange (ETDEWEB)

    Crosse, J.


    Hyundai's Santa Fe FCEV will be on sale by the end of 2002. Hyundai uses PEM stacks that are manufactured by International Fuel Cells (IFC), a division of United Technologies. Santa Fe is equipped with a 65 kW electric powertrain of Enova systems and Shell's new gasoline reformer called Hydrogen Source. Eugene Jang, Senior Engineer - Fuel Cell and Materials at Hyundai stated that the compressor related losses on IFC system are below 3%. The maximum speed offered by the vehicle is estimated as 123km/hr while the petrol equivalent fuel consumption is quoted between 5.6L/100 km and 4.8L/100 km. Santa Fe is a compact vehicle offering better steering response and a pleasant drive. (author)

  3. New macrocycles with potent antituberculosis activity accessed by one-pot multicomponent reactions

    NARCIS (Netherlands)

    Kim, D.; Huang, Y.; Wang, K.; Doemling, A.

    Based on modeling studies, we hypothesized that tylosin derivatives without formyl group should rather adopt an erythromycin-like binding mode to the ribosome. Twenty four 16-membered macrocyclic compounds were accessed by multicomponent reactions (Gewald, Ugi) of tylosin and investigated for their

  4. Dimetal Complexes of a Bibrachial 2+2 Thiolate-based Macrocycle

    DEFF Research Database (Denmark)

    Lennartson, Anders; McKee, Vickie; Nelson, Jane


    Protocols for accessing the [2+3] and [2+2] tren + thiophenolate-based cryptands and macrocycles, respectively, have been devised; however, a propensity towards incomplete crypt formation is clear: Cd(II)2, Mn(II)2, Ni(II)2 and Pd(II)2 complexes of the [2+2] bibrachial systems in which one arm of...

  5. Study of behaviour of Ni(III) macrocyclic complexes in acidic ...

    Indian Academy of Sciences (India)

    Study of behaviour of Ni(III) macrocyclic complexes in acidic aqueous medium through kinetic measurement involving hydrogen peroxide oxidation and DFT calculations. ANURADHA SANKARANa,b, E J PADMA MALARc,∗ and. VENKATAPURAM RAMANUJAM VIJAYARAGHAVANa,∗. aDepartment of Physical Chemistry, ...

  6. Sulfur-Switch Ugi Reaction for Macrocyclic Disulfide-Bridged Peptidomimetics

    NARCIS (Netherlands)

    Vishwanatha, Thimmalapura M; Bergamaschi, Enrico; Dömling, Alexander


    A general strategy is introduced for the efficient synthetic access of disulfide linked artificial macrocycles via a Ugi four-component reaction (U4CR) followed by oxidative cyclization. The double-mercapto input is proposed for use in the Ugi reaction, thereby yielding all six topologically

  7. Design and synthesis of macrocyclic peptidyl hydroxamates as peptide deformylase inhibitors. (United States)

    Shen, Gang; Zhu, Jinge; Simpson, Anthony M; Pei, Dehua


    Macrocyclic peptidyl hydroxamates were designed, synthesized, and evaluated as peptide deformylase (PDF) inhibitors. The most potent compound exhibited tight, slow-binding inhibition of Escherichia coli PDF (K(I)(*)=4.4 nM) and had potent antibacterial activity against Gram-positive bacterium Bacillus subtilis (MIC=2-4 microg/mL).

  8. Synthesis and extended activity of triazole-containing macrocyclic protease inhibitors

    DEFF Research Database (Denmark)

    Pehere, A.D.; Pietsch, M.; Gütschow, M.


    Peptide-derived protease inhibitors are an important class of compounds with the potential to treat a wide range of diseases. Herein, we describe the synthesis of a series of triazole- containing macrocyclic protease inhibitors pre-organized into a b-strand conformation and an evaluation...

  9. Macrocyclic ligands for uranium complexation: Progress report, August 15, 1986--January 28, 1989

    Energy Technology Data Exchange (ETDEWEB)

    Potts, K.T.


    Macrocycles, designed for complexation of the uranyl ion by computer modeling studies and utilizing six ligating atoms in the equatorial plane of the uranyl ion, have been prepared and their ability to complex the uranyl ion evaluated. The ligating atoms, either oxygen or sulfur, were part of acylurea, biuret or thiobiuret subunits with alkane chains or pyridine units completing the macrocyclic periphery. The macrocycles studied formed uranyl complexes in solution but no crystalline complexes have been isolated to date. Acyclic ligands containing the same atoms in equivalent functional entities were found to form a crystalline 1:1 uranyl-ligand complex whose structure was established by X-ray data. This complex underwent a facile, DMSO-induced rearrangement to a 2:1 uranyl-ligand complex whose structure was also established by X-ray data. The intermediates to the macrocycles all behave as excellent ligands for the complexation of transition metals. Acylthiourea complexes of copper and nickel as well as intermolecular, binuclear copper and nickel complexes of bidentate carbonyl thioureas formed readily and their structures were established in several representative instances by X-ray structural determinations. Tetradentate bis(carbonylthioureas) were found to be very efficient selective reagents for the complexation of copper in the presence of nickel ions. 21 refs., 7 figs., 10 tabs.

  10. Fe(III) complex of biuret-amide based macrocyclic ligand as peroxidase enzyme mimic. (United States)

    Panda, Chakadola; Ghosh, Munmun; Panda, Tamas; Banerjee, Rahul; Sen Gupta, Sayam


    An Fe(III) complex of a biuret-amide based macrocyclic ligand that exhibits both excellent reactivity for the activation of H(2)O(2) and high stability, especially at low pH and high ionic strength, is reported.

  11. Macrocyclic Peptoid–Peptide Hybrids as Inhibitors of Class I Histone Deacetylases

    DEFF Research Database (Denmark)

    Olsen, Christian Adam; Montero, Ana; Leman, Luke J.


    We report the design, synthesis, and biological evaluation of the first macrocyclic peptoid-containing histone deacetylase (HDAC) inhibitors. The compounds selectively inhibit human class I HDAC isoforms in vitro, with no inhibition of the tubulin deacetylase activity associated with class IIb HDAC...

  12. Complexation of Eu3+ with a macrocyclic lactam receptor: Experimental and theoretical study

    Czech Academy of Sciences Publication Activity Database

    Makrlík, E.; Záliš, Stanislav; Sedláková, Zdeňka; Vaňura, P.


    Roč. 1038, APR 2013 (2013), s. 216-219 ISSN 0022-2860 Institutional support: RVO:61388955 ; RVO:61389013 Keywords : europium * macrocyclic lactam receptor * complexation Subject RIV: CF - Physical ; Theoretical Chemistry ; CD - Macromolecular Chemistry (UMCH-V) Impact factor: 1.599, year: 2013

  13. Experimental and DFT study on complexation of Eu3+ with a macrocyclic lactam receptor

    Czech Academy of Sciences Publication Activity Database

    Makrlík, E.; Záliš, Stanislav; Vaňura, P.; Sedláková, Zdeňka


    Roč. 24, č. 6 (2013), s. 2149-2153 ISSN 1040-0400 Institutional support: RVO:61388955 ; RVO:61389013 Keywords : europium * macrocyclic lactam receptor * complexation Subject RIV: CF - Physical ; Theoretical Chemistry ; CD - Macromolecular Chemistry (UMCH-V) Impact factor: 1.900, year: 2013

  14. Studies of Flerovium and Element 115 Homologs with Macrocyclic Extractants

    Energy Technology Data Exchange (ETDEWEB)

    Despotopulos, John D. [Univ. of Nevada, Las Vegas, NV (United States)


    Study of the chemistry of the heaviest elements, Z ≥ 104, poses a unique challenge due to their low production cross-sections and short half-lives. Chemistry also must be studied on the one-atom-at-a-time scale, requiring automated, fast, and very efficient chemical schemes. Recent studies of the chemical behavior of copernicium (Cn, element 112) and flerovium (Fl, element 114) together with the discovery of isotopes of these elements with half-lives suitable for chemical studies have spurred a renewed interest in the development of rapid systems designed to study the chemical properties of elements with Z ≥ 114. This dissertation explores both extraction chromatography and solvent extraction as methods for development of a rapid chemical separation scheme for the homologs of flerovium (Pb, Sn, Hg) and element 115 (Bi, Sb), with the goal of developing a chemical scheme that, in the future, can be applied to on-line chemistry of both Fl and element 115. Carrier-free radionuclides, used in these studies, of the homologs of Fl and element 115 were obtained by proton activation of high-purity metal foils at the Lawrence Livermore National Laboratory (LLNL) Center for Accelerator Mass Spectrometry (CAMS): natIn(p,n)113Sn, natSn(p,n)124Sb, and Au(p,n)197m,gHg. The carrier-free activity was separated from the foils by novel separation schemes based on ion exchange and extraction chromatography techniques. Carrier-free Pb and Bi isotopes were obtained from development of a novel generator based on cation exchange chromatography using the 232U parent to generate 212Pb and 212Bi. Macrocyclic extractants, specifically crown ethers and their derivatives, were chosen for these studies; crown ethers show high selectivity for metal ions. Finally. a potential chemical system for Fl was established based on the Eichrom Pb resin, and insight to an improved system based on thiacrown ethers is

  15. Stacking technology for a space constrained microsystem

    DEFF Research Database (Denmark)

    Heschel, Matthias; Kuhmann, Jochen Friedrich; Bouwstra, Siebe


    In this paper we present a stacking technology for an integrated packaging of an intelligent transducer which is formed by a micromachined silicon transducer and an integrated circuit chip. Transducer and circuitry are stacked on top of each other with an intermediate chip in between. The bonding...

  16. Vector Fields and Flows on Differentiable Stacks

    DEFF Research Database (Denmark)

    A. Hepworth, Richard


    This paper introduces the notions of vector field and flow on a general differentiable stack. Our main theorem states that the flow of a vector field on a compact proper differentiable stack exists and is unique up to a uniquely determined 2-cell. This extends the usual result on the existence...... of vector fields....

  17. 40 CFR 61.44 - Stack sampling. (United States)


    ... 40 Protection of Environment 8 2010-07-01 2010-07-01 false Stack sampling. 61.44 Section 61.44 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS (CONTINUED) NATIONAL... Firing § 61.44 Stack sampling. (a) Sources subject to § 61.42(b) shall be continuously sampled, during...

  18. Learning OpenStack networking (Neutron)

    CERN Document Server

    Denton, James


    If you are an OpenStack-based cloud operator with experience in OpenStack Compute and nova-network but are new to Neutron networking, then this book is for you. Some networking experience is recommended, and a physical network infrastructure is required to provide connectivity to instances and other network resources configured in the book.

  19. Project W-420 stack monitoring system upgrades

    International Nuclear Information System (INIS)



    This project will execute the design, procurement, construction, startup, and turnover activities for upgrades to the stack monitoring system on selected Tank Waste Remediation System (TWRS) ventilation systems. In this plan, the technical, schedule, and cost baselines are identified, and the roles and responsibilities of project participants are defined for managing the Stack Monitoring System Upgrades, Project W-420

  20. On the "stacking fault" in copper

    NARCIS (Netherlands)

    Fransens, J.R.; Pleiter, F


    The results of a perturbed gamma-gamma angular correlations experiment on In-111 implanted into a properly cut single crystal of copper show that the defect known in the literature as "stacking fault" is not a planar faulted loop but a stacking fault tetrahedron with a size of 10-50 Angstrom.

  1. Status of MCFC stack technology at IHI

    Energy Technology Data Exchange (ETDEWEB)

    Hosaka, M.; Morita, T.; Matsuyama, T.; Otsubo, M. [Ishikawajima-Harima Heavy Industries Co., Ltd., Tokyo (Japan)


    The molten carbonate fuel cell (MCFC) is a promising option for highly efficient power generation possible to enlarge. IHI has been studying parallel flow MCFC stacks with internal manifolds that have a large electrode area of 1m{sup 2}. IHI will make two 250 kW stacks for MW plant, and has begun to make cell components for the plant. To improve the stability of stack, soft corrugated plate used in the separator has been developed, and a way of gathering current from stacks has been studied. The DC output potential of the plant being very high, the design of electric insulation will be very important. A 20 kW short stack test was conducted in 1995 FY to certificate some of the improvements and components of the MW plant. These activities are presented below.

  2. The impact of stack geometry and mean pressure on cold end temperature of stack in thermoacoustic refrigeration systems (United States)

    Wantha, Channarong


    This paper reports on the experimental and simulation studies of the influence of stack geometries and different mean pressures on the cold end temperature of the stack in the thermoacoustic refrigeration system. The stack geometry was tested, including spiral stack, circular pore stack and pin array stack. The results of this study show that the mean pressure of the gas in the system has a significant impact on the cold end temperature of the stack. The mean pressure of the gas in the system corresponds to thermal penetration depth, which results in a better cold end temperature of the stack. The results also show that the cold end temperature of the pin array stack decreases more than that of the spiral stack and circular pore stack geometry by approximately 63% and 70%, respectively. In addition, the thermal area and viscous area of the stack are analyzed to explain the results of such temperatures of thermoacoustic stacks.

  3. MacroEvoLution: A New Method for the Rapid Generation of Novel Scaffold-Diverse Macrocyclic Libraries. (United States)

    Saupe, Jörn; Kunz, Oliver; Haustedt, Lars Ole; Jakupovic, Sven; Mang, Christian


    Macrocycles are a structural class bearing great promise for future challenges in medicinal chemistry. Nevertheless, there are few flexible approaches for the rapid generation of structurally diverse macrocyclic compound collections. Here, an efficient method for the generation of novel macrocyclic peptide-based scaffolds is reported. The process, named here as "MacroEvoLution", is based on a cyclization screening approach that gives reliable access to novel macrocyclic architectures. Classification of building blocks into specific pools ensures that scaffolds with orthogonally addressable functionalities are generated, which can easily be used for the generation of structurally diverse compound libraries. The method grants rapid access to novel scaffolds with scalable synthesis (multi gram scale) and the introduction of further diversity at a late stage. Despite being developed for peptidic systems, the approach can easily be extended for the synthesis of systems with a decreased peptidic character. © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

  4. MacroEvoLution: A New Method for the Rapid Generation of Novel Scaffold‐Diverse Macrocyclic Libraries (United States)

    Saupe, Jörn; Kunz, Oliver; Haustedt, Lars Ole; Jakupovic, Sven


    Abstract Macrocycles are a structural class bearing great promise for future challenges in medicinal chemistry. Nevertheless, there are few flexible approaches for the rapid generation of structurally diverse macrocyclic compound collections. Here, an efficient method for the generation of novel macrocyclic peptide‐based scaffolds is reported. The process, named here as “MacroEvoLution”, is based on a cyclization screening approach that gives reliable access to novel macrocyclic architectures. Classification of building blocks into specific pools ensures that scaffolds with orthogonally addressable functionalities are generated, which can easily be used for the generation of structurally diverse compound libraries. The method grants rapid access to novel scaffolds with scalable synthesis (multi gram scale) and the introduction of further diversity at a late stage. Despite being developed for peptidic systems, the approach can easily be extended for the synthesis of systems with a decreased peptidic character. PMID:28715083

  5. Construction and screening of vast libraries of natural product-like macrocyclic peptides using in vitro display technologies. (United States)

    Bashiruddin, Nasir K; Suga, Hiroaki


    Macrocyclic structure and backbone N-methylation represent characteristic features of peptidic natural products, which play critical roles in their biological activity. Although natural products have been the traditional source of such peptides, recent developments in synthesizing natural product-like macrocyclic peptides using reconstituted translation systems have enabled us to construct vast trillion-member libraries of non-standard macrocyclic peptides. In addition, a method for displaying such libraries on their corresponding mRNA templates allows us to rapidly screen them for potent ligands against various drug targets. This review describes methodologies for the ribosomal synthesis of novel natural product-like macrocyclic peptides and their recent applications in the discovery of bioactive molecules using in vitro display technologies. Copyright © 2014 The Authors. Published by Elsevier Ltd.. All rights reserved.

  6. Synergistic extraction of some divalent metal cations into nitrobenzene by using strontium dicarbollylcobaltate and electroneutral macrocyclic lactam receptor

    Czech Academy of Sciences Publication Activity Database

    Makrlík, E.; Sedláková, Zdeňka; Vaňura, P.; Selucký, P.


    Roč. 295, č. 3 (2013), s. 2263-2266 ISSN 0236-5731 Institutional support: RVO:61389013 Keywords : divalent metal cations * macrocyclic lactam receptor * complexation Subject RIV: CD - Macromolecular Chemistry Impact factor: 1.415, year: 2013

  7. Density of oxidation-induced stacking faults in damaged silicon

    NARCIS (Netherlands)

    Kuper, F.G.; Hosson, J.Th.M. De; Verwey, J.F.


    A model for the relation between density and length of oxidation-induced stacking faults on damaged silicon surfaces is proposed, based on interactions of stacking faults with dislocations and neighboring stacking faults. The model agrees with experiments.

  8. Chemical Editing of Macrocyclic Natural Products and Kinetic Profiling Reveal Slow, Tight-Binding Histone Deacetylase Inhibitors with Picomolar Affinities

    DEFF Research Database (Denmark)

    Kitir, Betül; Maolanon, Alex R.; Ohm, Ragnhild G.


    medicines. Therefore, detailed mechanistic information and precise characterization of the chemical probes used to investigate the effects of HDAC enzymes are vital. We interrogated Nature's arsenal of macrocyclic nonribosomal peptide HDAC inhibitors by chemical synthesis and evaluation of more than 30...... natural products and analogues. This furnished surprising trends in binding affinities for the various macrocycles, which were then exploited for the design of highly potent class I and IIb HDAC inhibitors. Furthermore, thorough kinetic investigation revealed unexpected inhibitory mechanisms of important...

  9. Tunable electro-optic filter stack

    Energy Technology Data Exchange (ETDEWEB)

    Fontecchio, Adam K.; Shriyan, Sameet K.; Bellingham, Alyssa


    A holographic polymer dispersed liquid crystal (HPDLC) tunable filter exhibits switching times of no more than 20 microseconds. The HPDLC tunable filter can be utilized in a variety of applications. An HPDLC tunable filter stack can be utilized in a hyperspectral imaging system capable of spectrally multiplexing hyperspectral imaging data acquired while the hyperspectral imaging system is airborne. HPDLC tunable filter stacks can be utilized in high speed switchable optical shielding systems, for example as a coating for a visor or an aircraft canopy. These HPDLC tunable filter stacks can be fabricated using a spin coating apparatus and associated fabrication methods.

  10. Dynamical stability of slip-stacking particles

    Energy Technology Data Exchange (ETDEWEB)

    Eldred, Jeffrey; Zwaska, Robert


    We study the stability of particles in slip-stacking configuration, used to nearly double proton beam intensity at Fermilab. We introduce universal area factors to calculate the available phase space area for any set of beam parameters without individual simulation. We find perturbative solutions for stable particle trajectories. We establish Booster beam quality requirements to achieve 97% slip-stacking efficiency. We show that slip-stacking dynamics directly correspond to the driven pendulum and to the system of two standing-wave traps moving with respect to each other.

  11. Stacking fault tetrahedra formation in the neighbourhood of grain boundaries

    CERN Document Server

    Samaras, M; Van Swygenhoven, H; Victoria, M


    Large scale molecular dynamics computer simulations are performed to study the role of the grain boundary (GB) during the cascade evolution in irradiated nanocrystalline Ni. At all primary knock-on atom (PKA) energies in cascades near GBs, the damage produced after cooling down is vacancy dominated. Truncated stacking fault tetrahedra (TSFTs) are easily formed at 10 keV and higher PKA energies. At the higher energies a complex partial dislocation network forms, consisting of TSFTs. The GB acts as an interstitial sink without undergoing major structural changes.

  12. The addition of a second lanthanide ion to increase the luminescence of europium(III) macrocyclic complexes

    Energy Technology Data Exchange (ETDEWEB)

    Bromm, A.J. Jr.; Vallarino, L.M. [Virginia Commonwealth Univ., Richmond, VA (United States). Dept. of Chemistry; Leif, R.C. [Newport Instruments, San Diego, CA (United States); Quagliano, J.R. [Los Alamos National Lab., NM (United States)


    At present, the microscopic visualization of luminescent labels containing lanthanide(III) ions, primarily europium(III), as light-emitting centers is best performed with time-gated instrumentation, which by virtually eliminating the background fluorescence results in an improved signal to noise ratio. However, the use of the europium(III) macrocycle, Quantum Dye{trademark}, in conjunction with the strong luminescence enhancing effect (cofluorescence) of yttrium(III) or gadolinium(III), can eliminate the need for such specialized instrumentation. In the presence of Gd(III), the luminescence of the Eu(III)-macrocycles can be conveniently observed with conventional fluorescence instrumentation at previously unattainable low levels. The Eu(III) {sup 5}D{sub 0} {r_arrow} {sup 7}F{sub 2} emission of the Eu(III)-macrocycles was observed as an extremely sharp band with a maximum at 619 nm and a clearly resolved characteristic pattern. At very low Eu(III)-macrocycle concentrations, another sharp emission was detected at 614 nm, arising from traces of Eu(III) present in even the purest commercially available gadolinium products. Discrimination of the resolved emissions of the Eu(III)-macrocycle and Eu(III) contaminant should provide a means to further lower the limit of detection of the Eu(III)-macrocycle.

  13. Technologies for the Synthesis of mRNA-Encoding Libraries and Discovery of Bioactive Natural Product-Inspired Non-Traditional Macrocyclic Peptides

    Directory of Open Access Journals (Sweden)

    Hiroaki Suga


    Full Text Available In this review, we discuss emerging technologies for drug discovery, which yields novel molecular scaffolds based on natural product-inspired non-traditional peptides expressed using the translation machinery. Unlike natural products, these technologies allow for constructing mRNA-encoding libraries of macrocyclic peptides containing non-canonical sidechains and N-methyl-modified backbones. The complexity of sequence space in such libraries reaches as high as a trillion (>1012, affording initial hits of high affinity ligands against protein targets. Although this article comprehensively covers several related technologies, we discuss in greater detail the technical development and advantages of the Random non-standard Peptide Integration Discovery (RaPID system, including the recent identification of inhibitors against various therapeutic targets.

  14. Wearable solar cells by stacking textile electrodes. (United States)

    Pan, Shaowu; Yang, Zhibin; Chen, Peining; Deng, Jue; Li, Houpu; Peng, Huisheng


    A new and general method to produce flexible, wearable dye-sensitized solar cell (DSC) textiles by the stacking of two textile electrodes has been developed. A metal-textile electrode that was made from micrometer-sized metal wires was used as a working electrode, while the textile counter electrode was woven from highly aligned carbon nanotube fibers with high mechanical strengths and electrical conductivities. The resulting DSC textile exhibited a high energy conversion efficiency that was well maintained under bending. Compared with the woven DSC textiles that are based on wire-shaped devices, this stacked DSC textile unexpectedly exhibited a unique deformation from a rectangle to a parallelogram, which is highly desired in portable electronics. This lightweight and wearable stacked DSC textile is superior to conventional planar DSCs because the energy conversion efficiency of the stacked DSC textile was independent of the angle of incident light. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.


    Directory of Open Access Journals (Sweden)

    Eva Mazancová


    Full Text Available Stacking fault energy of high manganese alloys (marked as TWIP and TRIPLEX is an important parameter determining deformation mechanism type realized in above mentioned alloys. Stacking fault energy level can be asserted with a gliding of partial and/or full dislocations, b gliding mechanism and twinning deformation process in connection with increasing of fracture deformation level (deformation elongation and with increasing of simultaneously realized work hardening proces., c gliding mechanism and deformation induced e-martensite formation. In contribution calculated stacking fault energies are presented for various chemical compositions of high manganese alloys. Stacking fault energy dependences on manganese, carbon, iron and alluminium contents are presented. Results are confronted with some accessible papers.The aim of work is to deepen knowledge of presented data. The TWIP and TRIPLEX alloys can be held for promissing new automotive materials.

  16. Stack-Based Typed Assembly Language

    National Research Council Canada - National Science Library

    Morrisett, Greg


    .... This paper also formalizes the typing connection between CPS based compilation and stack based compilation and illustrates how STAL can formally model calling conventions by specifying them as formal translations of source function types to STAL types.

  17. Characterization of Piezoelectric Stacks for Space Applications (United States)

    Sherrit, Stewart; Jones, Christopher; Aldrich, Jack; Blodget, Chad; Bao, Xiaoqi; Badescu, Mircea; Bar-Cohen, Yoseph


    Future NASA missions are increasingly seeking to actuate mechanisms to precision levels in the nanometer range and below. Co-fired multilayer piezoelectric stacks offer the required actuation precision that is needed for such mechanisms. To obtain performance statistics and determine reliability for extended use, sets of commercial PZT stacks were tested in various AC and DC conditions at both nominal and high temperatures and voltages. In order to study the lifetime performance of these stacks, five actuators were driven sinusoidally for up to ten billion cycles. An automated data acquisition system was developed and implemented to monitor each stack's electrical current and voltage waveforms over the life of the test. As part of the monitoring tests, the displacement, impedance, capacitance and leakage current were measured to assess the operation degradation. This paper presents some of the results of this effort.

  18. The stack on software and sovereignty

    CERN Document Server

    Bratton, Benjamin H


    A comprehensive political and design theory of planetary-scale computation proposing that The Stack -- an accidental megastructure -- is both a technological apparatus and a model for a new geopolitical architecture.

  19. Stacking for Cosmic Magnetism with SKA Surveys


    Stil, J. M.; Keller, B. W.


    Stacking polarized radio emission in SKA surveys provides statistical information on large samples that is not accessible otherwise due to limitations in sensitivity, source statistics in small fields, and averaging over frequency (including Faraday synthesis). Polarization is a special case because one obvious source of stacking targets is the Stokes I source catalog, possibly in combination with external catalogs, for example an SKA HI survey or a non-radio survey. We point out the signific...

  20. Environmental Modeling Framework using Stacked Gaussian Processes


    Abdelfatah, Kareem; Bao, Junshu; Terejanu, Gabriel


    A network of independently trained Gaussian processes (StackedGP) is introduced to obtain predictions of quantities of interest with quantified uncertainties. The main applications of the StackedGP framework are to integrate different datasets through model composition, enhance predictions of quantities of interest through a cascade of intermediate predictions, and to propagate uncertainties through emulated dynamical systems driven by uncertain forcing variables. By using analytical first an...

  1. Generalized data stacking programming model with applications


    Hala Samir Elhadidy; Rawya Yehia Rizk; Hassen Taher Dorrah


    Recent researches have shown that, everywhere in various sciences the systems are following stacked-based stored change behavior when subjected to events or varying environments “on and above” their normal situations. This paper presents a generalized data stack programming (GDSP) model which is developed to describe the system changes under varying environment. These changes which are captured with different ways such as sensor reading are stored in matrices. Extraction algorithm and identif...

  2. Representations of stack triangulations in the plane


    Selig, Thomas


    Stack triangulations appear as natural objects when defining an increasing family of triangulations by successive additions of vertices. We consider two different probability distributions for such objects. We represent, or "draw" these random stack triangulations in the plane $\\R^2$ and study the asymptotic properties of these drawings, viewed as random compact metric spaces. We also look at the occupation measure of the vertices, and show that for these two distributions it converges to som...

  3. Polymers containing nickel(II) complexes of Goedken's macrocycle: optimized synthesis and electrochemical characterization. (United States)

    Paquette, Joseph A; Sauvé, Ethan R; Gilroy, Joe B


    The synthesis and characterization of a new class of nickel-containing polymers is described. The optimized copolymerization of alkyne-bearing nickel(II) complexes of Goedken's macrocycle (4,11-dihydro-5,7,12,14-tetramethyldibenzo[b,i][1,4,8,11]tetraazacyclotetradecine) and brominated 9,9-dihexylfluorene produced polymers with potential application as functional redox-active materials. The title polymers exhibit electrochemically reversible, ligand-centered oxidation events at 0.24 and 0.73 V versus the ferrocene/ferrocenium redox couple. They also display exceptional thermal stability and interesting absorption properties due to the presence of the macrocyclic nickel(II) complexes and π-conjugated units incorporated in their backbones. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. A toxicological and dermatological assessment of macrocyclic lactone and lactide derivatives when used as fragrance ingredients

    DEFF Research Database (Denmark)

    Belsito, D.; Bickers, D.; Bruze, M.


    The Macrocyclic Lactone and Lactide derivative (ML) group of fragrance ingredients was critically evaluated for safety following a complete literature search. For high end users, calculated maximum dermal exposures vary from 0.47% to 11.15%; systemic exposures vary from 0.0008 to 0.25 mg/kg/day. ......The Macrocyclic Lactone and Lactide derivative (ML) group of fragrance ingredients was critically evaluated for safety following a complete literature search. For high end users, calculated maximum dermal exposures vary from 0.47% to 11.15%; systemic exposures vary from 0.0008 to 0.25 mg...... on these findings, the Panel is of the opinion that there are no safety concerns for the MLs at reported levels of use and exposure as fragrance ingredients...

  5. Biodegradable polyester-based eco-composites containing hemp fibers modified with macrocyclic oligomers (United States)

    Conzatti, Lucia; Utzeri, Roberto; Hodge, Philip; Stagnaro, Paola


    An original compatibilizing pathway for hemp fibers/poly(1,4-butylene adipate-co-terephtalate) (PBAT) eco-composites was explored exploiting the capability of macrocyclic oligomers (MCOs), obtained by cyclodepolymerization (CDP) of PBAT at high dilution, of being re-converted into linear chains by entropically-driven ring-opening polymerization (ED-ROP) that occurs simply heating the MCOS in the bulk. CDP reaction of PBAT was carried out varying solvent, catalyst and reaction time. Selected MCOs were used to adjust the conditions of the ED-ROP reaction. The best experimental conditions were then adopted to modify hemp fibers. Eco-composites based on PBAT and hemp fibers as obtained or modified with PBAT macrocyclics or oligomers were prepared by different process strategies. The best fiber-PBAT compatibility was observed when the fibers were modified with PBAT oligomers before incorporation in the polyester matrix.

  6. Physical Removal of Anions from Aqueous Media by Means of a Macrocycle-Containing Polymeric Network

    KAUST Repository

    Ji, Xiaofan


    Reported here is a hydrogel-forming polymer network that contains a water-soluble tetracationic macrocycle. Upon immersion of this polymer network in aqueous solutions containing various inorganic and organic salts, changes in the physical properties are observed that are consistent with absorption of the constituent anions into the polymer network. This absorption is ascribed to host-guest interactions involving the tetracationic macrocyclic receptor. Removal of the anions may then be achieved by lifting the resulting hydrogels out of the aqueous phase. Treating the anion-containing hydrogels with dilute HCl leads to the protonation-induced release of the bound anions. This allows the hydrogels to be recycled for reuse. The present polymer network thus provides a potentially attractive approach to removing undesired anions from aqueous environments.

  7. The influence of intraannular templates on the liquid crystallinity of shape-persistent macrocycles

    Directory of Open Access Journals (Sweden)

    Joscha Vollmeyer


    Full Text Available A series of shape-persistent phenylene–ethynylene–naphthylene–butadiynylene macrocycles with different extraannular alkyl groups and intraannular bridges is synthesized by oxidative Glaser-coupling of the appropriate precursors. The intraannular bridges serve in this case as templates that reduce the oligomerization even when the reaction is not performed under pseudo high-dilution conditions. The extraannular as well as the intraannular substituents have a strong influence on the thermal behavior of the compounds. With branched alkyl chains at the periphery, the macrocycles exhibit liquid crystalline (lc phases when the interior is empty or when the length of the alkyl bridge is just right to cross the ring. With a longer alkyl or an oligoethylene oxide bridge no lc phase is observed, most probably because the mesogene is no longer planar.

  8. A Time-predictable Stack Cache

    DEFF Research Database (Denmark)

    Abbaspour, Sahar; Brandner, Florian; Schoeberl, Martin


    Real-time systems need time-predictable architectures to support static worst-case execution time (WCET) analysis. One architectural feature, the data cache, is hard to analyze when different data areas (e.g., heap allocated and stack allocated data) share the same cache. This sharing leads to le...... of a cache for stack allocated data. Our port of the LLVM C++ compiler supports the management of the stack cache. The combination of stack cache instructions and the hardware implementation of the stack cache is a further step towards timepredictable architectures.......Real-time systems need time-predictable architectures to support static worst-case execution time (WCET) analysis. One architectural feature, the data cache, is hard to analyze when different data areas (e.g., heap allocated and stack allocated data) share the same cache. This sharing leads to less...... precise results of the cache analysis part of the WCET analysis. Splitting the data cache for different data areas enables composable data cache analysis. The WCET analysis tool can analyze the accesses to these different data areas independently. In this paper we present the design and implementation...

  9. Detailed Electrochemical Characterisation of Large SOFC Stacks

    DEFF Research Database (Denmark)

    Mosbæk, Rasmus Rode; Hjelm, Johan; Barfod, R.


    As solid oxide fuel cell (SOFC) technology is moving closer to a commercial break through, lifetime limiting factors, determination of the limits of safe operation and methods to measure the “state-of-health” of operating cells and stacks are becoming of increasing interest. This requires applica...... out at a range of ac perturbation amplitudes in order to investigate linearity of the response and the signal-to-noise ratio. Separation of the measured impedance into series and polarisation resistances was possible....... to analyse in detail. Today one is forced to use mathematical modelling to extract information about existing gradients and cell resistances in operating stacks, as mature techniques for local probing are not available. This type of spatially resolved information is essential for model refinement...... and validation, and helps to further the technological stack development. Further, more detailed information obtained from operating stacks is essential for developing appropriate process monitoring and control protocols for stack and system developers. An experimental stack with low ohmic resistance from Topsoe...

  10. Total synthesis of haterumalides NA and NC via a chromium-mediated macrocyclization. (United States)

    Schomaker, Jennifer M; Borhan, Babak


    The syntheses of haterumalides NA and NC were accomplished via the macrocyclization of a chlorovinylidene chromium carbenoid onto a pendant aldehyde to generate the C8-C9 bond with the desired stereoisomer as the major product. Utilizing the latter chemistry enables access to both C9 hydroxylated (haterumalides NC and ND) and C9 deoxygenated forms (haterumalides NA, NB, and NE; via deoxygenation of the C9-hydroxyl).

  11. Synthesis and Photophysical Properties of Biphenyl and Terphenyl Arylene?Ethynylene Macrocycles


    Korich, Andrew L.; McBee, Ian A.; Bennion, Jonathan C.; Gifford, Jenna I.; Hughes, Thomas S.


    A series of single-walled carbon nanotube precursors, C 3h -symmetric cyclotri(ethynylene)(biphenyl-2,4?-diyl) and cyclotri(ethynylene)(p-terphenyl-2,4?-diyl), have been prepared by a linear stepwise oligomerization?cyclization route and by statistical intermolecular cyclooligomerization. In addition to producing these members of a novel class of arylene ethynylene macrocycles, 1 and 2, the latter statistical process produces the smaller cyclic dimer, cyclodi(ethynylene)(p-terphenyl-2,4?-diyl...

  12. Sceliphrolactam, a polyene macrocyclic lactam from a wasp-associated Streptomyces sp

    DEFF Research Database (Denmark)

    Oh, Dong-Chan; Poulsen, Michael; Currie, Cameron R


    A previously unreported 26-membered polyene macrocyclic lactam, sceliphrolactam, was isolated from an actinomycete, Streptomyces sp., associated with the mud dauber, Sceliphron caementarium. Sceliphrolactam's structure was determined by 1D- and 2D-NMR, MS, UV, and IR spectral analysis. Sceliphrol....... Sceliphrolactam displays antifungal activity against amphotericin B-resistant Candida albicans (MIC = 4 µg/mL, 8.3 µM)....

  13. Stability and kinetics of uranyl ion complexation by macrocycles in propylene carbonate

    International Nuclear Information System (INIS)

    Fux, P.


    A thermodynamic study of uranyl ion complexes formation with different macrocyclic ligands was realized in propylene carbonate as solvent using spectrophotometric and potentiometric techniques. Formation kinetics of two UO 2 complexes: a crown ether (18C6) and a coronand (22) was studied by spectrophotometry in propylene carbonate with addition of tetraethylammonium chlorate 0.1M at 25 0 C. Possible structures of complexes in solution are discussed [fr

  14. Synthesis and characterization of two new tetrapyrazolic macrocycles for the selective extraction of cesium cation

    Czech Academy of Sciences Publication Activity Database

    Harit, T.; Malek, F.; El Bali, B.; Dušek, Michal; Kučeráková, Monika


    Roč. 72, č. 27-28 (2016), s. 3966-3973 ISSN 0040-4020 R&D Projects: GA MŠk LO1603; GA ČR(CZ) GA14-03276S EU Projects: European Commission(XE) CZ.2.16/3.1.00/24510 Institutional support: RVO:68378271 Keywords : cesium cation * liquid–liquid extraction * macrocycle * pyrazole * crystal structure Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 2.651, year: 2016

  15. Biomechanical Assessment of Strength and Jumping Ability in Male Volleyball Players During the Annual Training Macrocycle

    Directory of Open Access Journals (Sweden)

    Czaplicki Adam


    Full Text Available Introduction. The aim of the study was to determine the changes in the peak torque of the knee extensors and flexors of the dominant lower limb, the shoulder internal and external rotators of the dominant upper limb, and the shoulder extensors and flexors of the dominant upper limb as well as the changes in jump height in volleyball players during the annual training macrocycle.

  16. Chemical and Biological Significance of Oenothein B and Related Ellagitannin Oligomers with Macrocyclic Structure

    Directory of Open Access Journals (Sweden)

    Takashi Yoshida


    Full Text Available In 1990, Okuda et al. reported the first isolation and characterization of oenothein B, a unique ellagitannin dimer with a macrocyclic structure, from the Oenothera erythrosepala leaves. Since then, a variety of macrocyclic analogs, including trimeric–heptameric oligomers have been isolated from various medicinal plants belonging to Onagraceae, Lythraceae, and Myrtaceae. Among notable in vitro and in vivo biological activities reported for oenothein B are antioxidant, anti-inflammatory, enzyme inhibitory, antitumor, antimicrobial, and immunomodulatory activities. Oenothein B and related oligomers, and/or plant extracts containing them have thus attracted increasing interest as promising targets for the development of chemopreventive agents of life-related diseases associated with oxygen stress in human health. In order to better understand the significance of this type of ellagitannin in medicinal plants, this review summarizes (1 the structural characteristics of oenothein B and related dimers; (2 the oxidative metabolites of oenothein B up to heptameric oligomers; (3 the distribution of oenotheins and other macrocyclic analogs in the plant kingdom; and (4 the pharmacological activities hitherto documented for oenothein B, including those recently found by our laboratory.

  17. Hydrolyzable tannins of tamaricaceous plants. III. Hellinoyl- and macrocyclic-type ellagitannins from Tamarix nilotica. (United States)

    Orabi, Mohamed A A; Taniguchi, Shoko; Yoshimura, Morio; Yoshida, Takashi; Kishino, Kaori; Sakagami, Hiroshi; Hatano, Tsutomu


    Three new hellinoyl-type ellagitannins, nilotinins M4 (7), D7 (8), and D8 (9), and a new macrocyclic-type, nilotinin D9 (10), together with eight known tannins, hirtellins B (2), C (11), and F (12), isohirtellin C (13), tamarixinin A (3), tellimagrandins I and II, and 1,2,6-tri-O-galloyl-beta-d-glucose (14), were isolated from an aqueous acetone extract of Tamarix nilotica dried leaves. Nilotinin M4 (7) is a monomeric tannin possessing a hellinoyl moiety. The structure of 8 demonstrated replacement of one of the HHDP groups at the glucose core O-4/O-6 in ordinary dimeric tannins with a galloyl moiety at O-6. This is a new structural feature among the tamaricaceous ellagitannins. On the basis of the results, reported spectroscopic assignments for 2, 3, and the macrocyclic tannins 11-13 were revised. Unusual shifts in the NMR spectra of these macrocyclic tannins are also discussed in relation to their conformations. Several tannins isolated from T. nilotica were assessed for possible cytotoxic activity against four human tumor cell lines, and nilotinin D8 (9) and hirtellin A (1) showed high cytotoxic effects.

  18. Insulin mimetic effects of macrocyclic binuclear oxovanadium complexes on streptozotocin-induced experimental diabetes in rats. (United States)

    Ramachandran, B; Kandaswamy, M; Narayanan, V; Subramanian, S


    The vanadium complexes so far tested for their insulin mimetic effects are either mono- or binuclear and contain only acyclic ligands. The leaching or hydrolysis of vanadyl ions from these complexes is much easier, and hence they elicit side effects. In the present study, a new binuclear macrocyclic oxovanadium complex was synthesized, and its efficacy was studied on streptozotocin (STZ)-induced diabetic rats over a period of 30 days. The insulin mimetic effect of the complex was tested on the blood sugar level in the STZ-diabetic rats and on the activities of the carbohydrate-metabolizing enzymes present in the liver. Administration of vanadium complex to STZ-induced diabetic rats decreased blood glucose levels from hyperglycaemic to normoglycaemic when compared to diabetic rats. The activity of carbohydrate-metabolizing enzymes such as hexokinase, glucose-6-phosphate dehydrogenase, glycogen synthase and glycogen content were increased to near normal in vanadium complex-administered diabetic rats. The biochemical studies such as assay of blood urea and glutamate oxaloacetate transaminases revealed that the complex is not toxic to the system. The nontoxic nature of this complex may be due to the presence of the vanadyl ions in an intact macrocyclic form. Further, the vanadyl ions present in the macrocyclic binuclear oxovanadium complex are very close to each other, and this may enhance the insulin mimetic activity by synergic effect.

  19. Macrocycle peptides delineate locked-open inhibition mechanism for microorganism phosphoglycerate mutases

    Energy Technology Data Exchange (ETDEWEB)

    Yu, Hao; Dranchak, Patricia; Li, Zhiru; MacArthur, Ryan; Munson, Matthew S.; Mehzabeen, Nurjahan; Baird, Nathan J.; Battalie, Kevin P.; Ross, David; Lovell, Scott; Carlow, Clotilde K.S.; Suga, Hiroaki; Inglese, James (U of Tokyo); (NEB); (Kansas); (NIH); (NIST); (HHMI)


    Glycolytic interconversion of phosphoglycerate isomers is catalysed in numerous pathogenic microorganisms by a cofactor-independent mutase (iPGM) structurally distinct from the mammalian cofactor-dependent (dPGM) isozyme. The iPGM active site dynamically assembles through substrate-triggered movement of phosphatase and transferase domains creating a solvent inaccessible cavity. Here we identify alternate ligand binding regions using nematode iPGM to select and enrich lariat-like ligands from an mRNA-display macrocyclic peptide library containing >1012 members. Functional analysis of the ligands, named ipglycermides, demonstrates sub-nanomolar inhibition of iPGM with complete selectivity over dPGM. The crystal structure of an iPGM macrocyclic peptide complex illuminated an allosteric, locked-open inhibition mechanism placing the cyclic peptide at the bi-domain interface. This binding mode aligns the pendant lariat cysteine thiolate for coordination with the iPGM transition metal ion cluster. The extended charged, hydrophilic binding surface interaction rationalizes the persistent challenges these enzymes have presented to small-molecule screening efforts highlighting the important roles of macrocyclic peptides in expanding chemical diversity for ligand discovery.

  20. Structural and EPR studies on single-crystal and polycrystalline samples of copper(II) and cobalt(II) complexes with N2S2-based macrocyclic ligands. (United States)

    Tamayo, Abel; Casabó, Jaume; Escriche, Lluís; González, Pablo; Lodeiro, Carlos; Rizzi, Alberto C; Brondino, Carlos D; Passeggi, M C G; Kivekäs, Raikko; Sillanpää, Reijo


    The properties of Cu(II) and Co(II) complexes with oxygen- or nitrogen-containing macrocycles have been extensively studied; however, less attention has been paid to the study of complexes containing sulfur atoms in the first coordination sphere. Herein we present the interaction between these two metal ions and two macrocyclic ligands with N2S2 donor sets. Cu(II) and Co(II) complexes with the pyridine-containing 14-membered macrocycles 3,11-dithia-7,17-diazabicyclo[11.3.1]heptadeca-1(17),13,15-triene (L) and 7-(9-anthracenylmethyl)-3,11-dithia-7,17-diazabicyclo[11.3.1]heptadeca-1(17),13,15-triene (L1) have been synthesized. The X-ray structural analysis of {[Co(ClO4)(H2O)(L)][Co(H2O)2(L)]}(ClO4)3 shows two different metal sites in octahedral coordination. The EPR spectra of powdered samples of this compound are typical of distorted six-coordinated Co(II) ions in a high-spin (S=3/2) configuration, with the ground state being S=1/2 (g1=5.20, g2=3.20, g3=1.95). The EPR spectrum of [Cu(ClO4)(L)](ClO4) was simulated assuming an axial g tensor (g1=g2=2.043, g3=2.145), while that of [Cu(ClO4)(L1)](ClO4) slightly differs from an axial symmetry (g1=2.025, g2=2.060, g3=2.155). These results are compatible with a Cu(II) ion in square-pyramidal coordination with N2S2 as basal ligands. Single-crystal EPR experiment performed on [Cu(ClO4)(L1)](ClO4) allowed determining the eigenvalues of the molecular g tensor associated with the copper site, as well as the two possible orientations for the tensor. On the basis of symmetry arguments, an assignment in which the eigenvectors are nearly along the Cu(II)-ligand bonds is chosen.

  1. Parallel β-sheet vibrational couplings revealed by 2D IR spectroscopy of an isotopically labeled macrocycle: quantitative benchmark for the interpretation of amyloid and protein infrared spectra. (United States)

    Woys, Ann Marie; Almeida, Aaron M; Wang, Lu; Chiu, Chi-Cheng; McGovern, Michael; de Pablo, Juan J; Skinner, James L; Gellman, Samuel H; Zanni, Martin T


    Infrared spectroscopy is playing an important role in the elucidation of amyloid fiber formation, but the coupling models that link spectra to structure are not well tested for parallel β-sheets. Using a synthetic macrocycle that enforces a two stranded parallel β-sheet conformation, we measured the lifetimes and frequency for six combinations of doubly (13)C═(18)O labeled amide I modes using 2D IR spectroscopy. The average vibrational lifetime of the isotope labeled residues was 550 fs. The frequencies of the labels ranged from 1585 to 1595 cm(-1), with the largest frequency shift occurring for in-register amino acids. The 2D IR spectra of the coupled isotope labels were calculated from molecular dynamics simulations of a series of macrocycle structures generated from replica exchange dynamics to fully sample the conformational distribution. The models used to simulate the spectra include through-space coupling, through-bond coupling, and local frequency shifts caused by environment electrostatics and hydrogen bonding. The calculated spectra predict the line widths and frequencies nearly quantitatively. Historically, the characteristic features of β-sheet infrared spectra have been attributed to through-space couplings such as transition dipole coupling. We find that frequency shifts of the local carbonyl groups due to nearest neighbor couplings and environmental factors are more important, while the through-space couplings dictate the spectral intensities. As a result, the characteristic absorption spectra empirically used for decades to assign parallel β-sheet secondary structure arises because of a redistribution of oscillator strength, but the through-space couplings do not themselves dramatically alter the frequency distribution of eigenstates much more than already exists in random coil structures. Moreover, solvent exposed residues have amide I bands with >20 cm(-1) line width. Narrower line widths indicate that the amide I backbone is solvent

  2. Restricting rotation of triple bond through π-stacking interactions in ...

    Indian Academy of Sciences (India)


    Photophysical properties - well understood. -monomer and excimer emission – well characterized. Applications – sensors – molecular photonics devices. Static excimer – preorganization in the ground state – π-π stacking in the GS. Dynamic excimer – interaction in the excited state after diffusional encounter. 3.4 - 3.5 A ...

  3. From Multi to Single Stack Automata (United States)

    Atig, Mohamed Faouzi

    We investigate the issue of reducing the verification problem of multi-stack machines to the one for single-stack machines. For instance, elegant (and practically efficient) algorithms for bounded-context switch analysis of multi-pushdown systems have been recently defined based on reductions to the reachability problem of (single-stack) pushdown systems [10,18]. In this paper, we extend this view to both bounded-phase visibly pushdown automata (BVMPA) [16] and ordered multi-pushdown automata (OMPA) [1] by showing that each of their emptiness problem can be reduced to the one for a class of single-stack machines. For these reductions, we introduce effective generalized pushdown automata (EGPA) where operations on stacks are (1) pop the top symbol of the stack, and (2) push a word in some (effectively) given set of words L over the stack alphabet, assuming that L is in some class of languages for which checking whether L intersects regular languages is decidable. We show that the automata-based saturation procedure for computing the set of predecessors in standard pushdown automata can be extended to prove that for EGPA too the set of all predecessors of a regular set of configurations is an effectively constructible regular set. Our reductions from OMPA and BVMPA to EGPA, together with the reachability analysis procedure for EGPA, allow to provide conceptually simple algorithms for checking the emptiness problem for each of these models, and to significantly simplify the proofs for their 2ETIME upper bounds (matching their lower-bounds).

  4. Start-Stop Test Procedures on the PEMFC Stack Level

    DEFF Research Database (Denmark)

    Mitzel, Jens; Nygaard, Frederik; Veltzé, Sune

    The test is addressed to investigate the influence on stack durability of a long stop followed by a restart of a stack. Long stop should be defined as a stop in which the anodic compartment is fully filled by air due to stack leakages. In systems, leakage level of the stack is low and time to fil...

  5. EmuStack: An OpenStack-Based DTN Network Emulation Platform (Extended Version

    Directory of Open Access Journals (Sweden)

    Haifeng Li


    Full Text Available With the advancement of computing and network virtualization technology, the networking research community shows great interest in network emulation. Compared with network simulation, network emulation can provide more relevant and comprehensive details. In this paper, EmuStack, a large-scale real-time emulation platform for Delay Tolerant Network (DTN, is proposed. EmuStack aims at empowering network emulation to become as simple as network simulation. Based on OpenStack, distributed synchronous emulation modules are developed to enable EmuStack to implement synchronous and dynamic, precise, and real-time network emulation. Meanwhile, the lightweight approach of using Docker container technology and network namespaces allows EmuStack to support a (up to hundreds of nodes large-scale topology with only several physical nodes. In addition, EmuStack integrates the Linux Traffic Control (TC tools with OpenStack for managing and emulating the virtual link characteristics which include variable bandwidth, delay, loss, jitter, reordering, and duplication. Finally, experiences with our initial implementation suggest the ability to run and debug experimental network protocol in real time. EmuStack environment would bring qualitative change in network research works.

  6. Levitation characteristics of HTS tape stacks

    Energy Technology Data Exchange (ETDEWEB)

    Pokrovskiy, S. V.; Ermolaev, Y. S.; Rudnev, I. A. [National Research Nuclear University MEPhI (Moscow Engineering Physics Institute), Moscow (Russian Federation)


    Due to the considerable development of the technology of second generation high-temperature superconductors and a significant improvement in their mechanical and transport properties in the last few years it is possible to use HTS tapes in the magnetic levitation systems. The advantages of tapes on a metal substrate as compared with bulk YBCO material primarily in the strength, and the possibility of optimizing the convenience of manufacturing elements of levitation systems. In the present report presents the results of the magnetic levitation force measurements between the stack of HTS tapes containing of tapes and NdFeB permanent magnet in the FC and ZFC regimes. It was found a non- linear dependence of the levitation force from the height of the array of stack in both modes: linear growth at small thickness gives way to flattening and constant at large number of tapes in the stack. Established that the levitation force of stacks comparable to that of bulk samples. The numerical calculations using finite element method showed that without the screening of the applied field the levitation force of the bulk superconductor and the layered superconductor stack with a critical current of tapes increased by the filling factor is exactly the same, and taking into account the screening force slightly different.

  7. Forced Air-Breathing PEMFC Stacks

    Directory of Open Access Journals (Sweden)

    K. S. Dhathathreyan


    Full Text Available Air-breathing fuel cells have a great potential as power sources for various electronic devices. They differ from conventional fuel cells in which the cells take up oxygen from ambient air by active or passive methods. The air flow occurs through the channels due to concentration and temperature gradient between the cell and the ambient conditions. However developing a stack is very difficult as the individual cell performance may not be uniform. In order to make such a system more realistic, an open-cathode forced air-breathing stacks were developed by making appropriate channel dimensions for the air flow for uniform performance in a stack. At CFCT-ARCI (Centre for Fuel Cell Technology-ARC International we have developed forced air-breathing fuel cell stacks with varying capacity ranging from 50 watts to 1500 watts. The performance of the stack was analysed based on the air flow, humidity, stability, and so forth, The major advantage of the system is the reduced number of bipolar plates and thereby reduction in volume and weight. However, the thermal management is a challenge due to the non-availability of sufficient air flow to remove the heat from the system during continuous operation. These results will be discussed in this paper.

  8. Contemporary sample stacking in analytical electrophoresis. (United States)

    Malá, Zdena; Šlampová, Andrea; Křivánková, Ludmila; Gebauer, Petr; Boček, Petr


    This contribution is a methodological review of the publications about the topic from the last 2 years. Therefore, it is primarily organized according to the methods and procedures used in surveyed papers and the origin and type of sample and specification of analytes form the secondary structure. The introductory part about navigation in the architecture of stacking brings a brief characterization of the various stacking methods, with the description of mutual links to each other and important differences among them. The main body of the article brings a survey of publications organized according to main principles of stacking and then according to the origin and type of the sample. Provided that the paper cited gave explicitly the relevant data, information about the BGE(s) used, procedure, detector employed, and reached LOD and/or concentration effect is given. The papers where the procedure used is a combination of diverse fragments and parts of various stacking techniques are mentioned in a special section on combined techniques. The concluding remarks in the final part of the review evaluate present state of art and the trends of sample stacking in CE. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Enhanced dynamical stability with harmonic slip stacking

    Directory of Open Access Journals (Sweden)

    Jeffrey Eldred


    Full Text Available We develop a configuration of radio-frequency (rf cavities to dramatically improve the performance of slip stacking. Slip stacking is an accumulation technique used at Fermilab to nearly double proton intensity by maintaining two beams of different momenta in the same storage ring. The two particle beams are longitudinally focused in the Recycler by two 53 MHz 100 kV rf cavities with a small frequency difference between them. We propose an additional 106 MHz 20 kV rf cavity with a frequency at the double the average of the upper and lower main rf frequencies. We show the harmonic rf cavity cancels out the resonances generated between the two main rf cavities and we derive the relationship between the harmonic rf voltage and the main rf voltage. We find the area factors that can be used to calculate the available phase space area for any set of beam parameters without individual simulation. We establish Booster beam quality requirements to achieve 99% slip stacking efficiency. We measure the longitudinal distribution of the Booster beam and use it to generate a realistic beam model for slip stacking simulation. We demonstrate that the harmonic rf cavity can not only reduce particle loss during slip stacking, but also reduce the final longitudinal emittance.

  10. Long-Range Charge Transport in Adenine-Stacked RNA:DNA Hybrids. (United States)

    Li, Yuanhui; Artés, Juan M; Hihath, Joshua


    An extremely important biological component, RNA:DNA can also be used to design nanoscale structures such as molecular wires. The conductance of single adenine-stacked RNA:DNA hybrids is rapidly and reproducibly measured using the break junction approach. The conductance decreases slightly over a large range of molecular lengths, suggesting that RNA:DNA can be used as an oligonucleotide wire. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Macrocyclic θ-defensins suppress tumor necrosis factor-α (TNF-α) shedding by inhibition of TNF-α-converting enzyme. (United States)

    Schaal, Justin B; Maretzky, Thorsten; Tran, Dat Q; Tran, Patti A; Tongaonkar, Prasad; Blobel, Carl P; Ouellette, André J; Selsted, Michael E


    Theta-defensins (θ-defensins) are macrocyclic peptides expressed exclusively in granulocytes and selected epithelia of Old World monkeys. They contribute to anti-pathogen host defense responses by directly killing a diverse range of microbes. Of note, θ-defensins also modulate microbe-induced inflammation by affecting the production of soluble tumor necrosis factor (sTNF) and other proinflammatory cytokines. Here, we report that natural rhesus macaque θ-defensin (RTD) isoforms regulate sTNF cellular release by inhibiting TNF-α-converting enzyme (TACE; also known as a d isintegrin a nd m etalloprotease 17; ADAM17), the primary pro-TNF sheddase. Dose-dependent inhibition of cellular TACE activity by RTDs occurred when leukocytes were stimulated with live Escherichia coli cells as well as numerous Toll-like receptor agonists. Moreover, the relative inhibitory potencies of the RTD isoforms strongly correlated with their suppression of TNF release by stimulated blood leukocytes and THP-1 monocytes. RTD isoforms also inhibited ADAM10, a sheddase closely related to TACE. TACE inhibition was abrogated by introducing a single opening in the RTD-1 backbone, demonstrating that the intact macrocycle is required for enzyme inhibition. Enzymologic analyses showed that RTD-1 is a fast binding, reversible, non-competitive inhibitor of TACE. We conclude that θ-defensin-mediated inhibition of pro-TNF proteolysis by TACE represents a rapid mechanism for the regulation of sTNF and TNF-dependent inflammatory pathways. Molecules with structural and functional features mimicking those of θ-defensins may have clinical utility as TACE inhibitors for managing TNF-driven diseases. © 2018 by The American Society for Biochemistry and Molecular Biology, Inc.

  12. A Macrocyclic Peptide that Serves as a Cocrystallization Ligand and Inhibits the Function of a MATE Family Transporter

    Directory of Open Access Journals (Sweden)

    Hiroaki Suga


    Full Text Available The random non-standard peptide integrated discovery (RaPID system has proven to be a powerful approach to discover de novo natural product-like macrocyclic peptides that inhibit protein functions. We have recently reported three macrocyclic peptides that bind to Pyrococcus furiosus multidrug and toxic compound extrusion (PfMATE transporter and inhibit the transport function. Moreover, these macrocyclic peptides were successfully employed as cocrystallization ligands of selenomethionine-labeled PfMATE. In this report, we disclose the details of the RaPID selection strategy that led to the identification of these three macrocyclic peptides as well as a fourth macrocyclic peptide, MaD8, which is exclusively discussed in this article. MaD8 was found to bind within the cleft of PfMATE’s extracellular side and blocked the path of organic small molecules being extruded. The results of an ethidium bromide efflux assay confirmed the efflux inhibitory activity of MaD8, whose behavior was similar to that of previously reported MaD5.

  13. Progress of MCFC stack technology at Toshiba

    Energy Technology Data Exchange (ETDEWEB)

    Hori, M.; Hayashi, T.; Shimizu, Y. [Toshiba Corp., Tokyo (Japan)


    Toshiba is working on the development of MCFC stack technology; improvement of cell characteristics, and establishment of separator technology. For the cell technology, Toshiba has concentrated on both the restraints of NiO cathode dissolution and electrolyte loss from cells, which are the critical issues to extend cell life in MCFC, and great progress has been made. On the other hand, recognizing that the separator is one of key elements in accomplishing reliable and cost-competitive MCFC stacks, Toshiba has been accelerating the technology establishment and verification of an advanced type separator. A sub-scale stack with such a separator was provided for an electric generating test, and has been operated for more than 10,000 hours. This paper presents several topics obtained through the technical activities in the MCFC field at Toshiba.

  14. Peptide Macrocycles Featuring a Backbone Secondary Amine: A Convenient Strategy for the Synthesis of Lipidated Cyclic and Bicyclic Peptides on Solid Support

    DEFF Research Database (Denmark)

    Oddo, Alberto; Münzker, Lena; Hansen, Paul Robert


    A convenient strategy for the on-resin synthesis of macrocyclic peptides (3- to 13-mers) via intramolecular halide substitution by a diamino acid is described. The method is compatible with standard Fmoc/tBu SPPS and affords a tail-to-side-chain macrocyclic peptide featuring an endocyclic secondary...

  15. Design Handbook for a Stack Foundation


    Tuominen, Vilma


    This thesis was made for Citec Engineering Oy Ab as a handbook and as a design tool for concrete structure designers. Handbook is about the Wärtsilä Power Plant stack structure, which is a base for about 40 meters high stack pipe. The purpose is to make a calculation base to support the design work, which helps the designer to check the right dimensions of the structure. Thesis is about to be for the concrete designers and also other designers and authorities. As an example I have used an...

  16. Simple model of stacking-fault energies

    DEFF Research Database (Denmark)

    Stokbro, Kurt; Jacobsen, Lærke Wedel


    A simple model for the energetics of stacking faults in fcc metals is constructed. The model contains third-nearest-neighbor pairwise interactions and a term involving the fourth moment of the electronic density of states. The model is in excellent agreement with recently published local-density ......A simple model for the energetics of stacking faults in fcc metals is constructed. The model contains third-nearest-neighbor pairwise interactions and a term involving the fourth moment of the electronic density of states. The model is in excellent agreement with recently published local...

  17. Use of tetraaza-macrocycles for complexation of actinides in aqueous solutions. Validation of the process for the treatment of waste waters

    International Nuclear Information System (INIS)

    Chollet, Herve


    This report makes one's contribution to the study of the reactivity of free or fixed tetraaza-macrocycles. The major interest of this work concerns the following key-points: - Synthesis, spectral characterization and X-ray diffraction study of tetraaza-macrocycles N-tetra-functionalized, - Synthesis, physicochemical, chemicals and X-ray studies of macrocyclic complex in lanthanides and actinides series, - Synthesis and characterization of tetraaza-macrocycles grafted on organic and inorganic polymers, - Reactivity of macrocyclic ligands grafted on Merrifield's resin or silica gel in cerium, europium, uranium, plutonium and americium series, - Extraction of heavy metals in a solid-liquid process and measurements of a pilot. (author) [fr

  18. Contemporary sample stacking in analytical electrophoresis

    Czech Academy of Sciences Publication Activity Database

    Šlampová, Andrea; Malá, Zdeňka; Pantůčková, Pavla; Gebauer, Petr; Boček, Petr


    Roč. 34, č. 1 (2013), s. 3-18 ISSN 0173-0835 R&D Projects: GA ČR GAP206/10/1219 Institutional support: RVO:68081715 Keywords : biological samples * stacking * trace analysis * zone electrophoresis Subject RIV: CB - Analytical Chemistry, Separation Impact factor: 3.161, year: 2013

  19. SRS reactor stack plume marking tests

    International Nuclear Information System (INIS)

    Petry, S.F.


    Tests performed in 105-K in 1987 and 1988 demonstrated that the stack plume can successfully be made visible (i.e., marked) by introducing smoke into the stack breech. The ultimate objective of these tests is to provide a means during an emergency evacuation so that an evacuee can readily identify the stack plume and evacuate in the opposite direction, thus minimizing the potential of severe radiation exposure. The EPA has also requested DOE to arrange for more tests to settle a technical question involving the correct calculation of stack downwash. New test canisters were received in 1988 designed to produce more smoke per unit time; however, these canisters have not been evaluated, because normal ventilation conditions have not been reestablished in K Area. Meanwhile, both the authorization and procedure to conduct the tests have expired. The tests can be performed during normal reactor operation. It is recommended that appropriate authorization and procedure approval be obtained to resume testing after K Area restart

  20. Testing of Electrodes, Cells and Short Stacks

    DEFF Research Database (Denmark)

    Hauch, Anne; Mogensen, Mogens Bjerg


    The present contribution describes the electrochemical testing and characterization of electrodes, cells, and short stacks. To achieve the maximum insight and results from testing of electrodes and cells, it is obviously necessary to have a good understanding of the fundamental principles...

  1. Stack Gas Scrubber Makes the Grade (United States)

    Chemical and Engineering News, 1975


    Describes a year long test of successful sulfur dioxide removal from stack gas with a calcium oxide slurry. Sludge disposal problems are discussed. Cost is estimated at 0.6 mill per kwh not including sludge removal. A flow diagram and equations are included. (GH)

  2. OpenStack Object Storage (Swift) essentials

    CERN Document Server

    Kapadia, Amar; Varma, Sreedhar


    If you are an IT administrator and you want to enter the world of cloud storage using OpenStack Swift, then this book is ideal for you. Basic knowledge of Linux and server technology is beneficial to get the most out of the book.

  3. Stacked spheres and lower bound theorem

    Indian Academy of Sciences (India)



    Nov 20, 2011 ... Preliminaries. Lower bound theorem. On going work. Definitions. An n-simplex is a convex hull of n + 1 affinely independent points. (called vertices) in some Euclidean space R. N . Stacked spheres and lower bound theorem. Basudeb Datta. Indian Institute of Science. 2 / 27 ...

  4. Contemporary sample stacking in analytical electrophoresis

    Czech Academy of Sciences Publication Activity Database

    Malá, Zdeňka; Šlampová, Andrea; Křivánková, Ludmila; Gebauer, Petr; Boček, Petr


    Roč. 36, č. 1 (2015), s. 15-35 ISSN 0173-0835 R&D Projects: GA ČR(CZ) GA13-05762S Institutional support: RVO:68081715 Keywords : biological samples * stacking * trace analysis * zone electrophoresis Subject RIV: CB - Analytical Chemistry, Separation Impact factor: 2.482, year: 2015

  5. The data type variety of stack algebras

    NARCIS (Netherlands)

    Bergstra, J.A.; Tucker, J.V.


    We define and study the class of all stack algebras as the class of all minimal algebras in a variety defined by an infinite recursively enumerable set of equations. Among a number of results, we show that the initial model of the variety is computable, that its equational theory is decidable,

  6. Photoswitchable Intramolecular H-Stacking of Perylenebisimide

    NARCIS (Netherlands)

    Wang, Jiaobing; Kulago, Artem; Browne, Wesley R.; Feringa, Ben L.


    Dynamic control over the formation of H- or J-type aggregates of chromophores is of fundamental importance for developing responsive organic optoelectronic materials. In this study, the first example of photoswitching between a nonstacked and an intramolecularly H-stacked arrangement of

  7. 40 CFR 61.53 - Stack sampling. (United States)


    ... 40 Protection of Environment 8 2010-07-01 2010-07-01 false Stack sampling. 61.53 Section 61.53 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS (CONTINUED) NATIONAL... sampling. (a) Mercury ore processing facility. (1) Unless a waiver of emission testing is obtained under...

  8. 40 CFR 61.33 - Stack sampling. (United States)


    ... 40 Protection of Environment 8 2010-07-01 2010-07-01 false Stack sampling. 61.33 Section 61.33 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS (CONTINUED) NATIONAL... sampling. (a) Unless a waiver of emission testing is obtained under § 61.13, each owner or operator...

  9. OpenStack cloud computing cookbook

    CERN Document Server

    Jackson, Kevin


    A Cookbook full of practical and applicable recipes that will enable you to use the full capabilities of OpenStack like never before.This book is aimed at system administrators and technical architects moving from a virtualized environment to cloud environments with familiarity of cloud computing platforms. Knowledge of virtualization and managing linux environments is expected.

  10. The Synthesis, Structures and Chemical Properties of Macrocyclic Ligands Covalently Bonded into Layered Arrays

    International Nuclear Information System (INIS)

    Clearfield, Abraham


    OAK-B135 The immobilization of crown ethers tends to limit the leveling effect of solvents making the macrocycles more selective. In addition immobilization has the added advantage of relative ease of recovery of the otherwise soluble crown. We have affixed CH2PO3H2 groups to azacrown ethers. The resultant phosphorylated macrocycles may spontaneously aggregate into crystalline supramolecular linear arrays or contacted with cations produce layered or linear polymers. In the linear polymers the metal and phosphonic acids covalently bond into a central stem with the macrocyclic rings protruding from the stem as leaves on a twig. Two types of layered compounds were obtained with group 4 metals. Monoaza-crown ethers form a bilayer where the M4+ plus phosphonic acid groups build the layer and the rings fill the interlayer space. 1, 10-diazadiphosphonic acids cross-link the metal phosphonate layers forming a three-dimensional array of crown ethers. In order to improve diffusion into these 3-D arrays they are spaced by inclusion of phosphate or phosphate groups. Two series of azamacrocylic crown ethers were prepared containing rings with 20 to 32 atoms. These larger rings can complex two cations per ring. Methylene phosphonic acid groups have been bonded to the aza ring atoms to increase the complexing ability of these ligands. Our approach is to carry out acid-base titrations in the absence and presence of cations to determine the pKa values of the protons, both those bonded to aza groups and those associated with the phosphonic acid groups. From the differences in the titration curves obtained with and without the cations present we obtain the stoichiometry of complex formation and the complex stability constants. Some of the applications we are targeting include phase transfer catalysis, separation of cations and the separation of radioisotopes for diagnostic and cancer therapeutic purposes

  11. Immobilized copper(II) macrocyclic complex on MWCNTs with antibacterial activity

    Energy Technology Data Exchange (ETDEWEB)

    Tarlani, Aliakbar, E-mail: [Inorganic Nanostructures and Catalysts Research Lab., Chemistry & Chemical Engineering Research Center of Iran, Pajoohesh Blvd., km 17, Karaj Hwy, Tehran 14968-13151 (Iran, Islamic Republic of); Narimani, Khashayar [Inorganic Nanostructures and Catalysts Research Lab., Chemistry & Chemical Engineering Research Center of Iran, Pajoohesh Blvd., km 17, Karaj Hwy, Tehran 14968-13151 (Iran, Islamic Republic of); Mohammadipanah, Fatemeh; Hamedi, Javad [Department of Microbial Biotechnology, School of Biology and Center of Excellence in Phylogeny of Living Organisms, College of Science, University of Tehran, Tehran 14155-6455 (Iran, Islamic Republic of); University of Tehran Biocompound Collection (UTBC), Microbial Technology and Products Research Center, University of Tehran, Tehran (Iran, Islamic Republic of); Tahermansouri, Hasan [Department of Chemistry, Ayatollah Amoli Branch, Islamic Azad University, Amol (Iran, Islamic Republic of); Amini, Mostafa M. [Department of Chemistry, Shahid Behshti University, 1983963113, Tehran (Iran, Islamic Republic of)


    Graphical abstract: In an antibacterial test, grafted copper(II) macrocyclic complex on the surface of MWCNT showed higher antibacterial activity against Bacillus subtilis compared to the individual MWCNT-COOH and the complex. - Highlights: • Copper(II) tetraaza macrocyclic complex covalently bonded to modified MWCNT. • Grafting of the complex carried out via an interaction between −C(=O)Cl group and NH of the ligand. • The samples were subjected in an antibacterial assessment to compare their activity. • Immobilized complex showed higher antibacterial activity against Bacillus subtilis ATCC 6633 compared to separately MWCNT-C(C=O)-OH and CuTAM. - Abstract: In a new approach, a copper(II) tetraaza macrocyclic complex (CuTAM) was covalently bonded on modified multi-walled carbon nanotubes (MWCNTs). To achieve this purpose, MWCNTs were converted to MWCNT-COCl and then reacted to NH groups of TAM ligand. The prepared material was characterized by Fourier Transform Infrared (FT-IR), X-ray diffraction (XRD), Raman spectroscopy, thermal gravimetric analysis (TGA), and FESEM (field emission scanning electron microscopy). FT-IR and TGA demonstrated the presence of the organic moieties, and XRD proved that the structure of MWCNTs remained intact during the three modification steps. An increase in the I{sub D}/I{sub G} ratio in Raman spectra confirmed the surface modifications. Finally, the samples were subjected to an antibacterial assessment to compare their biological activity. The antibacterial test showed that the grafted complex on the surface of the nanotube (MWCNT-CO-CuTAM) has higher antibacterial activity against Bacillus subtilis ATCC 6633 than the MWCNT-COOH and CuTAM with 1000 and 2000 μg/mL.

  12. Stacking fault tetrahedron induced plasticity in copper single crystal

    International Nuclear Information System (INIS)

    Zhang, Liang; Lu, Cheng; Tieu, Kiet; Su, Lihong; Zhao, Xing; Pei, Linqing


    Stacking fault tetrahedron (SFT) is the most common type of vacancy clustered defects in fcc metals and alloys, and can play an important role in the mechanical properties of metallic materials. In this study, molecular dynamics (MD) simulations were carried out to investigate the incipience of plasticity and the underlying atomic mechanisms in copper single crystals with SFT. Different deformation mechanisms of SFT were reported due to the crystal orientations and loading directions (compression and tension). The results showed that the incipient plasticity in crystals with SFT resulted from the heterogeneous dislocation nucleation from SFT, so the stress required for plastic deformation was less than that needed for perfect single crystals. Three crystal orientations ([1 0 0], [1 1 0] and [1 1 1]) were specified in this study because they can represent most of the typical deformation mechanisms of SFT. MD simulations revealed that the structural transformation of SFT was frequent under the applied loading; a metastable SFT structure and the collapse of SFT were usually observed. The structural transformation resulted in a different reduction of yield stress in compression and tension, and also caused a decreased or reversed compression/tension asymmetry. Compressive stress can result in the unfaulting of Frank loop in some crystal orientations. According to the elastic theory of dislocation, the process of unfaulting was closely related to the size of the dislocation loop and the stacking fault energy.

  13. Kinetic Analysis for Macrocyclizations Involving Anionic Template at the Transition State

    Directory of Open Access Journals (Sweden)

    Vicente Martí-Centelles


    competitive oligomerization/polymerization processes yielding undesired oligomeric/polymeric byproducts. The effect of anions has also been included in the kinetic models, as they can act as catalytic templates in the transition state reducing and stabilizing the transition state. The corresponding differential equation systems for each kinetic model can be solved numerically. Through a comprehensive analysis of these results, it is possible to obtain a better understanding of the different parameters that are involved in the macrocyclization reaction mechanism and to develop strategies for the optimization of the desired processes.

  14. Neighbor-directed histidine N(τ) alkylation. A route to imidazolium-containing phosphopeptide macrocycles

    Energy Technology Data Exchange (ETDEWEB)

    Qian, Wen-Jian [National Cancer Inst., Frederick, MD (United States); Park, Jung-Eun [National Cancer Inst., Bethesda, MD (United States); Grant, Robert [Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States); Lai, Christopher C. [National Cancer Inst., Frederick, MD (United States); Kelley, James A. [National Cancer Inst., Frederick, MD (United States); Yaffe, Michael B. [Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States); Lee, Kyung S. [National Cancer Inst., Bethesda, MD (United States); Burke, Terrence R. [National Cancer Inst., Frederick, MD (United States)


    Our recently discovered, selective, on-resin route to N(τ)-alkylated imidazolium-containing histidine residues affords new strategies for peptide mimetic design. In this, we demonstrate the use of this chemistry to prepare a series of macrocyclic phosphopeptides, in which imidazolium groups serve as ring-forming junctions. These cationic moieties subsequently serve to charge-mask the phosphoamino acid group that directed their formation. Furthermore, neighbor-directed histidine N(τ)-alkylation opens the door to new families of phosphopeptidomimetics for use in a range of chemical biology contexts.

  15. Crystal Structures, Properties and Reactivity of Selected Macrocyclic and Chelate Complexes of Ni(II)


    Churchard, Andrew James


    In this dissertation we describe the structure, properties and decomposition reactions of a series of Ni(II) coordination complexes formed from reaction of the appropriate macrocyclic or chelating ligand with a simple nickel salt. The ligands used were 12aneS4 (1,4,7,10-tetrathiacyclododecane), 14aneS4 (1,4,8,11-tetrathiacyclotetradecane), cyclam (1,4,8,11-tetraazacyclotetradecane), dppe (1,2- (diphenylphosphino)ethane), and PP3 (tris-(2-(diphenylphosphino)ethyl)phosphine). The wo...

  16. Biomechanical Assessment of the Strength of Volleyball Players in Different Stages of the Training Macrocycle

    Directory of Open Access Journals (Sweden)

    Śliwa Marcin


    Full Text Available Introduction. In order to help volleyball players achieve superior results, their coaches are constantly seeking new training methods. One of the methods used to improve the effectiveness of the training that is being implemented is conducting tests which make it possible to assess the player’s locomotor system in terms of its motor and biomechanical functions. The aim of the study was to determine the torque of the knee flexor and extensor muscles of volleyball players in three stages of the annual macrocycle.

  17. Potent toxic macrocyclic trichothecenes from the marine-derived fungus Myrothecium verrucaria Hmp-F73. (United States)

    Zhao, Li; Liu, Li; Wang, Nan; Wang, Shu-Jin; Hu, Jing-Chun; Gao, Jin-Ming


    Activity-guided fractionation of a methanol extract from the culture broth of Myrothecium verrucaria Hmp-F73, a fungus associated with the sponge Hymeniacidon perleve, afforded six macrocyclic trichothecenes, verrucarin J (1), 8-hydroxyverrucarin J (2), verrucarin A (3), 8-acetoxyroridin H (4), isororidin E (5), and roridin E (6), along with trichoverrin B (7). All seven metabolites displayed potent toxicity to the brine shrimp (Artemia salina). In addition, compounds 2, 3, and 6 showed weak phytotoxic activities against lettuce seeds. A preliminary structure-activity relationship of the metabolites is also discussed.

  18. Application of Calixarenes as Macrocyclic Ligands for Uranium(VI: A Review

    Directory of Open Access Journals (Sweden)

    Katarzyna Kiegiel


    Full Text Available Calixarenes represent a well-known family of macrocyclic molecules with broad range of potential applications in chemical, analytical, and engineering materials fields. This paper covers the use of calixarenes as complexing agents for uranium(VI. The high effectiveness of calix[6]arenes in comparison to other calixarenes in uranium(VI separation process is also presented. Processes such as liquid-liquid extraction (LLE, liquid membrane (LM separation, and ion exchange are considered as potential fields for application of calixarenes as useful agents for binding UO22+ for effective separation from aqueous solutions containing other metal components.

  19. Cyclooctane metathesis catalyzed by silica-supported tungsten pentamethyl [(ΞSiO)W(Me)5]: Distribution of macrocyclic alkanes

    KAUST Repository

    Riache, Nassima


    Metathesis of cyclic alkanes catalyzed by the new surface complex [(ΞSiO)W(Me)5] affords a wide distribution of cyclic and macrocyclic alkanes. The major products with the formula CnH2n are the result of either a ring contraction or ring expansion of cyclooctane leading to lower unsubstituted cyclic alkanes (5≤n≤7) and to an unprecedented distribution of unsubstituted macrocyclic alkanes (12≤n≤40), respectively, identified by GC/MS and by NMR spectroscopies.

  20. Project W-420 Stack Monitoring system upgrades conceptual design report

    Energy Technology Data Exchange (ETDEWEB)

    TUCK, J.A.


    This document describes the scope, justification, conceptual design, and performance of Project W-420 stack monitoring system upgrades on six NESHAP-designated, Hanford Tank Farms ventilation exhaust stacks.

  1. Heuristic Solution Approaches to the Double TSP with Multiple Stacks

    DEFF Research Database (Denmark)

    Petersen, Hanne Løhmann

    This paper introduces the Double Travelling Salesman Problem with Multiple Stacks and presents a three different metaheuristic approaches to its solution. The Double Travelling Salesman Problem with Multiple Stacks is concerned with finding the shortest route performing pickups and deliveries...

  2. Heuristic Solution Approaches to the Double TSP with Multiple Stacks

    DEFF Research Database (Denmark)

    Petersen, Hanne Løhmann


    This paper introduces the Double Travelling Salesman Problem with Multiple Stacks and presents a three different metaheuristic approaches to its solution. The Double Travelling Salesman Problem with Multiple Stacks is concerned with finding the shortest route performing pickups and deliveries...

  3. DEVS Models of Palletized Ground Stacking in Storeyed Grain Warehouse

    Directory of Open Access Journals (Sweden)

    Hou Shu-Yi


    Full Text Available Processed grain stored in storeyed warehouse is generally stacked on the ground without pallets. However, in order to improve the storing way, we developed a new stacking method, palletized ground stacking. Simulation should be used to present this new storing way. DEVS provides a formalized way to describe the system model. In this paper, DEVS models of palletized ground stacking in storeyed grain warehouse are given and a simulation model is developed by AutoMod.

  4. 14-Methylpentadecano-15-lactone (muscolide): a new macrocyclic lactone from the oil of Angelica archangelica L. (United States)

    Lopes, Daíse; Strobl, Herbert; Kolodziejczyk, Paul


    The chemical composition of seed and root oils from Angelica archangelica L. was investigated. Analyses were performed by GC/MS and GC using two columns of different polarities (polyethylene glycol (DB-Wax) and 5% phenyl/95% polydimethylsiloxane (HP-5)), for the separation of several co-eluting components. A total of 58 compounds were identified, accounting for 96.3% (seed) and 93.5% (root) of the oils, respectively. A high content of beta-phellandrene (74.7%) was found in Angelica seed oil. Root oil contained a larger amount of macrocyclic lactones (1.3%) in comparison to the seed oil (0.4%). Different harvest dates produced only slight changes in the root-oil composition. In root oil harvested in summer, the beta-phellandrene content increased by ca. 36%, but no significant changes in the relative compositions of other components were observed. Fresh root oils were collected in five fractions (constant time intervals) during steam distillation (see Table). The highest-boiling fraction contained 9.3% of macrocyclic lactones such as tridecano-13-lactone (5.0%), 12-methyltridecano-13-lactone (0.4%), tetradecano-14-lactone (0.1%), pentadecano-15-lactone (3.5%), 14-methylpentadecano-15-lactone (1; trace), hexadecano-16-lactone (trace), and heptadecano-17-lactone (0.2%). This is the first report of the occurrence of 14-methylpentadecano-15-lactone (muscolide; 1) in a natural product.

  5. Response of Critical Speed to Different Macrocycle Phases during Linear Periodization on Young Swimmers

    Directory of Open Access Journals (Sweden)

    João Bartholomeu NETO


    Full Text Available Sport training programs to young swimmers have to aggregate different physical stimulus to collaborate with overall physical development, which can lead to reach best results in competitions. Linear periodization seems to be a powerful tool that allow the organization of these stimulus. However, this model has been not studied. Regarding physical capacities, aerobic fitness is inversely related with fatigue and exercise performance. Although aerobic capacity evaluation used to be expensive, critical speed (CS is easy and non - expensive tool capable to make this measurement. Thus, the aim of this study was evaluate the effects of linear periodization in CS on well - trained young swimmers. Sixteen athletes (age: 14.06  1.22 years, height: 163.52  10.99 cm, weight: 57.4  12.7 kg, body mass index: 21.24  37; 7 ♀, were underwent to a linear macrocycle training with 23 weeks divided in four mesocycles: general endurance (i.e., 4 weeks, specific endurance (i.e., 8 weeks, competitive (i.e., 7 weeks and taper (i.e., 4 weeks. Results showed significantly improve on CS after competitive and taper mesocycle phases, which was composed by higher training intensity in comparison with other macrocycle phases. Therefore, the results of the present study indicate a collaboration of mesocycle intensity on the cumulative effects of linear periodization in CS improve on young swimmers.

  6. Thermal stability of antiparasitic macrocyclic lactones milk residues during industrial processing. (United States)

    Imperiale, F A; Farias, C; Pis, A; Sallovitz, J M; Lifschitz, A; Lanusse, C


    The chemical stability of residues of different antiparasitic macrocyclic lactone compounds in milk subjected to thermal treatment was assessed. Concentrations of ivermectin (IVM), moxidectin (MXD) and eprinomectin (EPM) in sheep milk, equivalent to those measured in vivo in milk excretion studies, were subjected to 65 degrees C over 30 min or to 75 degrees C for 15 s. Residue concentrations of IVM, MXD and EPM in milk were measured by high-performance liquid chromatography (HPLC) (fluorescence detection) before and after heat treatment of the drug-fortified milk samples. No evidence of chemical loss was obtained in either of the thermal treatments under evaluation. The stability of the parent compounds in milk was evidenced by the lack of bioconversion products (metabolites) after both thermal treatments. Only very minor changes on drug concentrations were observed at the end of the treatments, which fell within the limits of the variation of the validated analytical method. In conclusion, residue concentrations of macrocyclic lactones are unaffected by industrial-simulated milk thermal procedures. Based on the reported findings, it can be postulated that residue concentrations of IVM, MXD and EPM measured in raw sheep milk may be used to estimate consumer exposure and dietary intake for these veterinary drugs.

  7. Sport stacking motor intervention programme for children with ...

    African Journals Online (AJOL)

    The purpose of this study was to explore sport stacking as an alternative intervention approach with typically developing children and in addition to improve DCD. Sport stacking consists of participants stacking and unstacking 12 specially designed plastic cups in predetermined sequences in as little time as possible.

  8. Notes on G-theory of Deligne-Mumford stacks


    Toen, B.


    Based on the methods used by the author to prove the Riemann-Roch formula for algebraic stacks, this paper contains a description of the rationnal G-theory of Deligne-Mumford stacks over general bases. We will use these results to study equivariant K-theory, and also to define new filtrations on K-theory of algebraic stacks.

  9. Learning algorithms for stack filter classifiers

    Energy Technology Data Exchange (ETDEWEB)

    Porter, Reid B [Los Alamos National Laboratory; Hush, Don [Los Alamos National Laboratory; Zimmer, Beate G [TEXAS A& M


    Stack Filters define a large class of increasing filter that is used widely in image and signal processing. The motivations for using an increasing filter instead of an unconstrained filter have been described as: (1) fast and efficient implementation, (2) the relationship to mathematical morphology and (3) more precise estimation with finite sample data. This last motivation is related to methods developed in machine learning and the relationship was explored in an earlier paper. In this paper we investigate this relationship by applying Stack Filters directly to classification problems. This provides a new perspective on how monotonicity constraints can help control estimation and approximation errors, and also suggests several new learning algorithms for Boolean function classifiers when they are applied to real-valued inputs.

  10. Industrial stacks design; Diseno de chimeneas industriales

    Energy Technology Data Exchange (ETDEWEB)

    Cacheux, Luis [Instituto de Investigaciones Electricas, Cuernavaca (Mexico)


    The Instituto de Investigaciones Electricas (IIE) though its Civil Works Department, develops, under contract with CFE`s Gerencia de Proyectos Termoelectricos (Management of Fossil Power Plant Projects), a series of methods for the design of stacks, which pretends to solve the a present day problem: the stack design of the fossil power plants that will go into operation during the next coming years in the country. [Espanol] El Instituto de Investigaciones Electricas (IIE), a traves del Departamento de Ingenieria Civil, desarrolla, bajo contrato con la Gerencia de Proyectos Termoelectricos, de la Comision Federal de Electricidad (CFE), un conjunto de metodos para el diseno de chimeneas, con el que se pretende resolver un problema inmediato: el diseno de las chimeneas de las centrales termoelectricas que entraran en operacion durante los proximos anos, en el pais.

  11. Annular feed air breathing fuel cell stack (United States)

    Wilson, Mahlon S.


    A stack of polymer electrolyte fuel cells is formed from a plurality of unit cells where each unit cell includes fuel cell components defining a periphery and distributed along a common axis, where the fuel cell components include a polymer electrolyte membrane, an anode and a cathode contacting opposite sides of the membrane, and fuel and oxygen flow fields contacting the anode and the cathode, respectively, wherein the components define an annular region therethrough along the axis. A fuel distribution manifold within the annular region is connected to deliver fuel to the fuel flow field in each of the unit cells. In a particular embodiment, a single bolt through the annular region clamps the unit cells together. In another embodiment, separator plates between individual unit cells have an extended radial dimension to function as cooling fins for maintaining the operating temperature of the fuel cell stack.

  12. System for inspection of stacked cargo containers (United States)

    Derenzo, Stephen [Pinole, CA


    The present invention relates to a system for inspection of stacked cargo containers. One embodiment of the invention generally comprises a plurality of stacked cargo containers arranged in rows or tiers, each container having a top, a bottom a first side, a second side, a front end, and a back end; a plurality of spacers arranged in rows or tiers; one or more mobile inspection devices for inspecting the cargo containers, wherein the one or more inspection devices are removeably disposed within the spacers, the inspection means configured to move through the spacers to detect radiation within the containers. The invented system can also be configured to inspect the cargo containers for a variety of other potentially hazardous materials including but not limited to explosive and chemical threats.

  13. Multistage Force Amplification of Piezoelectric Stacks (United States)

    Xu, Tian-Bing (Inventor); Siochi, Emilie J. (Inventor); Zuo, Lei (Inventor); Jiang, Xiaoning (Inventor); Kang, Jin Ho (Inventor)


    Embodiments of the disclosure include an apparatus and methods for using a piezoelectric device, that includes an outer flextensional casing, a first cell and a last cell serially coupled to each other and coupled to the outer flextensional casing such that each cell having a flextensional cell structure and each cell receives an input force and provides an output force that is amplified based on the input force. The apparatus further includes a piezoelectric stack coupled to each cell such that the piezoelectric stack of each cell provides piezoelectric energy based on the output force for each cell. Further, the last cell receives an input force that is the output force from the first cell and the last cell provides an output apparatus force In addition, the piezoelectric energy harvested is based on the output apparatus force. Moreover, the apparatus provides displacement based on the output apparatus force.

  14. Radiation-Tolerant Intelligent Memory Stack - RTIMS (United States)

    Ng, Tak-kwong; Herath, Jeffrey A.


    This innovation provides reconfigurable circuitry and 2-Gb of error-corrected or 1-Gb of triple-redundant digital memory in a small package. RTIMS uses circuit stacking of heterogeneous components and radiation shielding technologies. A reprogrammable field-programmable gate array (FPGA), six synchronous dynamic random access memories, linear regulator, and the radiation mitigation circuits are stacked into a module of 42.7 42.7 13 mm. Triple module redundancy, current limiting, configuration scrubbing, and single- event function interrupt detection are employed to mitigate radiation effects. The novel self-scrubbing and single event functional interrupt (SEFI) detection allows a relatively soft FPGA to become radiation tolerant without external scrubbing and monitoring hardware

  15. Absorption spectra of AA-stacked graphite

    International Nuclear Information System (INIS)

    Chiu, C W; Lee, S H; Chen, S C; Lin, M F; Shyu, F L


    AA-stacked graphite shows strong anisotropy in geometric structures and velocity matrix elements. However, the absorption spectra are isotropic for the polarization vector on the graphene plane. The spectra exhibit one prominent plateau at middle energy and one shoulder structure at lower energy. These structures directly reflect the unique geometric and band structures and provide sufficient information for experimental fitting of the intralayer and interlayer atomic interactions. On the other hand, monolayer graphene shows a sharp absorption peak but no shoulder structure; AA-stacked bilayer graphene has two absorption peaks at middle energy and abruptly vanishes at lower energy. Furthermore, the isotropic features are expected to exist in other graphene-related systems. The calculated results and the predicted atomic interactions could be verified by optical measurements.

  16. Development of on-site PAFC stacks

    Energy Technology Data Exchange (ETDEWEB)

    Hotta, K.; Matsumoto, Y. [Kansai Electric Power Co., Amagasaki (Japan); Horiuchi, H.; Ohtani, T. [Mitsubishi Electric Corp., Kobe (Japan)


    PAFC (Phosphoric Acid Fuel Cell) has been researched for commercial use and demonstration plants have been installed in various sites. However, PAFC don`t have a enough stability yet, so more research and development must be required in the future. Especially, cell stack needs a proper state of three phases (liquid, gas and solid) interface. It is very difficult technology to keep this condition for a long time. In the small size cell with the electrode area of 100 cm{sup 2}, gas flow and temperature distributions show uniformity. But in the large size cell with the electrode area of 4000 cm{sup 2}, the temperature distributions show non-uniformity. These distributions would cause to be shorten the cell life. Because these distributions make hot-spot and gas poverty in limited parts. So we inserted thermocouples in short-stack for measuring three-dimensional temperature distributions and observed effects of current density and gas utilization on temperature.

  17. CAM and stack air sampler design guide

    International Nuclear Information System (INIS)

    Phillips, T.D.


    About 128 air samplers and CAMs presently in service to detect and document potential radioactive release from 'H' and 'F' area tank farm ventilation stacks are scheduled for replacement and/or upgrade by Projects S-5764, S-2081, S-3603, and S-4516. The seven CAMs scheduled to be upgraded by Project S-4516 during 1995 are expected to provide valuable experience for the three remaining projects. The attached document provides design guidance for the standardized High Level Waste air sampling system

  18. Contemporary sample stacking in analytical electrophoresis

    Czech Academy of Sciences Publication Activity Database

    Malá, Zdeňka; Gebauer, Petr; Boček, Petr


    Roč. 32, č. 1 (2011), s. 116-126 ISSN 0173-0835 R&D Projects: GA ČR GA203/08/1536; GA ČR GAP206/10/1219; GA AV ČR IAA400310703 Institutional research plan: CEZ:AV0Z40310501 Keywords : biological samples * stacking * trace analysis * zone electrophoresis Subject RIV: CB - Analytical Chemistry, Separation Impact factor: 3.303, year: 2011

  19. Stacked Switched Capacitor Energy Buffer Architecture


    Chen, Minjie; Perreault, David J.; Afridi, Khurram


    Electrolytic capacitors are often used for energy buffering applications, including buffering between single-phase ac and dc. While these capacitors have high energy density compared to film and ceramic capacitors, their life is limited. This paper presents a stacked switched capacitor (SSC) energy buffer architecture and some of its topological embodiments, which when used with longer life film capacitors overcome this limitation while achieving effective energy densities comparable to elect...

  20. Organic carbonates as solvents in macrocyclic Mn(III) salen catalyzed asymmetric epoxidation of non-functionalized olefins

    Czech Academy of Sciences Publication Activity Database

    Maity, N. Ch.; Rao, G. V. S.; Prathap, Kaniraj Jeya; Abdi, S. H. R.; Kureshy, R. I.; Khan, N. H.; Bajaj, H. C.


    Roč. 366, January (2013), s. 380-389 ISSN 1381-1169 Institutional support: RVO:61388963 Keywords : asymmetric epoxidation * organic carbonate * macrocyclic Mn(III) salen complex Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.679, year: 2013

  1. Characterization and crystal structure of a 17-membered macrocyclic Schiff base compound MeO-sal-pn-bn

    Czech Academy of Sciences Publication Activity Database

    Khalaji, A.D.; Ghoran, S.H.; Rohlíček, Jan; Dušek, Michal


    Roč. 56, č. 2 (2015), s. 259-265 ISSN 0022-4766 Grant - others:AV ČR(CZ) Praemium Academiae Institutional support: RVO:68378271 Keywords : macrocyclic * Schiff base * spectroscopy * powder diffraction * orthorhombic Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 0.536, year: 2015

  2. When is stacking confusing? The impact of confusion on stacking in deep H I galaxy surveys (United States)

    Jones, Michael G.; Haynes, Martha P.; Giovanelli, Riccardo; Papastergis, Emmanouil


    We present an analytic model to predict the H I mass contributed by confused sources to a stacked spectrum in a generic H I survey. Based on the ALFALFA (Arecibo Legacy Fast ALFA) correlation function, this model is in agreement with the estimates of confusion present in stacked Parkes telescope data, and was used to predict how confusion will limit stacking in the deepest Square Kilometre Array precursor H I surveys. Stacking with LADUMA (Looking At the Distant Universe with MeerKAT) and DINGO UDEEP (Deep Investigation of Neutral Gas Origins - Ultra Deep) data will only be mildly impacted by confusion if their target synthesized beam size of 10 arcsec can be achieved. Any beam size significantly above this will result in stacks that contain a mass in confused sources that is comparable to (or greater than) that which is detectable via stacking, at all redshifts. CHILES (COSMOS H I Large Extragalactic Survey) 5 arcsec resolution is more than adequate to prevent confusion influencing stacking of its data, throughout its bandpass range. FAST (Five hundred metre Aperture Spherical Telescope) will be the most impeded by confusion, with H I surveys likely becoming heavily confused much beyond z = 0.1. The largest uncertainties in our model are the redshift evolution of the H I density of the Universe and the H I correlation function. However, we argue that the two idealized cases we adopt should bracket the true evolution, and the qualitative conclusions are unchanged regardless of the model choice. The profile shape of the signal due to confusion (in the absence of any detection) was also modelled, revealing that it can take the form of a double Gaussian with a narrow and wide component.

  3. Thyristor stack for pulsed inductive plasma generation. (United States)

    Teske, C; Jacoby, J; Schweizer, W; Wiechula, J


    A thyristor stack for pulsed inductive plasma generation has been developed and tested. The stack design includes a free wheeling diode assembly for current reversal. Triggering of the device is achieved by a high side biased, self supplied gate driver unit using gating energy derived from a local snubber network. The structure guarantees a hard firing gate pulse for the required high dI/dt application. A single fiber optic command is needed to achieve a simultaneous turn on of the thyristors. The stack assembly is used for switching a series resonant circuit with a ringing frequency of 30 kHz. In the prototype pulsed power system described here an inductive discharge has been generated with a pulse duration of 120 micros and a pulse energy of 50 J. A maximum power transfer efficiency of 84% and a peak power of 480 kW inside the discharge were achieved. System tests were performed with a purely inductive load and an inductively generated plasma acting as a load through transformer action at a voltage level of 4.1 kV, a peak current of 5 kA, and a current switching rate of 1 kA/micros.

  4. Electrochemical Detection in Stacked Paper Networks. (United States)

    Liu, Xiyuan; Lillehoj, Peter B


    Paper-based electrochemical biosensors are a promising technology that enables rapid, quantitative measurements on an inexpensive platform. However, the control of liquids in paper networks is generally limited to a single sample delivery step. Here, we propose a simple method to automate the loading and delivery of liquid samples to sensing electrodes on paper networks by stacking multiple layers of paper. Using these stacked paper devices (SPDs), we demonstrate a unique strategy to fully immerse planar electrodes by aqueous liquids via capillary flow. Amperometric measurements of xanthine oxidase revealed that electrochemical sensors on four-layer SPDs generated detection signals up to 75% higher compared with those on single-layer paper devices. Furthermore, measurements could be performed with minimal user involvement and completed within 30 min. Due to its simplicity, enhanced automation, and capability for quantitative measurements, stacked paper electrochemical biosensors can be useful tools for point-of-care testing in resource-limited settings. © 2015 Society for Laboratory Automation and Screening.

  5. HfO2/Pr2O3 gate dielectric stacks (United States)

    Sidorov, F.; Molchanova, A.; Rogozhin, A.


    Electrical properties of MOS structures based on molecular beam epitaxy formed HfO2/Pr2O3 gate dielectric stacks have been studied by CV, GV and IV characteristics. Electrical properties of the structures with HfO2/Pr2O3 and PEALD HfO2 dielectric layers were compared. Higher gate leakage current and lower interface trap level density in the structure with HfO2/Pr2O3 dielectric layer was observed.

  6. Synthesis and optoelectronic properties of a monodispersed macrocycle oligomer consisting of three triarylamine units

    Energy Technology Data Exchange (ETDEWEB)

    Kong, Qinggang, E-mail: [Jiangsu Key Laboratory of Atmospheric Environment Monitoring and Pollution Control, College of Environmental Science and Engineering, Nanjing University of Information Science and Technology, 219 Ningliu Road, Pukou District, Nanjing 210044 (China); Qian, Haiyan, E-mail: [College of Material Science and Technology, Nanjing University of Technology, 5 Xinmofan Road, Nanjing 210009 (China); Zhou, Yonghui; Li, Jun; Xiao, Huining [Jiangsu Key Laboratory of Atmospheric Environment Monitoring and Pollution Control, College of Environmental Science and Engineering, Nanjing University of Information Science and Technology, 219 Ningliu Road, Pukou District, Nanjing 210044 (China)


    A monodispersed macrocyclic oligomer constructed by three triarylmine units ((TPAT){sub 3}) was designed and readily synthesized from the monomer of 3-(4 Prime -(phenyl(4 Double-Prime -methylphenyl)amino)-phenyl)pentan-3-ol (TPAT) by means of a simple Friedel-Crafts alkylation reaction. The structure of the resultant macrocycle was examined using FT-IR, NMR and MALDI-TOF mass spectroscopy. Compared with 1,10-bis(di-4-tolylaminophenyl) cyclohexane (TAPC) and tri-p-tolylamine (TTA), (TPAT){sub 3} possesses the three-dimensional chair conformation and the higher T{sub g}. In the photoluminescence (PL) spectrum of (TPAT){sub 3} film, there are no excimer emission peaks in the range of 400-550 nm region as those of TAPC and TTA. Besides an EL peak at 386 nm, the single-layer device occured only the 438 nm excimer emission peak, whose intensity increased with the excitation voltage increase. Using 1,3,5-Tris(N-phenylbenzimidazol-2-yl)-benzene (TPBI) as the electron-transporting layer, the resulting double-layer device ITO/(TPAT){sub 3} (40 nm)/TPBI (40 nm)/Mg:Ag (10:1; 50 nm)/Ag (100 nm) only exhibited a 438 nm maximum symmetrical emission peak under an excitation voltage of 14 V. However, as the applied voltage was increased from 14 V to 19 V, the intensity of the symmetrical curve with a 468 nm peak from exciplex emission gets stronger and stronger. In fact, the resultant emission curve was asymmetrical, due to the overlap of two symmetrical curves with 438 nm and 468 nm peaks, respectively. The maximum luminance and luminous efficiency are 2240 cd m{sup -2} at 18.8 V and 1.73 cd A{sup -1} at 1878 cd m{sup -2} (13.9 V). Highlights: Black-Right-Pointing-Pointer The monodispersed macrocyclic oligomer constructed by three triarylamine units was synthesized and characterized. Black-Right-Pointing-Pointer The PL of (TPAT){sub 3} film does not emerge TAPC and TTA's emission peaks of over 400 nm region. Black-Right-Pointing-Pointer The 438 nm emission peak was found from

  7. Macrocyclic chelator-coupled gastrin-based radiopharmaceuticals for targeting of gastrin receptor-expressing tumours

    International Nuclear Information System (INIS)

    Good, Stephan; Wang, Xuejuan; Maecke, Helmut R.; Walter, Martin A.; Mueller-Brand, Jan; Waser, Beatrice; Reubi, Jean-Claude; Behe, Martin P.


    Diethylenetriamine-pentaacetic acid (DTPA)-coupled minigastrins are unsuitable for therapeutic application with the available β-emitting radiometals due to low complex stability. Low tumour-to-kidney ratio of the known radiopharmaceuticals is further limiting their potency. We used macrocyclic chelators for coupling to increase complex stability, modified the peptide sequence to enhance radiolytic stability and studied tumour-to-kidney ratio and metabolic stability using 111 In-labelled derivatives. Gastrin derivatives with decreasing numbers of glutamic acids were synthesised using 111 In as surrogate for therapeutic radiometals for in vitro and in vivo studies. Gastrin receptor affinities of the nat In-metallated compounds were determined by receptor autoradiography using 125 I-CCK as radioligand. Internalisation was evaluated in AR4-2J cells. Enzymatic stability was determined by incubating the 111 In-labelled peptides in human serum. Biodistribution was performed in AR4-2J-bearing Lewis rats. IC 50 values of the nat In-metallated gastrin derivatives vary between 1.2 and 4.8 nmol/L for all methionine-containing derivatives. Replacement of methionine by norleucine, isoleucine, methionine-sulfoxide and methionine-sulfone resulted in significant decrease of receptor affinity (IC 50 between 9.9 and 1,195 nmol/L). All cholecystokinin receptor affinities were >100 nmol/L. All 111 In-labelled radiopeptides showed receptor-specific internalisation. Serum mean-life times varied between 2.0 and 72.6 h, positively correlating with the number of Glu residues. All 111 In-labelled macrocyclic chelator conjugates showed higher tumour-to-kidney ratios after 24 h (0.37-0.99) compared to 111 In-DTPA-minigastrin 0(0.05). Tumour wash out between 4 and 24 h was low. Imaging studies confirmed receptor-specific blocking of the tumour uptake. Reducing the number of glutamates increased tumour-to-kidney ratio but resulted in lower metabolic stability. The properties of the macrocyclic

  8. Diversity-oriented approach to macrocyclic cyclophane derivatives by Suzuki-Miyaura cross-coupling and olefin metathesis as key steps. (United States)

    Kotha, Sambasivarao; Chavan, Arjun S; Shaikh, Mobin


    Palladium-catalyzed Suzuki-Miyaura (SM) cross-coupling reaction with allylboronic acid pinacol ester and titanium assisted cross-metathesis (CM)/ring-closing metathesis (RCM) cascade has been used to synthesize macrocyclic cyclophane derivatives.

  9. Design, synthesis, X-ray studies, and biological evaluation of novel macrocyclic HIV-1 protease inhibitors involving the P1'-P2' ligands

    Energy Technology Data Exchange (ETDEWEB)

    Ghosh, Arun K.; Sean Fyvie, W.; Brindisi, Margherita; Steffey, Melinda; Agniswamy, Johnson; Wang, Yuan-Fang; Aoki, Manabu; Amano, Masayuki; Weber, Irene T.; Mitsuya, Hiroaki


    Design, synthesis, and evaluation of a new class of HIV-1 protease inhibitors containing diverse flexible macrocyclic P1'-P2' tethers are reported. Inhibitor 5a with a pyrrolidinone-derived macrocycle exhibited favorable enzyme inhibitory and antiviral activity (Ki = 13.2 nM, IC50 = 22 nM). Further incorporation of heteroatoms in the macrocyclic skeleton provided macrocyclic inhibitors 5m and 5o. These compounds showed excellent HIV-1 protease inhibitory (Ki = 62 pM and 14 pM, respectively) and antiviral activity (IC50 = 5.3 nM and 2.0 nM, respectively). Inhibitor 5o also remained highly potent against a DRV-resistant HIV-1 variant.

  10. Great isotope effects in compounding of sodium isotopes by macrocyclic polyether

    International Nuclear Information System (INIS)

    Knoechel, A.; Wilken, R.D.


    Isotope effects appear in the compounding of the two sodium isotopes 24 Na + and 22 Na + with macrocyclic polyethers, whose value was determined for the 13 best known polyethers. A radiometric process was used for determining the different half life periods of the nuclides used. To separate the compound and non-compound types, these were distributed between water and chloroform. The isotope ratio in the chloroform phase was compared with the output isotope ratio and the separation facfor determined from this. When using crown ethers, there was enrichment of 24 Na + by a significant amount (large crown ether) up to 3.1 +- 0.4% for 18 crown 6. The remarkably high results can be correlated by Biegeleisen's theory with other chemical conditions. There is a report on the first results of transferring these conditions to the H + /T + system. (orig.) [de

  11. Head-to-tail macrocyclization of cysteine-free peptides using an o-aminoanilide linker. (United States)

    Ohara, Takumi; Kaneda, Masato; Saito, Tomo; Fujii, Nobutaka; Ohno, Hiroaki; Oishi, Shinya


    A head-to-tail macrocyclization protocol for the preparation of cysteine-free cyclic peptides was investigated. The o-aminoanilide linker constructed in the peptide sequence by a standard Fmoc-based peptide synthesis procedure was subjected to nitrite-mediated activation under acidic conditions toward N-acyl benzotriazole as the active ester species. The subsequent cyclization smoothly proceeded by neutralization in the presence of additives such as 1-hydroxybenzotriazole (HOBt) and 1-hydroxy-7-azabenzotriazole (HOAt) to afford the expected cyclic pentapeptide, a CXCR4 antagonist. The cyclization efficiencies were dependent on the precursor open-chain sequence. The application of this step-wise activation-cyclization protocol to microflow reaction systems is also described. Copyright © 2018 Elsevier Ltd. All rights reserved.

  12. Versatile protein recognition by the encoded display of multiple chemical elements on a constant macrocyclic scaffold (United States)

    Li, Yizhou; De Luca, Roberto; Cazzamalli, Samuele; Pretto, Francesca; Bajic, Davor; Scheuermann, Jörg; Neri, Dario


    In nature, specific antibodies can be generated as a result of an adaptive selection and expansion of lymphocytes with suitable protein binding properties. We attempted to mimic antibody-antigen recognition by displaying multiple chemical diversity elements on a defined macrocyclic scaffold. Encoding of the displayed combinations was achieved using distinctive DNA tags, resulting in a library size of 35,393,112. Specific binders could be isolated against a variety of proteins, including carbonic anhydrase IX, horseradish peroxidase, tankyrase 1, human serum albumin, alpha-1 acid glycoprotein, calmodulin, prostate-specific antigen and tumour necrosis factor. Similar to antibodies, the encoded display of multiple chemical elements on a constant scaffold enabled practical applications, such as fluorescence microscopy procedures or the selective in vivo delivery of payloads to tumours. Furthermore, the versatile structure of the scaffold facilitated the generation of protein-specific chemical probes, as illustrated by photo-crosslinking.

  13. HPLC Enantioseparation of Phenylcarbamic Acid Derivatives by Using Macrocyclic Chiral Stationary Phases

    Directory of Open Access Journals (Sweden)

    Hroboňová Katarína


    Full Text Available The HPLC by using chiral stationary phases based on macrocyclic antibiotics, dimethylphenyl carbamate cyklofructan 7 and β-cyclodextrin in terms of polar-organic separation mode (mobile phase methanol/acetonitrile/acetic acid/triethylamine were used for enantioseparation of alkoxy derivatives of phenylcarbamic acid. The effect of the analyte structures on the efficiency of enantioseparation was investigated. The most suitable stationary phase was teicoplanin aglycone, where the separations of the enantiomers were obtained (the resolution value from 0.65 to 2.90, depending on the structure of the analyte. Significant effect on the resolution of the enantiomers has position of alkoxy substituent in the hydrophobic part of the molecule. The enantiorecognition was achieved for 3-alkoxysubstituted derivatives.

  14. Cobalt(II)-selective membrane electrode based on a recently synthesized benzo-substituted macrocyclic diamide. (United States)

    Shamsipur, M; Poursaberi, T; Rouhani, S; Niknam, K; Sharghi, H; Ganjali, M R


    A PVC-membrane electrode based on a recently synthesized 18-membered macrocyclic diamide is presented. The electrode reveals a Nernstian potentiometric response for Co2+ over a wide concentration range (2.0 x 10(-6)-1.0 x 10(-2) M). The electrode has a response time of about 10 s and can be used for at least 2 months without any divergence. The proposed sensor revealed very good selectivities for Co2+ over a wide variety of other metal ions, and could be used over a wide pH range (3.0-8.0). The detection limit of the sensor is 6.0 x 10(-7) M. It was successfully applied to the direct determination and potentiometric titration of cobalt ion.

  15. Fast and versatile microwave-assisted intramolecular Heck reaction in peptide macrocyclization using microwave energy. (United States)

    Byk, Gerardo; Cohen-Ohana, Mirit; Raichman, Daniel


    We have revisited the intramolecular Heck reaction and investigated the microwave-assisted macrocyclization on preformed peptides using a model series of ring-varying peptides acryloyl-Gly-[Gly](n)-Phe(4-I)NHR; n = 0-4. The method was applied to both solution and solid supported cyclizations. We demonstrate that the intramolecular Heck reaction can be performed in peptides both in solution and solid support using a modified domestic microwave within 1 to 30 minutes in DMF under reflux with moderate yields ranging from 15 to 25% for a scale between 2-45 mg of linear precursors. The approach was applied to the synthesis of a constrained biologically relevant peptidomimetic bearing an Arg-Gly-Asp (RGD) sequence. These results make the microwave-assisted Heck reaction an attractive renovated approach for peptidomimetics. Copyright 2006 Wiley Periodicals, Inc.

  16. Improved Direct Methanol Fuel Cell Stack (United States)

    Wilson, Mahlon S.; Ramsey, John C.


    A stack of direct methanol fuel cells exhibiting a circular footprint. A cathode and anode manifold, tie-bolt penetrations and tie-bolts are located within the circular footprint. Each fuel cell uses two graphite-based plates. One plate includes a cathode active area that is defined by serpentine channels connecting the inlet and outlet cathode manifold. The other plate includes an anode active area defined by serpentine channels connecting the inlet and outlet of the anode manifold, where the serpentine channels of the anode are orthogonal to the serpentine channels of the cathode. Located between the two plates is the fuel cell active region.

  17. NSF tandem stack support structure deflection characteristics

    International Nuclear Information System (INIS)

    Cook, J.


    Results are reported of load tests carried out on the glass legs of the insulating stack of the 30 MV tandem Van de Graaff accelerator now under construction at Daresbury Laboratory. The tests to investigate the vulnerability of the legs when subjected to tensile stresses were designed to; establish the angle of rotation of the pads from which the stresses in the glass legs may be calculated, proof-test the structure and at the same time reveal any asymmetry in pad rotations or deflections, and to confirm the validity of the computer design analysis. (UK)

  18. Compliant Glass Seals for SOFC Stacks

    Energy Technology Data Exchange (ETDEWEB)

    Chou, Yeong -Shyung [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Choi, Jung-Pyung [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Xu, Wei [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Stephens, Elizabeth V. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Koeppel, Brian J. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Stevenson, Jeffry W. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Lara-Curzio, Edgar [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)


    This report summarizes results from experimental and modeling studies performed by participants in the Solid-State Energy Conversion Alliance (SECA) Core Technology Program, which indicate that compliant glass-based seals offer a number of potential advantages over conventional seals based on de-vitrifying glasses, including reduced stresses during stack operation and thermal cycling, and the ability to heal micro-damage induced during thermal cycling. The properties and composition of glasses developed and/or investigated in these studies are reported, along with results from long-term (up to 5,800h) evaluations of seals based on a compliant glass containing ceramic particles or ceramic fibers.

  19. Effects of combustible stacking in large compartments

    DEFF Research Database (Denmark)

    Gentili, Filippo; Giuliani, Luisa; Bontempi, Franco


    This paper focuses on the modelling of fire in case of various distributions of combustible materials in a large compartment. Large compartments often represent a challenge for structural fire safety, because of lack of prescriptive rules to follow and difficulties of taking into account the effect...... to different stacking configurations of the pallets with the avail of a CFD code. The results in term of temperatures of the hot gasses and of the steel elements composing the structural system are compared with simplified analytical model of localized and post-flashover fires, with the aim of highlighting...

  20. Displacive phase transformations and generalized stacking faults

    Czech Academy of Sciences Publication Activity Database

    Paidar, Václav; Ostapovets, Andriy; Duparc, O. H.; Khalfallah, O.


    Roč. 122, č. 3 (2012), s. 490-492 ISSN 0587-4246. [International Symposium on Physics of Materials, ISPMA /12./. Praha, 04.09.2011-08.09.2011] R&D Projects: GA AV ČR IAA100100920 Institutional research plan: CEZ:AV0Z10100520 Keywords : ab-initio calculations * close-packed structures * generalized stacking faults * homogeneous deformation * lattice deformation * many-body potentials Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 0.531, year: 2012

  1. Snapshot and crystallographic observations of kinetic and thermodynamic products for NO2S2 macrocyclic complexes

    Directory of Open Access Journals (Sweden)

    In-Hyeok Park


    Full Text Available Direct observation and structural characterization of a kinetic product and a thermodynamic product for complexes with an NO2S2 macrocycle (L are reported. L reacts with copper(I iodide to give a mononuclear complex [Cu(L]2(Cu2I4·2CH2Cl2 (1, featuring three separate units. When cadmium(II iodide was reacted with L, an anion-coordinated complex [Cd(LI]2(Cd2I6·4CH3CN (2 with a needle-type crystal shape was formed as the kinetic product. Interestingly, when the needle-type kinetic product was left undisturbed in the mother solution it gradually transformed to the pseudo-dimer complex [Cd2(L2I2](Cd2I6 (3 with a brick-type crystal shape as the thermodynamic product. The dissolution–recrystallization process resulted in the elimination of the lattice solvent molecules (acetonitrile in 2 and the contraction of two neighboring macrocyclic complex units [Cd(LI]+, forming the pseudo-dimer 3 via an intermolecular Cd...I interaction between two monomers. For the entire process from kinetic to thermodynamic products, it was possible to obtain sequential photographic snapshots, single-crystal X-ray structures and powder X-ray diffraction patterns. For the copper(I and cadmium(II complexes, competitive NMR results agree with the solid-state data that show copper(I has a higher affinity for L than does cadmium(II.

  2. Sampled-time control of a microbial fuel cell stack (United States)

    Boghani, Hitesh C.; Dinsdale, Richard M.; Guwy, Alan J.; Premier, Giuliano C.


    Research into microbial fuel cells (MFCs) has reached the point where cubic metre-scale systems and stacks are being built and tested. Apart from performance enhancement through catalysis, materials and design, an important research area for industrial applicability is stack control, which can enhance MFCs stack power output. An MFC stack is controlled using a sampled-time digital control strategy, which has the advantage of intermittent operation with consequent power saving, and when used in a hybrid series stack connectivity, can avoid voltage reversals. A MFC stack comprising four tubular MFCs was operated hydraulically in series. Each MFC was connected to an independent controller and the stack was connected electrically in series, creating a hybrid-series connectivity. The voltage of each MFC in the stack was controlled such that the overall series stack voltage generated was the algebraic sum (1.26 V) of the individual MFC voltages (0.32, 0.32, 0.32 and 0.3). The controllers were able to control the individual voltages to the point where 2.52 mA was drawn from the stack at a load of 499.9 Ω (delivering 3.18 mW). The controllers were able to reject the disturbances and perturbations caused by electrical loading, temperature and substrate concentration.

  3. Density functional MO calculation for stacked DNA base-pairs with backbones. (United States)

    Kurita, N; Kobayashi, K


    In order to elucidate the effect of the sugar and phosphate backbones on the stable structure and electronic properties of stacked DNA base-pairs, we performed ab initio molecular orbital (MO) calculations based on the density functional theory and Slater-type basis set. As a model cluster for stacked base-pairs, we employed three isomers for the dimer unit of stacked guanine-cytosine pairs composed with backbones as well as base-pairs. These structures were fully optimized and their electronic properties were self-consistently investigated. By including the backbones, the difference in total energy among the isomers was largely enhanced, while the trend in relative stability was not changed. The effect of backbones on the electronic properties is remarkable: the MOs with the character of the PO4 parts of backbones appear just below the highest-occupied MO. This result indicates that the PO4 parts might play a rule as a reaction site in chemical processes concerning DNA. Therefore, we conclude that the DNA backbones are indispensable for investigating the stability and electronic properties of the stacked DNA base-pairs.

  4. Non-destructive separation of metal ions from wastewater containing excess aminopolycarboxylate chelant in solution with an ion-selective immobilized macrocyclic material. (United States)

    Hasegawa, Hiroshi; Rahman, Ismail M M; Kinoshita, Sanae; Maki, Teruya; Furusho, Yoshiaki


    Although the excellent metal-binding capacities of aminopolycarboxylate chelants (APCs) facilitate their extensive use, pre- and post-toxicity of APCs and their high persistence in aquatic environments evoke concerns. Several treatment techniques with a principal focus on the degradation of APCs at the pre-release step have been proposed. Here, we report a technique for the separation of metal ions from waste solution containing excess APCs using a solid phase extraction system with an ion-selective immobilized macrocyclic material, commonly known as a molecular recognition technology (MRT) gel. Synthetic metal solutions with 100-fold chelant content housed in H2O matrices were used as samples. The MRT gel showed a higher recovery rate compared with other SPE materials at 20 degrees C using a flow rate of 0.2 mL min(-1). The effects of solution pH, metal-chelant stability constants and ionic radii were assessed for 32 metals. Compared to the conventional treatment options for such waste solutions, our proposed technique has the advantage of non-destructive separation of both metal ions and chelants. 2010 Elsevier Ltd. All rights reserved.

  5. AC impedance diagnosis of a 500 W PEM fuel cell stack . Part I: Stack impedance (United States)

    Yuan, Xiaozi; Sun, Jian Colin; Blanco, Mauricio; Wang, Haijiang; Zhang, Jiujun; Wilkinson, David P.

    Diagnosis of stack performance is of importance to proton exchange membrane (PEM) fuel cell research. This paper presents the diagnostic testing results of a 500 W Ballard Mark V PEM fuel cell stack with an active area of 280 cm 2 by electrochemical impedance spectroscopy (EIS). The EIS was measured using a combination of a FuelCon test station, a TDI loadbank, and a Solartron 1260 Impedance/Gain-Phase Analyzer operating in the galvanostatic mode. The method described in this work can obtain the impedance spectra of fuel cells with a larger geometric surface area and power, which are normally difficult to measure due to the limitations on commercial load banks operating at high currents. By using this method, the effects of temperature, flow rate, and humidity on the stack impedance spectra were examined. The results of the electrochemical impedance analysis show that with increasing temperature, the charge transfer resistance decreases due to the slow oxygen reduction reaction (ORR) process at low temperature. If the stack is operated at a fixed air flow rate, a low frequency arc appears and grows with increasing current due to the shortage of air. The anode humidification cut-off does not affect the spectra compared to the cut-off for cathode humidification.

  6. Stray field interaction of stacked amorphous tapes

    International Nuclear Information System (INIS)

    Guenther, Wulf; Flohrer, Sybille


    In this study, magnetic cores made of amorphous rectangular tape layers are investigated. The quality factor Q of the tape material decreases rapidly, however, when stacking at least two tape layers. The hysteresis loop becomes non-linear, and the coercivity increases. These effects are principally independent of the frequency and occur whether tape layers are insulated or not. The Kerr-microscopy was used to monitor local hysteresis loops by varying the distance of two tape layers. The magnetization direction of each magnetic domain is influenced by the anisotropy axis, the external magnetic field and the stray field of magnetic domains of the neighboring tape layers. We found that crossed easy axes (as the extreme case for inclined axes) of congruent domains retain the remagnetization and induce a plateau of the local loop. Summarizing local loops leads to the observed increase of coercivity and non-linearity of the inductively measured loop. A high Q-factor can be preserved if the easy axes of stacked tape layers are identical within the interaction range in the order of mm

  7. Annular feed air breathing fuel cell stack (United States)

    Wilson, Mahlon S.; Neutzler, Jay K.


    A stack of polymer electrolyte fuel cells is formed from a plurality of unit cells where each unit cell includes fuel cell components defining a periphery and distributed along a common axis, where the fuel cell components include a polymer electrolyte membrane, an anode and a cathode contacting opposite sides of the membrane, and fuel and oxygen flow fields contacting the anode and the cathode, respectively, wherein the components define an annular region therethrough along the axis. A fuel distribution manifold within the annular region is connected to deliver fuel to the fuel flow field in each of the unit cells. The fuel distribution manifold is formed from a hydrophilic-like material to redistribute water produced by fuel and oxygen reacting at the cathode. In a particular embodiment, a single bolt through the annular region clamps the unit cells together. In another embodiment, separator plates between individual unit cells have an extended radial dimension to function as cooling fins for maintaining the operating temperature of the fuel cell stack.

  8. Stacking Analysis of Binary Systems with HAWC (United States)

    Brisbois, Chad; HAWC Collaboration


    Detecting binary systems at TeV energies is an important problem because only a handful of such systems are currently known. The nature of such systems is typically thought to be composed of a compact object and a massive star. The TeV emission from these systems does not obviously correspond to emission in GeV or X-ray, where many binary systems have previously been found. This study focuses on a stacking method to detect TeV emission from LS 5039, a known TeV binary, to test its efficacy in HAWC data. Stacking is a widely employed method for increasing signal to noise ratio in optical astronomy, but has never been attempted previously with HAWC. HAWC is an ideal instrument to search for TeV binaries, because of its wide field of view and high uptime. Applying this method to the entire sky may allow HAWC to detect binary sources of very short or very long periods not sensitive to current analyses. NSF, DOE, Los Alamos, Michigan Tech, CONACyt, UNAM, BUAP.

  9. High performance zinc air fuel cell stack (United States)

    Pei, Pucheng; Ma, Ze; Wang, Keliang; Wang, Xizhong; Song, Mancun; Xu, Huachi


    A zinc air fuel cell (ZAFC) stack with inexpensive manganese dioxide (MnO2) as the catalyst is designed, in which the circulation flowing potassium hydroxide (KOH) electrolyte carries the reaction product away and acts as a coolant. Experiments are carried out to investigate the characteristics of polarization, constant current discharge and dynamic response, as well as the factors affecting the performance and uniformity of individual cells in the stack. The results reveal that the peak power density can be as high as 435 mW cm-2 according to the area of the air cathode sheet, and the influence factors on cell performance and uniformity are cell locations, filled state of zinc pellets, contact resistance, flow rates of electrolyte and air. It is also shown that the time needed for voltages to reach steady state and that for current step-up or current step-down are both in milliseconds, indicating the ZAFC can be excellently applied to vehicles with rapid dynamic response demands.

  10. Generalized stacking fault energies of alloys. (United States)

    Li, Wei; Lu, Song; Hu, Qing-Miao; Kwon, Se Kyun; Johansson, Börje; Vitos, Levente


    The generalized stacking fault energy (γ surface) provides fundamental physics for understanding the plastic deformation mechanisms. Using the ab initio exact muffin-tin orbitals method in combination with the coherent potential approximation, we calculate the γ surface for the disordered Cu-Al, Cu-Zn, Cu-Ga, Cu-Ni, Pd-Ag and Pd-Au alloys. Studying the effect of segregation of the solute to the stacking fault planes shows that only the local chemical composition affects the γ surface. The calculated alloying trends are discussed using the electronic band structure of the base and distorted alloys.Based on our γ surface results, we demonstrate that the previous revealed 'universal scaling law' between the intrinsic energy barriers (IEBs) is well obeyed in random solid solutions. This greatly simplifies the calculations of the twinning measure parameters or the critical twinning stress. Adopting two twinnability measure parameters derived from the IEBs, we find that in binary Cu alloys, Al, Zn and Ga increase the twinnability, while Ni decreases it. Aluminum and gallium yield similar effects on the twinnability.

  11. Computerized plutonium laboratory-stack monitoring system

    International Nuclear Information System (INIS)

    Stafford, R.G.; DeVore, R.K.


    The Los Alamos Scientific Laboratory has recently designed and constructed a Plutonium Research and Development Facility to meet design criteria imposed by the United States Energy Research and Development Administration. A primary objective of the design criteria is to assure environmental protection and to reliably monitor plutonium effluent via the ventilation exhaust systems. A state-of-the-art facility exhaust air monitoring system is described which establishes near ideal conditions for evaluating plutonium activity in the stack effluent. Total and static pressure sensing manifolds are incorporated to measure average velocity and integrated total discharge air volume. These data are logged at a computer which receives instrument data through a multiplex scanning system. A multipoint isokinetic sampling assembly with associated instrumentation is described. Continuous air monitors have been designed to sample from the isokinetic sampling assembly and transmit both instantaneous and integrated stack effluent concentration data to the computer and various cathode ray tube displays. The continuous air monitors also serve as room air monitors in the plutonium facility with the primary objective of timely evacuation of personnel if an above tolerance airborne plutonium concentration is detected. Several continuous air monitors are incorporated in the ventilation system to assist in identification of release problem areas

  12. Description of gasket failure in a 7 cell PEMFC stack

    Energy Technology Data Exchange (ETDEWEB)

    Husar, Attila; Serra, Maria [Institut de Robotica i Informatica Industrial, Parc Tecnologic de Barcelona, Edifici U, C. Llorens i Artigas, 4-6, 2a Planta, 08028 Barcelona (Spain); Kunusch, Cristian [Laboratorio de Electronica Industrial Control e Instrumentacion, Facultad de Ingenieria, UNLP (Argentina)


    This article presents the data and the description of a fuel cell stack that failed due to gasket degradation. The fuel cell under study is a 7 cell stack. The unexpected change in several variables such as temperature, pressure and voltage indicated the possible failure of the stack. The stack was monitored over a 6 h period in which data was collected and consequently analyzed to conclude that the fuel cell stack failed due to a crossover leak on the anode inlet port located on the cathode side gasket of cell 2. This stack failure analysis revealed a series of indicators that could be used by a super visional controller in order to initiate a shutdown procedure. (author)

  13. Quadratic forms and Clifford algebras on derived stacks


    Vezzosi, Gabriele


    In this paper we present an approach to quadratic structures in derived algebraic geometry. We define derived n-shifted quadratic complexes, over derived affine stacks and over general derived stacks, and give several examples of those. We define the associated notion of derived Clifford algebra, in all these contexts, and compare it with its classical version, when they both apply. Finally, we prove three main existence results for derived shifted quadratic forms over derived stacks, define ...

  14. Use of impedance tagging to monitor fuel cell stack performance (United States)

    Silva, Gregory

    Fuel cells are electrochemical device that are traditionally assembled in stacks to perform meaningful work. Monitoring the state of the stack is vitally important to ensure that it is operating efficiently and that constituent cells are not failing for one of a several common reasons including membrane dehydration, gas diffusion layer flooding, reactant starvation, and physical damage. Current state-of-the-art monitoring systems are costly and require at least one connection per cell on the stack, which introduces reliability concerns for stacks consisting of hundreds of cells. This thesis presents a novel approach for diagnosing problems in a fuel cell stack that attempts to reduce the cost and complexity of monitoring cells in a stack. The proposed solution modifies the electrochemical impedance spectroscopy (EIS) response of each cell in the stack by connecting an electrical tag in parallel with each cell. This approach allows the EIS response of the entire stack to identify and locate problems in the stack. Capacitors were chosen as tags because they do not interfere with normal stack operation and because they can generate distinct stack EIS responses. An experiment was performed in the Center for Automation Technologies an Systems (CATS) fuel cell laboratory at Rensselaer Polytechnic Institute (RPI) to perform EIS measurements on a single cell with and without capacitor tags to investigate the proposed solution. The EIS data collected from this experiment was used to create a fuel cell model to investigate the proposed solution under ideal conditions. This thesis found that, although the concept shows some promise in simulations, significant obstacles to implementing the proposed solution. Observed EIS response when the capacitor tags were connected did not match the expected EIS response. Constraints on the capacitor tags found by the model impose significant manufacturing challenges to the proposed solution. Further development of the proposed solution is

  15. Stacked Heterogeneous Neural Networks for Time Series Forecasting

    Directory of Open Access Journals (Sweden)

    Florin Leon


    Full Text Available A hybrid model for time series forecasting is proposed. It is a stacked neural network, containing one normal multilayer perceptron with bipolar sigmoid activation functions, and the other with an exponential activation function in the output layer. As shown by the case studies, the proposed stacked hybrid neural model performs well on a variety of benchmark time series. The combination of weights of the two stack components that leads to optimal performance is also studied.

  16. A novel configuration for direct internal reforming stacks (United States)

    Fellows, Richard

    This paper presents a stack concept that can be applied to both molten carbonate fuel cell (MCFC) and solid oxide fuel cell (SOFC) internal reforming stacks. It employs anode recycle and allows the design of very simple system configurations, while giving enhanced efficiencies and high specific power densities. The recycle of anode exit gas to the anode inlet has previously been proposed as a means of preventing carbon deposition in direct internal reforming (DIR) stacks. When applied to a normal stack this reduces the Nernst voltages because the recycle stream is relatively depleted in hydrogen. In the concept proposed here, known as the `Smarter' stack, there are two anode exit streams, one of which is depleted, while the other is relatively undepleted. The depleted stream passes directly to the burner, and the undepleted stream is recycled to the stack inlet. By this means high Nernst voltages are achieved in the stack. The concept has been simulated and assessed for parallel-flow and cross-flow MCFC and SOFC stacks and graphs are presented showing temperature distributions. The `Smarter' stacks employ a high recycle rate resulting in a reduced natural gas concentration at the stack inlet, and this reduces or eliminates the unfavourable temperature dip. Catalyst grading can further improve the temperature distribution. The concept allows simple system configurations in which the need for fuel pre-heat is eliminated. Efficiencies are up to 10 percentage points higher than for conventional stacks with the same cell area and maximum stack temperature. The concept presented here was devised in a project part-funded by the EU, and has been adopted by the European Advanced DIR-MCFC development programme led by BCN.

  17. Status of Slip Stacking at Fermilab Main Injector

    CERN Document Server

    Seiya, Kiyomi; Chase, Brian; Dey, Joseph; Kourbanis, Ioanis; MacLachlan, James A; Meisner, Keith G; Pasquinelli, Ralph J; Reid, John; Rivetta, Claudio H; Steimel, Jim


    In order to increase proton intensity on anti proton production cycle of the Main Injector we are going to use the technique of 'slip stacking' and doing machine studies. In slip stacking, one bunch train is injected at slightly lower energy and second train is at slightly higher energy. Afterwards they are aligned longitudinally and captured with one rf bucket. This longitudinal stacking process is expected to double the bunch intensity. The required intensity for anti proton production is 8·1012

  18. A novel design for solid oxide fuel cell stacks

    Energy Technology Data Exchange (ETDEWEB)

    Al-Qattan, A.M.; Chmielewski, D.J.; Al-Hallaj, S.; Selman, J.R. [Illinois Inst. of Technology, Chicago, IL (United States). Dept. of Chemical and Environmental Engineering


    Conventional fuel cell stack designs suffer from severe spatial nonuniformity in both temperature and current density. Such variations are known to create damaging thermal stresses within the stack and thus, impact overall lifespan. In this work, we propose a novel stack design aimed at reducing spatial variations at the source. We propose a mechanism of distributed fuel feed in which the heat generation profile can be influenced directly. Simulation results are presented to illustrate the potential of the proposed scheme. (author)

  19. Development of the electric utility dispersed use PAFC stack

    Energy Technology Data Exchange (ETDEWEB)

    Horiuchi, Hiroshi; Kotani, Ikuo [Mitsubishi Electric Co., Kobe (Japan); Morotomi, Isamu [Kansai Electric Power Co., Hyogo (Japan)] [and others


    Kansai Electric Power Co. and Mitsubishi Electric Co. have been developing the electric utility dispersed use PAFC stack operated under the ambient pressure. The new cell design have been developed, so that the large scale cell (1 m{sup 2} size) was adopted for the stack. To confirm the performance and the stability of the 1 m{sup 2} scale cell design, the short stack study had been performed.

  20. Method for monitoring stack gases for uranium activity

    International Nuclear Information System (INIS)

    Beverly, C.R.; Ernstberger, H.G.


    A method for sampling stack gases emanating from the purge cascade of a gaseous diffusion cascade system utilized to enrich uranium for determining the presence and extent of uranium in the stack gases in the form of gaseous uranium hexafluoride, is described comprising the steps of removing a side stream of gases from the stack gases, contacting the side stream of the stack gases with a stream of air sufficiently saturated with moisture for reacting with and converting any gaseous uranium hexafluroide contracted thereby in the side stream of stack gases to particulate uranyl fluoride. Thereafter contacting the side stream of stack gases containing the particulate uranyl fluoride with moving filter means for continuously intercepting and conveying the intercepted particulate uranyl fluoride away from the side stream of stack gases, and continually scanning the moving filter means with radiation monitoring means for sensing the presence and extent of particulate uranyl fluoride on the moving filter means which is indicative of the extent of particulate uranyl fluoride in the side stream of stack gases which in turn is indicative of the presence and extent of uranium hexafluoride in the stack gases

  1. Design and development of an automated uranium pellet stacking system

    International Nuclear Information System (INIS)

    Reiss, B.S.; Nokleby, S.B.


    A novel design for an automated uranium pellet stacking system is presented. This system is designed as a drop-in solution to the current production line to enhance the fuel pellet stacking process. The three main goals of this system are to reduce worker exposure to radiation to as low as reasonable achievable (ALARA), improve product quality, and increase productivity. The proposed system will reduce the potential for human error. This single automated system will replace the two existing pellet stacking stations while increasing the total output, eliminating pellet stacking as a bottleneck in the fuel bundle assembly process. (author)

  2. Highly Efficient, Durable Regenerative Solid Oxide Stack, Phase I (United States)

    National Aeronautics and Space Administration — Precision Combustion, Inc. (PCI) proposes to develop a highly efficient regenerative solid oxide stack design. Novel structural elements allow direct internal...

  3. Sharing programming resources between Bio* projects through remote procedure call and native call stack strategies. (United States)

    Prins, Pjotr; Goto, Naohisa; Yates, Andrew; Gautier, Laurent; Willis, Scooter; Fields, Christopher; Katayama, Toshiaki


    Open-source software (OSS) encourages computer programmers to reuse software components written by others. In evolutionary bioinformatics, OSS comes in a broad range of programming languages, including C/C++, Perl, Python, Ruby, Java, and R. To avoid writing the same functionality multiple times for different languages, it is possible to share components by bridging computer languages and Bio* projects, such as BioPerl, Biopython, BioRuby, BioJava, and R/Bioconductor. In this chapter, we compare the two principal approaches for sharing software between different programming languages: either by remote procedure call (RPC) or by sharing a local call stack. RPC provides a language-independent protocol over a network interface; examples are RSOAP and Rserve. The local call stack provides a between-language mapping not over the network interface, but directly in computer memory; examples are R bindings, RPy, and languages sharing the Java Virtual Machine stack. This functionality provides strategies for sharing of software between Bio* projects, which can be exploited more often. Here, we present cross-language examples for sequence translation, and measure throughput of the different options. We compare calling into R through native R, RSOAP, Rserve, and RPy interfaces, with the performance of native BioPerl, Biopython, BioJava, and BioRuby implementations, and with call stack bindings to BioJava and the European Molecular Biology Open Software Suite. In general, call stack approaches outperform native Bio* implementations and these, in turn, outperform RPC-based approaches. To test and compare strategies, we provide a downloadable BioNode image with all examples, tools, and libraries included. The BioNode image can be run on VirtualBox-supported operating systems, including Windows, OSX, and Linux.

  4. Stacking faults and phase changes in Mg-doped InGaN grown on Si

    International Nuclear Information System (INIS)

    Liliental-Weber, Zuzanna; Yu, Kin M.; Reichertz, Lothar A.; Ager, Joel W.; Walukiewicz, Wladek; Schaff, William J.; Hawkridge, Michael E.


    We report evidence for the role of Mg in the formation of basal stacking faults and a phase transition in In x Ga 1-x N layers doped with Mg grown by molecular beam epitaxy on Si(111) substrates with AlN buffer layers. Several samples with varying In content between x∝0.1 and x∝0.3 are examined by transmission electron microscopy and other techniques. High densities of basal stacking faults are observed in the central region of the InGaN layer away from the substrate or layer surface, but at varying depths within this region. Selected area diffraction patterns show that while the InGaN layer is initially in the wurtzite phase (and of good quality) AlN buffer layer, there is a change to the zinc blende phase in the upper part of the InGaN layer. SIMS measurements show that the Mg concentration drops from a maximum to a steady concentration coinciding with the presence of the basal stacking faults. There is little change in In or Ga concentrations in the same area. High-resolution electron microscopy from the area of the stacking faults confirms that the change to the cubic phase is abrupt across one such fault. These results indicate that Mg plays a role in the formation of stacking faults and the phase change observed in In x Ga 1-x N alloys. We also consider the role of In in the formation of these defects. (copyright 2009 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  5. A Review on the Toxicity and Non-Target Effects of Macrocyclic Lactones in Terrestrial and Aquatic Environments


    Lumaret, Jean-Pierre; Errouissi, Faiek; Floate, Kevin; Römbke, Jörg; Wardhaugh, Keith


    The avermectins, milbemycins and spinosyns are collectively referred to as macrocyclic lactones (MLs) which comprise several classes of chemicals derived from cultures of soil micro-organisms. These compounds are extensively and increasingly used in veterinary medicine and agriculture. Due to their potential effects on non-target organisms, large amounts of information on their impact in the environment has been compiled in recent years, mainly caused by legal requirements related to their ma...

  6. Introduction of axial chirality at a spiro carbon atom in the synthesis of pentaerythritol-imine macrocycles. (United States)

    Grajewski, J; Piotrowska, K; Zgorzelak, M; Janiak, A; Biniek-Antosiak, K; Rychlewska, U; Gawronski, J


    Novel chiral macrocyclic polyimines with spiro carbon atoms are described. The key feature of the synthesis is the formation of an axially chiral quaternary carbon atom having four constitutionally identical substituents. This is possible either by the freezing of the labile conformation of a spiro-diboronate moiety or by the diastereomeric fitting of a conformationally stable spiro-acetal moiety into a chiral framework. A general model for the description of this type of axial chirality is proposed.

  7. Green chemistry for preparation of oligopyrrole macrocycles precursors: Novel methodology for dipyrromethanes and tripyrromethanes synthesis in water

    Czech Academy of Sciences Publication Activity Database

    Král, Vladimír; Vašek, P.; Dolenský, B.


    Roč. 69, č. 5 (2004), s. 1126-1136 ISSN 0010-0765 R&D Projects: GA ČR GA203/02/0933; GA ČR GA203/02/0420; GA ČR GP203/03/D049 Grant - others:QLRT(XE) 2000-02360 Keywords : oligopyrrole macrocycles * porphyrins * calixpyrrols Subject RIV: CC - Organic Chemistry Impact factor: 1.062, year: 2004

  8. Synthesis of Macrocyclic Organo-Peptide Hybrids from Ribosomal Polypeptide Precursors via CuAAC-/hydrazide-mediated cyclization


    Smith, Jessica M.; Fasan, Rudi


    Macrocyclic peptides have attracted increasing attention as a potential new source of chemical probes and therapeutics. In particular, their conformationally restricted structure combined with a high degree of functional and stereochemical complexity make them promising scaffolds for targeting biomolecules with high affinity and selectivity. The exploration of this structural class rely on the availability of efficient and versatile methods for the generation of large and diversified librarie...

  9. Through-space electronic communication of zinc phthalocyanine with substituted [60]Fullerene bearing O2Nxaza-crown macrocyclic ligands (United States)

    Ghanbari, Bahram; Shahhoseini, Leila; Mahlooji, Niloofar; Gholamnezhad, Parisa; Taheri Rizi, Zahra


    Two new macrocyclic ligands containing 17- and 19-membered O2N3-donor aza-crowns anchored to [60]Fullerene were synthesized and characterized by employing HPLC, electrospray ionization mass (ESI-MS), 1H and 13C NMR, UV-vis, IR spectroscopies, as well as powder X-ray diffraction (PXRD) and thermogravimetric analysis (TGA) in solid state. TGA measurements revealed that upon linking each of these macrocycle rings to [60]Fullerene, the decomposition point measured for [60]Fullerene moiety was increased, indicating on the promoted stability of [60]Fullerene backbone during binding to these macrocyclic ligands. Moreover, the ground state non-covalent interactions of [60]Fullerene derivatives of O2Nx (x = 2, and 3) aza-crown macrocyclic ligands namely, L1-L4 with zinc phthalocyanine (ZnPc) were also investigated by UV-vis absorption, steady state and time resolved fluorescence spectrophotometry in N-methyl-2-pyrrolidone (NMP). The calculation of Stern-Volmer constants (KSV) indicated on existence of an efficient quenching mechanism comprising of the excited singlet state of ZnPc in the presence of L1-L4. The observation of an appropriate correlation between decrease in fluorescence intensity and lifetime parameters led us to propose the occurrence of a static mechanism for the fluorescence quenching of ZnPc in the presence of L1-L3. The binding constants (KBH) of L1-L4/ZnPc were also determined applying the fluorescence quenching experiments. Meanwhile, the incompatibility of both KSV and KBH values found for L4 was also described in terms of structural features using DFT calculations using the B3LYP functional and 6-31G* basis set.

  10. Manifold seal structure for fuel cell stack (United States)

    Collins, William P.


    The seal between the sides of a fuel cell stack and the gas manifolds is improved by adding a mechanical interlock between the adhesive sealing strip and the abutting surface of the manifolds. The adhesive is a material which can flow to some extent when under compression, and the mechanical interlock is formed providing small openings in the portion of the manifold which abuts the adhesive strip. When the manifolds are pressed against the adhesive strips, the latter will flow into and through the manifold openings to form buttons or ribs which mechanically interlock with the manifolds. These buttons or ribs increase the bond between the manifolds and adhesive, which previously relied solely on the adhesive nature of the adhesive.

  11. Directive Stacked Patch Antenna for UWB Applications

    Directory of Open Access Journals (Sweden)

    Sharif I. Mitu Sheikh


    Full Text Available Directional ultrawideband (UWB antennas are popular in wireless signal-tracking and body-area networks. This paper presents a stacked microstrip antenna with an ultrawide impedance bandwidth of 114%, implemented by introducing defects on the radiating patches and the ground plane. The compact (20×34 mm antenna exhibits a directive radiation patterns for all frequencies of the 3–10.6 GHz band. The optimized reflection response and the radiation pattern are experimentally verified. The designed UWB antenna is used to maximize the received power of a software-defined radio (SDR platform. For an ultrawideband impulse radio system, this class of antennas is essential to improve the performance of the communication channels.

  12. ATLAS software stack on ARM64 (United States)

    Smith, Joshua Wyatt; Stewart, Graeme A.; Seuster, Rolf; Quadt, Arnulf; ATLAS Collaboration


    This paper reports on the port of the ATLAS software stack onto new prototype ARM64 servers. This included building the “external” packages that the ATLAS software relies on. Patches were needed to introduce this new architecture into the build as well as patches that correct for platform specific code that caused failures on non-x86 architectures. These patches were applied such that porting to further platforms will need no or only very little adjustments. A few additional modifications were needed to account for the different operating system, Ubuntu instead of Scientific Linux 6 / CentOS7. Selected results from the validation of the physics outputs on these ARM 64-bit servers will be shown. CPU, memory and IO intensive benchmarks using ATLAS specific environment and infrastructure have been performed, with a particular emphasis on the performance vs. energy consumption.

  13. ATLAS software stack on ARM64

    CERN Document Server

    AUTHOR|(INSPIRE)INSPIRE-00529764; The ATLAS collaboration; Stewart, Graeme; Seuster, Rolf; Quadt, Arnulf


    This paper reports on the port of the ATLAS software stack onto new prototype ARM64 servers. This included building the “external” packages that the ATLAS software relies on. Patches were needed to introduce this new architecture into the build as well as patches that correct for platform specific code that caused failures on non-x86 architectures. These patches were applied such that porting to further platforms will need no or only very little adjustments. A few additional modifications were needed to account for the different operating system, Ubuntu instead of Scientific Linux 6 / CentOS7. Selected results from the validation of the physics outputs on these ARM 64-bit servers will be shown. CPU, memory and IO intensive benchmarks using ATLAS specific environment and infrastructure have been performed, with a particular emphasis on the performance vs. energy consumption.

  14. Stacked generalization: an introduction to super learning. (United States)

    Naimi, Ashley I; Balzer, Laura B


    Stacked generalization is an ensemble method that allows researchers to combine several different prediction algorithms into one. Since its introduction in the early 1990s, the method has evolved several times into a host of methods among which is the "Super Learner". Super Learner uses V-fold cross-validation to build the optimal weighted combination of predictions from a library of candidate algorithms. Optimality is defined by a user-specified objective function, such as minimizing mean squared error or maximizing the area under the receiver operating characteristic curve. Although relatively simple in nature, use of Super Learner by epidemiologists has been hampered by limitations in understanding conceptual and technical details. We work step-by-step through two examples to illustrate concepts and address common concerns.

  15. Dinuclear Silver(I) and Copper(II) Complexes of Hexadentate Macrocyclic Ligands Containing p-Xylyl Spacers

    DEFF Research Database (Denmark)

    McKenzie, Christine J.; Nielsen, Lars Preuss; Søtofte, Inger


    The cyclocondensation of terephthalic aldehyde with N,N-bis(3-aminopropyl)-methylamine in the presence of silver(I) gives the dinuclear tetramine Schiff base macrocyclic complex, [Ag2L1](NO3)2 (L1=7,22-N,N'-dimethyl-3,7,11,18, 22,26-hexaazatricyclo[]-tetratricosa-2,11,13,15,1 7......,26,28,30,31,33-decaene). [Ag2L1](NO3)2 crystallizes in the monoclinic space group P21/c, with a=14.153(6), b=12.263(4), c=9.220(2) Å, beta=97.52(3) Å and Z=2. The silver ions are strongly coordinated at each end of the macrocycle by the two imine nitrogen atoms [2.177(3) and 2.182(3) Å] with close interatomic...... interactions to an oxygen atom of a nitrate ion and an amine nitrogen atom [2.580(2) and 2.690(2) Å]. The Ag...Ag distance is 6.892(3) Å. The free tetraimine macrocycle, L1, was obtained by treatment of [Ag2L1](NO3)2 with an excess of iodide, and the reduced derivative 7,22-N,N'-dimethyl-3...

  16. Macrocyclic-, polycyclic-, and nitro musks in cosmetics, household commodities and indoor dusts collected from Japan: implications for their human exposure. (United States)

    Nakata, Haruhiko; Hinosaka, Mari; Yanagimoto, Hayato


    This paper reported the occurrence and concentrations of macrocyclic-, polycyclic- and nitro musks in cosmetics and household commodities collected from Japan. The high concentrations and detection frequencies of Musk T, habanolide, and exaltolides were found in commercial products, suggesting their large amounts of production and usage in Japan. Polycyclic musks, HHCB and OTNE, also showed high concentrations in cosmetics and products. The estimated dairy intakes of Musk T and HHCB by the dermal exposure to commercial products were 7.8 and 7.9 μg/kg/day in human, respectively, and perfume and body lotion are dominant exposure sources. We also analyzed synthetic musks in house dusts. Polycyclic musks, HHCB and OTNE, showed high concentrations in samples, but macrocyclic musks were detected only in a few samples, although these types of musks were highly detected in commercial products. This is probably due to easy-degradation of macrocyclic musks in indoor environment. The dairy intakes of HHCB by dust ingestions were 0.22 ng/kg/day in human, which were approximately five orders of magnitudes lower than those of dermal absorption from commercial household commodities. Copyright © 2014 Elsevier Inc. All rights reserved.

  17. Investigation of the potential of silica-bonded macrocyclic ligands for separation of metal ions from nuclear waste

    International Nuclear Information System (INIS)

    Camaioni, D.M.; Colton, N.G.; Bruening, R.L.


    This report describes the testing of some novel separations materials known as SuperLig trademark materials for their ability to separate efficiently and selectively certain metal ions from a synthetic, nonradioactive nuclear waste solution. The materials, developed and patented by IBC Advanced Technologies, are highly selective macrocyclic ligands that have been covalently bonded to silica gel. The SuperLig trademark materials that were tested are: (1) SuperLig trademark 601 for barium (Ba 2+ ) and strontium (Sr 2+ ) separation, (2) SuperLig trademark 602 for cesium (Cs + ) and rubidium (Rb + ) separation, (3) SuperLig trademark 27 for palladium (Pd 2+ ) separation, and (4) SuperLig trademark II for silver (Ag + ) and ruthenium (Ru 3+ ) separation. Our observations show that the technology for separating metal ions using silica-bonded macrocycles is essentially sound and workable to varying degrees of success that mainly depend on the affinity of the macrocycle for the metal ion of interest. It is expected that ligands will be discovered or synthesized that are amenable to separating metal ions of interest using this technology. Certainly more development, testing, and evaluation is warranted. 3 figs., 11 tabs

  18. Through-Space Paramagnetic NMR Effects in Host-Guest Complexes: Potential Ruthenium(III) Metallodrugs with Macrocyclic Carriers. (United States)

    Chyba, Jan; Novák, Martin; Munzarová, Petra; Novotný, Jan; Marek, Radek


    The potential of paramagnetic ruthenium(III) compounds for use as anticancer metallodrugs has been investigated extensively during the past several decades. However, the means by which these ruthenium compounds are transported and distributed in living bodies remain relatively unexplored. In this work, we prepared several novel ruthenium(III) compounds with the general structure Na + [ trans-Ru III Cl 4 (DMSO)(L)] - (DMSO = dimethyl sulfoxide), where L stands for pyridine or imidazole linked with adamantane, a hydrophobic chemophore. The supramolecular interactions of these compounds with macrocyclic carriers of the cyclodextrin (CD) and cucurbit[ n]uril (CB) families were investigated by NMR spectroscopy, X-ray diffraction analysis, isothermal titration calorimetry, and relativistic DFT methods. The long-range hyperfine NMR effects of the paramagnetic guest on the host macrocycle are related to the distance between them and their relative orientation in the host-guest complex. The CD and CB macrocyclic carriers being studied in this account can be attached to a vector that attracts the drug-carrier system to a specific biological target and our investigation thus introduces a new possibility in the field of targeted delivery of anticancer metallodrugs based on ruthenium(III) compounds.

  19. Actuators Using Piezoelectric Stacks and Displacement Enhancers (United States)

    Bar-Cohen, Yoseph; Sherrit, Stewart; Bao, Xiaoqi; Badescu, Mircea; Lee, Hyeong Jae; Walkenmeyer, Phillip; Lih, Shyh-Shiuh


    Actuators are used to drive all active mechanisms including machines, robots, and manipulators to name a few. The actuators are responsible for moving, manipulating, displacing, pushing and executing any action that is needed by the mechanism. There are many types and principles of actuation that are responsible for these movements ranging from electromagnetic, electroactive, thermo-mechanic, piezoelectric, electrostrictive etc. Actuators are readily available from commercial producers but there is a great need for reducing their size, increasing their efficiency and reducing their weight. Studies at JPL’s Non Destructive Evaluation and Advanced Actuators (NDEAA) Laboratory have been focused on the use of piezoelectric stacks and novel designs taking advantage of piezoelectric’s potential to provide high torque/force density actuation and high electromechanical conversion efficiency. The actuators/motors that have been developed and reviewed in this paper are operated by various horn configurations as well as the use of pre-stress flexures that make them thermally stable and increases their coupling efficiency. The use of monolithic designs that pre-stress the piezoelectric stack eliminates the use of compression stress bolt. These designs enable the embedding of developed solid-state motors/actuators in any structure with the only macroscopically moving parts are the rotor or the linear translator. Finite element modeling and design tools were used to determine the requirements and operation parameters and the results were used to simulate, design and fabricate novel actuators/motors. The developed actuators and performance will be described and discussed in this paper.

  20. Evaluation of nitrogen-rich macrocyclic ligands for the chelation of therapeutic bismuth radioisotopes. (United States)

    Wilson, Justin J; Ferrier, Maryline; Radchenko, Valery; Maassen, Joel R; Engle, Jonathan W; Batista, Enrique R; Martin, Richard L; Nortier, Francois M; Fassbender, Michael E; John, Kevin D; Birnbaum, Eva R


    The use of α-emitting isotopes for radionuclide therapy is a promising treatment strategy for small micro-metastatic disease. The radioisotope (213)Bi is a nuclide that has found substantial use for targeted α-therapy (TAT). The relatively unexplored aqueous chemistry of Bi(3+), however, hinders the development of bifunctional chelating agents that can successfully deliver these Bi radioisotopes to the tumor cells. Here, a novel series of nitrogen-rich macrocyclic ligands is explored for their potential use as Bi-selective chelating agents. The ligands, 1,4,7,10-tetrakis(pyridin-2-ylmethyl)-1,4,7,10-tetraazacyclododecane (L(py)), 1,4,7,10-tetrakis(3-pyridazylmethyl)-1,4,7,10-tetraazacyclododecane (L(pyd)), 1,4,7,10-tetrakis(4-pyrimidylmethyl)-1,4,7,10-tetraazacyclododecane (L(pyr)), and 1,4,7,10-tetrakis(2-pyrazinylmethyl)-1,4,7,10-tetraazacyclododecane (L(pz)), were prepared by a previously reported method and investigated here for their abilities to bind Bi radioisotopes. The commercially available and commonly used ligands 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid (DOTA) and N-[(R)-2-amino-3-(p-isothiocyanato-phenyl)propyl]-trans-(S,S)- cyclohexane-1,2-diamine-N,N,N',N",N"-pentaacetic acid (CHX-A''-DTPA) were also explored for comparative purposes. Radio-thin-layer chromatography (TLC) was used to measure the binding kinetics and stabilities of the complexes formed. The long-lived isotope, (207)Bi (t(1/2)=32 years), was used for these studies. Density functional theory (DFT) calculations were also employed to probe the ligand interactions with Bi(3+) and the generator parent ion Ac(3+). In contrast to DOTA and CHX-A''-DTPA, these nitrogen-rich macrocycles selectively chelate Bi(3+) in the presence of the parent isotope Ac(3+). Among the four tested, L(py) was found to exhibit optimal Bi(3+)-binding kinetics and complex stability. L(py) complexes Bi(3+) more rapidly than DOTA, yet the resulting complexes are of similar stability. DFT calculations

  1. Aza-macrocyclic complexes of the Group 1 cations - synthesis, structures and density functional theory study. (United States)

    Dyke, John; Levason, William; Light, Mark E; Pugh, David; Reid, Gillian; Bhakhoa, Hanusha; Ramasami, Ponnadurai; Rhyman, Lydia


    The Group 1 complexes, [M(Me6[18]aneN6)][BAr(F)] (M = Li-Cs; Me6[18]aneN6 = 1,4,7,10,13,16-hexamethyl-1,4,7,10,13,16-hexaazacyclooctadecane; BAr(F) = tetrakis{3,5-bis(trifluoromethyl)-phenyl}borate), are obtained in high yield by reaction of the macrocycle with M[BAr(F)] in anhydrous CH2Cl2 solution, and characterised spectroscopically ((1)H, (13)C{(1)H}, (7)Li, (23)Na, and (133)Cs NMR), by microanalysis and, for M = Li, K, and Rb, by single crystal X-ray analysis. The structures show N6-coordination to the metal ion; the small ionic radius for Li(+) leads to a puckered conformation. In contrast, the K(+) ion fits well into the N6 plane, with the [BAr(F)](-) anions above and below, leading to two K(+) species in the asymmetric unit (a hexagonal planar [K(Me6[18]aneN6)](+) cation and a '[K(Me6[18]aneN6)(κ(1)-BAr(F))2](-) anion', with long axial KF interactions). The Rb(+) ion sits above the N6 plane, with two long axial RbF interactions in one cation and two long, mutually cis RbF interactions in the other. The unusual sandwich cations, [M(Me3tacn)2](+) (M = Na, K; distorted octahedral, N6 donor set) and half-sandwich cations [Li(Me3tacn)(thf)](+) (distorted tetrahedron, N3O donor set), [Li(Me4cyclen)(OH2)](+), and [Na(Me4cyclen)(thf)](+) (both distorted square pyramids with N4O donor sets) were also prepared (Me3tacn = 1,4,7-trimethyl-1,4,7-triazacyclononane, Me4cyclen = 1,4,7,10-tetramethyl-1,4,7,10-tetraazacyclododecane). Density functional theory (DFT) calculations, using the BP86 and B3LYP functionals, show that the accessibility of the [M(Me3tacn)2](+) sandwich cations depends strongly on the M(+) ionic radius, such that it is sufficiently large to avoid steric clashing between the Me groups of the two rings, and small enough to avoid very acute N-M-N chelate angles. The calculations also show that coordination to the Group 1 cation involves significant donation of electron density from the p-orbitals on the N atoms of the macrocycle, rather than purely

  2. Biomechanical Assessment of Motor Abilities in Male Handball Players During the Annual Training Macrocycle

    Directory of Open Access Journals (Sweden)

    Sacewicz Tomasz


    Full Text Available Introduction. The aim of the study was to determine the torque of the knee extensors and flexors of the lead lower limb, the torque of the shoulder extensors and flexors of the dominant upper limb, and the torque generated by the muscles of the kinematic chain going from the trail lower limb to the hand of the dominant limb in male handball players during the annual training macrocycle. Changes in jump height and throwing velocity were also investigated. Material and methods. The study involved 13 handball players from a Polish second-league team. The measurements were performed four times: at the beginning of the preparation period, at the beginning of the season, at the end of the first part of the season, and at the end of the second part of the season. Torque was measured in isokinetic and isometric conditions. Jumping ability was tested using a piezoelectric platform, and throwing velocity was measured with a speed radar gun. Results. The study found statistically significant differences between the relative torque values of the knee extensors (p < 0.002 and flexors (p < 0.003 of the lead leg measured in isokinetic conditions between the first three measurements and the final one. Isokinetic measurement of the torque of the muscles of the kinematic chain going from the trail leg to the hand of the dominant arm decreased in a statistically significant way at the end of the season. As for the results of the measurement of the torque of the shoulder extensors and flexors in static conditions, no statistically significant differences were observed between the four measurements. However, statistically significant differences were noted in jumping ability and throwing velocity in the annual training macrocycle. Conclusions. The results of the study indicate that there is a need to perform regular assessments of players’ strength and jumping ability during the competition period. There is a need to modify the training methods used during the

  3. Next generation macrocyclic and acyclic cationic lipids for gene transfer: Synthesis and in vitro evaluation. (United States)

    Jubeli, Emile; Maginty, Amanda B; Abdul Khalique, Nada; Raju, Liji; Abdulhai, Mohamad; Nicholson, David G; Larsen, Helge; Pungente, Michael D; Goldring, William P D


    Previously we reported the synthesis and in vitro evaluation of four novel, short-chain cationic lipid gene delivery vectors, characterized by acyclic or macrocyclic hydrophobic regions composed of, or derived from, two 7-carbon chains. Herein we describe a revised synthesis of an expanded library of related cationic lipids to include extended chain analogues, their formulation with plasmid DNA (pDNA) and in vitro delivery into Chinese hamster ovarian (CHO-K1) cells. The formulations were evaluated against each other based on structural differences in the hydrophobic domain and headgroup. Structurally the library is divided into four sets based on lipids derived from two 7- or two 11-carbon hydrophobic chains, C7 and C11 respectively, which possess either a dimethylamine or a trimethylamine derived headgroup. Each set includes four cationic lipids based on an acyclic or macrocyclic, saturated or unsaturated hydrophobic domain. All lipids were co-formulated with the commercial cationic lipid 1,2-dimyristoyl-sn-glycero-3-ethylphosphocholine (EPC) in a 1:1 molar ratio, along with one of two distinct neutral co-lipids, cholesterol or 1,2-dioleoyl-sn-glycero-3-phosphoethanolamine (DOPE) in an overall cationic-to-neutral lipid molar ratio of 3:2. Binding of lipid formulations with DNA, and packing morphology associated with the individual lipid-DNA complexes were characterized by gel electrophoresis and small angle X-ray diffraction (SAXD), respectively. As a general trend, lipoplex formulations based on mismatched binary cationic lipids, composed of a shorter C7 lipid and the longer lipid EPC (C14), were generally associated with higher transfection efficiency and lower cytotoxicity than their more closely matched C11/EPC binary lipid formulation counterparts. Furthermore, the cyclic lipids gave transfection levels as high as or greater than their acyclic counterparts, and formulations with cholesterol exhibited higher transfection and lower cytotoxicity than those

  4. Simultaneous stack-gas scrubbing and waste water treatment (United States)

    Poradek, J. C.; Collins, D. D.


    Simultaneous treatment of wastewater and S02-laden stack gas make both treatments more efficient and economical. According to results of preliminary tests, solution generated by stack gas scrubbing cycle reduces bacterial content of wastewater. Both processess benefit by sharing concentrations of iron.

  5. A Software Managed Stack Cache for Real-Time Systems

    DEFF Research Database (Denmark)

    Jordan, Alexander; Abbaspourseyedi, Sahar; Schoeberl, Martin


    In a real-time system, the use of a scratchpad memory can mitigate the difficulties related to analyzing data caches, whose behavior is inherently hard to predict. We propose to use a scratchpad memory for stack allocated data. While statically allocating stack frames for individual functions to ...

  6. Calculation of AC losses in large HTS stacks and coils

    DEFF Research Database (Denmark)

    Zermeno, Victor; Abrahamsen, Asger Bech; Mijatovic, Nenad


    In this work, we present a homogenization method to model a stack of HTS tapes under AC applied transport current or magnetic field. The idea is to find an anisotropic bulk equivalent for the stack of tapes, where the internal alternating structures of insulating, metallic, superconducting and su...

  7. Efficient Context Switching for the Stack Cache: Implementation and Analysis

    DEFF Research Database (Denmark)

    Abbaspourseyedi, Sahar; Brandner, Florian; Naji, Amine


    , the analysis of the stack cache was limited to individual tasks, ignoring aspects related to multitasking. A major drawback of the original stack cache design is that, due to its simplicity, it cannot hold the data of multiple tasks at the same time. Consequently, the entire cache content needs to be saved...

  8. The behaviour of stacking fault energy upon interstitial alloying. (United States)

    Lee, Jee-Yong; Koo, Yang Mo; Lu, Song; Vitos, Levente; Kwon, Se Kyun


    Stacking fault energy is one of key parameters for understanding the mechanical properties of face-centered cubic materials. It is well known that the plastic deformation mechanism is closely related to the size of stacking fault energy. Although alloying is a conventional method to modify the physical parameter, the underlying microscopic mechanisms are not yet clearly established. Here, we propose a simple model for determining the effect of interstitial alloying on the stacking fault energy. We derive a volumetric behaviour of stacking fault energy from the harmonic approximation to the energy-lattice curve and relate it to the contents of interstitials. The stacking fault energy is found to change linearly with the interstitial content in the usual low concentration domain. This is in good agreement with previously reported experimental and theoretical data.

  9. Dynamic Model of High Temperature PEM Fuel Cell Stack Temperature

    DEFF Research Database (Denmark)

    Andreasen, Søren Juhl; Kær, Søren Knudsen


    The present work involves the development of a model for predicting the dynamic temperature of a high temperature PEM (HTPEM) fuel cell stack. The model is developed to test different thermal control strategies before implementing them in the actual system. The test system consists of a prototype...... parts, where also the temperatures are measured. The heat balance of the system involves a fuel cell model to describe the heat added by the fuel cells when a current is drawn. Furthermore the model also predicts the temperatures, when heating the stack with external heating elements for start-up, heat...... the stack at a high stoichiometric air flow. This is possible because of the PBI fuel cell membranes used, and the very low pressure drop in the stack. The model consists of a discrete thermal model dividing the stack into three parts: inlet, middle and end and predicting the temperatures in these three...

  10. Direct methanol fuel cell stack based on MEMS technology (United States)

    Zhang, Yufeng; Tang, Xiaochuan; Yuan, Zhenyu; Liu, Xiaowei


    This paper presents a design configuration of silicon-based micro direct methanol fuel cell (DMFC) stack in a planar array. The integrated series connection is oriented in a "flip-flop" configuration with electrical interconnections made by thin-film metal layers that coat the flow channels etched in the silicon substrate. The configuration features small connection space and low contact resistance. The MEMS fabrication process was utilized to fabricate the silicon plates of DMFC stack. This DMFC stack with an active area of 64mm x 11mm was characterized at room temperature and normal atmosphere. Experimental results show that the prototype stack is able to generate an open-circuit voltage of 2.7V and a maximum power density of 2.2mW/cm2, which demonstrate the feasibility of this new DMFC stack configuration.

  11. Deformation Induced Microtwins and Stacking Faults in Aluminum Single Crystal (United States)

    Han, W. Z.; Cheng, G. M.; Li, S. X.; Wu, S. D.; Zhang, Z. F.


    Microtwins and stacking faults in plastically deformed aluminum single crystal were successfully observed by high-resolution transmission electron microscope. The occurrence of these microtwins and stacking faults is directly related to the specially designed crystallographic orientation, because they were not observed in pure aluminum single crystal or polycrystal before. Based on the new finding above, we propose a universal dislocation-based model to judge the preference or not for the nucleation of deformation twins and stacking faults in various face-centered-cubic metals in terms of the critical stress for dislocation glide or twinning by considering the intrinsic factors, such as stacking fault energy, crystallographic orientation, and grain size. The new finding of deformation induced microtwins and stacking faults in aluminum single crystal and the proposed model should be of interest to a broad community.

  12. Physical Sciences Laboratory 1 Rooftop Stack Mixing Study

    Energy Technology Data Exchange (ETDEWEB)

    Flaherty, Julia E. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Antonio, Ernest J. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States)


    To address concerns about worker exposures on the Physical Science Laboratory (PSL) rooftop, a tracer study was conducted to measure gaseous tracer concentrations downwind of six stacks on the southern half of the PSL building (PSL-1). These concerns were raised, in part, due to the non-standard configuration of the stacks on this building. Five of the six stacks were only about 8 feet tall, with one shorter stack that was essentially level with the roof deck. These stacks were reconfigured in August 2016, and these exhaust points on PSL-1 are now 18 feet tall. This report describes the objectives of the tracer tests performed on PSL-1, provides an overview of how the tests were executed, and presents results of the tests. The tests on the PSL rooftop were a follow-on project from a similar study performed on the LSL-II ventilation exhaust (Flaherty and Antonio, 2016).

  13. Occurrence and stability of lone pair–π stacking interactions between ribose and nucleobases in functional RNAs

    KAUST Repository

    Chawla, Mohit


    The specific folding pattern and function of RNA molecules lies in various weak interactions, in addition to the strong base-base pairing and stacking. One of these relatively weak interactions, characterized by the stacking of the O4′ atom of a ribose on top of the heterocycle ring of a nucleobase, has been known to occur but has largely been ignored in the description of RNA structures. We identified 2015 ribose–base stacking interactions in a high-resolution set of non-redundant RNA crystal structures. They are widespread in structured RNA molecules and are located in structural motifs other than regular stems. Over 50% of them involve an adenine, as we found ribose-adenine contacts to be recurring elements in A-minor motifs. Fewer than 50% of the interactions involve a ribose and a base of neighboring residues, while approximately 30% of them involve a ribose and a nucleobase at least four residues apart. Some of them establish inter-domain or inter-molecular contacts and often implicate functionally relevant nucleotides. In vacuo ribose-nucleobase stacking interaction energies were calculated by quantum mechanics methods. Finally, we found that lone pair–π stacking interactions also occur between ribose and aromatic amino acids in RNA–protein complexes.

  14. Mono- and multilayers of molecular spoked carbazole wheels on graphite

    Directory of Open Access Journals (Sweden)

    Stefan-S. Jester


    Full Text Available Self-assembled monolayers of a molecular spoked wheel (a shape-persistent macrocycle with an intraannular spoke/hub system and its synthetic precursor are investigated by scanning tunneling microscopy (STM at the liquid/solid interface of 1-octanoic acid and highly oriented pyrolytic graphite. The submolecularly resolved STM images reveal that the molecules indeed behave as more or less rigid objects of certain sizes and shapes – depending on their chemical structures. In addition, the images provide insight into the multilayer growth of the molecular spoked wheels (MSWs, where the first adlayer acts as a template for the commensurate adsorption of molecules in the second layer.

  15. Reflector imaging by diffraction stacking with stacking velocity analysis; Jugo sokudo kaiseki wo tomonau sanran jugoho ni yoru hanshamen imaging

    Energy Technology Data Exchange (ETDEWEB)

    Matsushima, J.; Rokugawa, S.; Kato, Y. [The University of Tokyo, Tokyo (Japan). Faculty of Engineering; Yokota, T. [Japan National Oil Corp., Tokyo (Japan); Miyazaki, T. [Geological Survey of Japan, Tsukuba (Japan)


    Concerning seismic reflection survey for geometrical arrangement between pits, the scattering stacking method with stacking velocity analysis is compared with the CDP (common depth point horizontal stacking method). The advantages of the CDP supposedly include the following. Since it presumes an average velocity field, it can determine velocities having stacking effects. The method presumes stratification and, since such enables the division of huge quantities of observed data into smaller groups, more data can be calculated in a shorter time period. The method has disadvantages, attributable to its presuming an average velocity field, that accuracy in processing is lower when the velocity field contrast is higher, that accuracy in processing is low unless stratification is employed, and that velocities obtained from stacking velocity analysis are affected by dipped structures. Such shortcomings may be remedied in the scattering stacking method with stacking velocity analysis. Possibilities are that, as far as the horizontal reflection plane is concerned, it may yield stack records higher in S/N ratio than the CDP. Findings relative to dipped reflection planes will be introduced at the presentation. 6 refs., 12 figs.

  16. Some aspects of the extraction separation of actinides by macrocyclic crown compounds

    International Nuclear Information System (INIS)

    Kumar, Anil; Singh, R.K.; Bajpai, D.D.; Shukla, J.P.


    Selective and effective extraction-separation of U(VI) and Pu(IV) from aqueous nitric acid media by several crown ethers have been investigated in detail. The critical study of various parameters namely aqueous phase acidity, reagent concentration, diluent, period of equilibration, aqueous to organic phase ratio, strippant and diverse ions, have established the conditions for their optimum extraction. Influence of the introduction of sulfur into a crown ether ring forming a mixed sulfur-oxygen containing macrohetrocycle for improved extraction of actinides is also studied. The species extracted appear to be of ion-pair type, UO 2 (CE) 2+ .2NO 3- and Pu(CE) 2 4+ .4NO 3- formed with U(VI) and Pu(IV), respectively. The apparent extraction equilibrium constant, log Kex, into toluene by DC18C6 with U(VI) is 0.44 and 4.44 for Pu(IV). Recovery of actinides from loaded macrocycles is easily accomplished using dilute oxalic acid, perchloric acid, sulphuric acid or sodium carbonate as the strippants. The lack of interference from even appreciable amounts of possible fission product contaminants is a notable feature of this separation procedure. (author). 20 refs., 6 figs., 6 tabs

  17. Synthesis and hydrogenation application of Pt-Pd bimetallic nanocatalysts stabilized by macrocycle-modified dendrimer (United States)

    Jin, Zhijun; Xiao, Haiyan; Zhou, Wei; Zhang, Dongqiao; Peng, Xiaohong


    Different generations of poly(propylene imine) (Gn-PPI) terminated with N-containing 15-membered triolefinic macrocycle (GnM) (n = 2, 3, 4, 5) were prepared. The bimetallic nanoparticle catalysts GnM-(Ptx/Pd10-x) (x = 0, 3, 5, 7, 10) were prepared by the synchronous ligand-exchange reaction between GnM and the complexes of Pt(PPh3)4 and Pd(PPh3)4. The structure and catalytic properties of GnM-(Ptx/Pd10-x) were characterized via Fourier transform infrared spectroscopy, 1H nuclear magnetic resonance spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, high-resolution transmission electron microscopy, energy-dispersive spectroscopy and inductively coupled plasma atomic emission spectroscopy. The novel bimetallic Pd-Pt nanoparticle catalysts stabilized by dendrimers (DSNs) present higher catalytic activities for the hydrogenation of dimeric acid (DA) than that of nitrile butadiene rubber (NBR). It can be concluded that bimetallic Pd-Pt DSNs possess alloying and synergistic electronic effects on account of the hydrogenation degree (HD) of DA and NBR. Furthermore, the HD of DA and NBR shows a remarkable decrease with the incremental generations (n) of GnM-(Pt3/Pd7) (n = 2, 3, 4, 5).

  18. Synthesis, characterization and biological activity of symmetric dinuclear complexes derived from a novel macrocyclic compartmental ligand

    International Nuclear Information System (INIS)

    Mruthyunjayaswamy, B.H.M.; Ijare, Omkar B.; Jadegoud, Y.


    A phenol based novel macrocyclic binucleating compartmental ligand N,N-bis(2,6-diiminomethyl-4-methyl-1-hydroxyphenyl)malonoyldicarboxamide was prepared. The complexes were prepared by template method by reacting 2,6-diformyl-4-methylphenol, malonoyl dihydrazide and the metal chlorides of Cu(II), Ni(II), Co(II), Cd(II), Zn(II) and Hg(II) in methanol to get a series of dinuclear complexes. The complexes were characterized by elemental analyses, conductivity measurements, magnetic susceptibility data, IR, UV-Vis, ESR, NMR and FAB mass spectral data. The dinuclear nature of the complexes was confirmed on the basis of elemental analyses, magnetic susceptibility, ESR and FAB mass spectral data. The ligand as well as Cu(II), Ni(II), Co(II) and Zn(II) complexes were tested for their antibacterial and antifungal properties against Escherichia coli, Staphyloccocus aureus, Aspergillus niger and Fusarium oxysporum. Magnetic susceptibility measurements of Cu(II), Ni(II) and Co(II) complexes reveal that these complexes exhibit antiferromagnetic coupling behavior due to the presence of two metal ions in close proximity. FAB mass spectrum of the Cu(II) complex gave a clear evidence for the dinuclear nature. The ligand and the complexes were found to be less active against the tested bacteria, but the ligand alone was found active against the fungus Fusarium oxysporum. (author)

  19. Macrocyclic cavitands cucurbit[n]urils: prospects for application in biochemistry, medicine and nanotechnology (United States)

    Gerasko, O. A.; Kovalenko, E. A.; Fedin, V. P.


    The prospects of using the organic macrocyclic cavitands cucurbit[n]urils (CB[n]) and their derivatives in biochemistry, medicine and nanotechnology are considered. A combination of CB[n] characteristics, such as a rigid highly symmetrical structure, polarized hydrophilic portals, a rather large intramolecular hydrophobic cavity, as well as high resistance to thermolysis and corrosive media and low toxicity, account for a wide range of unique opportunities for the deliberate design of new functional materials, which may find application in various areas of modern chemistry and new technologies. Inclusion compounds of CB[n] with biologically active molecules demonstrate a high potential for the design of a new generation of prolonged action pharmaceuticals. The review presents the prospects for the application of CB[n] to manufacture unique materials, such as CB[n]-containing vesicles, films and surfaces, suitable for immobilization of various molecules and nanoparticles on their surface and for the separation of complex mixtures. Potential applications of CB[n]-modified electrodes and hydrogels are analyzed, and the use of CB[n] in proton-conducting materials and materials for the gas sorption and separation are discussed. The bibliography includes 164 references.

  20. An eighteen-membered macrocyclic ligand for actinium-225 targeted alpha therapy

    Energy Technology Data Exchange (ETDEWEB)

    Thiele, Nikki A.; MacMillan, Samantha N.; Wilson, Justin J. [Cornell Univ., Ithaca, NY (United States). Chemistry and Chemical Biology; Brown, Victoria; Jermilova, Una; Ramogida, Caterina F.; Robertson, Andrew K.H.; Schaffer, Paul; Radchenko, Valery [TRIUMF, Vancouver, BC (Canada). Life Science Div.; Kelly, James M.; Amor-Coarasa, Alejandro; Nikolopoulou, Anastasia; Ponnala, Shashikanth; Williams, Clarence Jr.; Babich, John W. [Radiology, Weill Cornell Medicine, New York, NY (United States); Rodriguez-Rodriguez, Cristina [British Columbia Univ., Vancouver, BC (Canada). Dept. of Physics and Astronomy and Centre for Comparative Medicine


    The 18-membered macrocycle H{sub 2}macropa was investigated for {sup 225}Ac chelation in targeted alpha therapy (TAT). Radiolabeling studies showed that macropa, at submicromolar concentration, complexed all {sup 225}Ac (26 kBq) in 5 min at RT. [{sup 225}Ac(macropa)]{sup +} remained intact over 7 to 8 days when challenged with either excess La{sup 3+} ions or human serum, and did not accumulate in any organ after 5 h in healthy mice. A bifunctional analogue, macropa-NCS, was conjugated to trastuzumab as well as to the prostate-specific membrane antigen-targeting compound RPS-070. Both constructs rapidly radiolabeled {sup 225}Ac in just minutes at RT, and macropa-Tmab retained >99 % of its {sup 225}Ac in human serum after 7 days. In LNCaP xenograft mice, {sup 225}Ac-macropa-RPS-070 was selectively targeted to tumors and did not release free {sup 225}Ac over 96 h. These findings establish macropa to be a highly promising ligand for {sup 225}Ac chelation that will facilitate the clinical development of {sup 225}Ac TAT for the treatment of soft-tissue metastases. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  1. Unraveling the Multistimuli Responses of a Complex Dynamic System of Pseudopeptidic Macrocycles. (United States)

    Valdivielso, Angel M; Puig-Castellví, Francesc; Atcher, Joan; Solà, Jordi; Tauler, Romà; Alfonso, Ignacio


    Dynamic combinatorial libraries (DCLs) are excellent benchmark models to study the stimuli-responsiveness of chemical networks. However, increasingly complex systems are difficult to analyze with simple data analysis methods, because many variables and connections must be considered for their full understanding. Here we propose the use of multivariate data analysis methods to bisect the evolution of a complex synthetic dynamic library of pseudopeptidic macrocycles, containing side chains with charges of different sign. Several stimuli (ionic strength, pH and the presence of a biogenic polyamine) were applied to the same dynamic chemical mixture, and the adaptation of the whole system was characterized by HPLC and analyzed with principal component analysis (PCA) and multivariate curve resolution-alternating least squares (MCR-ALS) methods. Both multivariate data analysis chemometric approaches are an excellent combination to extract both qualitative and semi-quantitative information about the adaptive process of the library upon the action of each stimulus. The resolution of the system with these chemometric tools proved to be especially useful when two inter-connected stimuli were combined in the same dynamic system. Our results demonstrate the utility of these two approaches for the analysis of complex dynamic chemical systems and open the way toward the application of these powerful tools in the emergent field of systems chemistry. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Noncovalent Interactions Accompanying Encapsulation of Resorcinol within Azacalix[4]pyridine Macrocycle. (United States)

    Lande, Dipali N; Bhadane, Smita A; Gejji, Shridhar P


    Electronic structure and noncovalent interactions within the inclusion complexes of resorcinol and calix[4]pyridine (CXP[4]) or azacalix[4]pyridine (N-CXP[4]) macrocycles have been analyzed by employing hybrid M06-2X density functional theory. It has been demonstrated that substitution of a heteroatom (-NH-) at the bridging position of the CXP[4] alters the shape of the cavity from a "box-shaped" to funnel-like one. Penetration of resorcinol guest within the CXP[4] cavity renders a "butterfly-like" structure to the complex, whereas the N-CXP[4] complex reveals distorted geometry with the guest being nearer to one of the pyridine rings at the upper rim of the host. Underlying hydrogen bonding, π···π, and other weak interactions are characterized using the Quantum Theory of Atoms in Molecules (QTAIM) and Noncovalent Interactions Reduced Density Gradient (NCI-RDG) methods. The coexistence of multiple intermolecular interactions is envisaged through the frequency shifts of the characteristic -NH and -OH vibrations in their calculated vibrational spectra. The guest protons confined to the host cavity exhibit shielding, while those facilitating hydrogen bonding engender the downfield signals in their calculated 1 H NMR spectra.

  3. New ventures in the genotoxic and cytotoxic effects of macrocyclic lactones, abamectin and ivermectin. (United States)

    Molinari, G; Soloneski, S; Larramendy, M L


    Abamectin and Ivermectin are 2 closely related members of the Avermectin family of 16-membered macrocyclic lactones derived from the actinomycete Streptomyces avermectinius which exhibit extraordinary anthelmintic activity. They are used worldwide in veterinary and human medicine as well as in agriculture. In the present review we summarized the results published so far for estimating the genotoxicity and cytotoxicity exerted by both compounds in several cellular systems. Although both compounds do not induce in vitro and in vivo gene mutations in either bacterial or mammalian cells, there is no concrete evidence of a clear clastogenic effect exerted both in vitro and in vivo in mammalian cells. However, reports indicating that both anthelmintic agents are able to induce single DNA-strand breaks in vitro and inhibit cell growth either in vitro or in in vivo bioassays, are scarce. Taking into account the similarity of the genotoxicity and cytotoxicity exerted by both antibiotics, and that only Abamectin has been classified so far as a class II toxicity pesticide by the EPA, the necessity of reconsideration for a further hazard evaluation of Ivermectin by an international regulatory agency(ies) is strongly recommended. Copyright 2010 S. Karger AG, Basel.

  4. Liquid-Liquid Extraction of Transition Metal Cations by Glyoximes and Their Macrocyclic Glyoxime Ether Derivatives

    Directory of Open Access Journals (Sweden)

    Nazan Karapinar


    Full Text Available Liquid-liquid extraction of various alkalis (Li+, Na+, K+, and Cs+, transition metals (Co2+, Ni2+, Cu2+, Zn2+, Cd2+, and Hg2+, and Pb2+ cations with phenylglyoxime (L1, p-tolylglyoxime (L2, N′-(4′-Benzo[15-crown-5]phenylaminoglyoxime (L3, and N′-(4′-Benzo[15-crown-5]-p-tolylaminoglyoxime (L4 from the aqueous phase into the organic phase was carried out. For comparison, the corresponding two glyoximes and their macrocyclic glyoxime ether derivatives were also examined. Crown ether groups having ligands (L3, L4 carry especially Na+ cation from aqueous phase to organic phase. The extraction equilibrium constants (Kex for complexes of ligands with Cu2+ and Hg2+ metal picrates between dichloromethane and water have been determined at 25°C. The values of the extraction constants (logKex were determined to be 12.27, 13.37, 12.94, and 12.39 for Cu2+ and 10.29, 10.62, 11.53, and 11.97 for Hg2+ with L1–L4, respectively.

  5. Black Hole Spectroscopy with Coherent Mode Stacking. (United States)

    Yang, Huan; Yagi, Kent; Blackman, Jonathan; Lehner, Luis; Paschalidis, Vasileios; Pretorius, Frans; Yunes, Nicolás


    The measurement of multiple ringdown modes in gravitational waves from binary black hole mergers will allow for testing the fundamental properties of black holes in general relativity and to constrain modified theories of gravity. To enhance the ability of Advanced LIGO/Virgo to perform such tasks, we propose a coherent mode stacking method to search for a chosen target mode within a collection of multiple merger events. We first rescale each signal so that the target mode in each of them has the same frequency and then sum the waveforms constructively. A crucial element to realize this coherent superposition is to make use of a priori information extracted from the inspiral-merger phase of each event. To illustrate the method, we perform a study with simulated events targeting the ℓ=m=3 ringdown mode of the remnant black holes. We show that this method can significantly boost the signal-to-noise ratio of the collective target mode compared to that of the single loudest event. Using current estimates of merger rates, we show that it is likely that advanced-era detectors can measure this collective ringdown mode with one year of coincident data gathered at design sensitivity.

  6. Stacking faults in austempered ductile iron

    Energy Technology Data Exchange (ETDEWEB)

    Hermida, J.D. [CNEA, San Martin (Argentina). Dept. de Materiales


    During last decade, Austempered Ductile Iron (ADI) has been successfully used as an acceptable replacement material for steel in many applications, due to the relatively high strength and reasonable ductility obtained. These properties are the result of the special microstructure exhibited by this material at the end of the upper bainite reaction: ferrite platelets surrounded by high carbon stabilized austenite. However, at the beginning of the austempering treatment, the existence of interdendritic low carbon austenite is revealed by its transformation to martensite when cooling the sample or during subsequent deformation. The completion of the upper bainite reaction is of decisive importance to mechanical properties because the remaining martensite reduces ductility. It was observed that the rate of the upper bainite reaction is governed by the carbon content difference between the low and high carbon austenites. The carbon content is obtained by the lattice parameter measurement, because there exists a known expression that relates both magnitudes. Several works have used X-ray diffraction to measure the lattice parameter and phase concentrations as a function of austempering time. In these works, the lattice parameters were obtained directly from the {l_brace}220{r_brace} and {l_brace}311{r_brace} peaks position. The purpose of this work is to show more precise lattice parameters measurement and, very closely related to this, the existence of stacking faults in austenite, even at times within the processing window.

  7. ATLAS software stack on ARM64

    CERN Document Server

    Smith, Joshua Wyatt; The ATLAS collaboration


    The ATLAS experiment explores new hardware and software platforms that, in the future, may be more suited to its data intensive workloads. One such alternative hardware platform is the ARM architecture, which is designed to be extremely power efficient and is found in most smartphones and tablets. CERN openlab recently installed a small cluster of ARM 64-bit evaluation prototype servers. Each server is based on a single-socket ARM 64-bit system on a chip, with 32 Cortex-A57 cores. In total, each server has 128 GB RAM connected with four fast memory channels. This paper reports on the port of the ATLAS software stack onto these new prototype ARM64 servers. This included building the "external" packages that the ATLAS software relies on. Patches were needed to introduce this new architecture into the build as well as patches that correct for platform specific code that caused failures on non-x86 architectures. These patches were applied such that porting to further platforms will need no or only very little adj...

  8. Long Duration Balloon Charge Controller Stack Integration (United States)

    Clifford, Kyle

    NASA and the Columbia Scientific Balloon Facility are interested in updating the design of the charge controller on their long duration balloon (LDB) in order to enable the charge controllers to be directly interfaced via RS232 serial communication by a ground testing computers and the balloon's flight computer without the need to have an external electronics stack. The design involves creating a board that will interface with the existing boards in the charge controller in order to receive telemetry from and send commands to those boards, and interface with a computer through serial communication. The inputs to the board are digital status inputs indicating things like whether the photovoltaic panels are connected or disconnected; and analog inputs with information such as the battery voltage and temperature. The outputs of the board are 100ms duration command pulses that will switch relays that do things like connect the photovoltaic panels. The main component of this design is a PIC microcontroller which translates the outputs of the existing charge controller into serial data when interrogated by a ground testing or flight computer. Other components involved in the design are an AD7888 12-bit analog to digital converter, a MAX3232 serial transceiver, various other ICs, capacitors, resistors, and connectors.

  9. Lithiation-induced shuffling of atomic stacks

    KAUST Repository

    Nie, Anmin


    In rechargeable lithium-ion batteries, understanding the atomic-scale mechanism of Li-induced structural evolution occurring at the host electrode materials provides essential knowledge for design of new high performance electrodes. Here, we report a new crystalline-crystalline phase transition mechanism in single-crystal Zn-Sb intermetallic nanowires upon lithiation. Using in situ transmission electron microscopy, we observed that stacks of atomic planes in an intermediate hexagonal (h-)LiZnSb phase are "shuffled" to accommodate the geometrical confinement stress arising from lamellar nanodomains intercalated by lithium ions. Such atomic rearrangement arises from the anisotropic lithium diffusion and is accompanied by appearance of partial dislocations. This transient structure mediates further phase transition from h-LiZnSb to cubic (c-)Li2ZnSb, which is associated with a nearly "zero-strain" coherent interface viewed along the [001]h/[111]c directions. This study provides new mechanistic insights into complex electrochemically driven crystalline-crystalline phase transitions in lithium-ion battery electrodes and represents a noble example of atomic-level structural and interfacial rearrangements.

  10. Weyl magnons in noncoplanar stacked kagome antiferromagnets (United States)

    Owerre, S. A.


    Weyl nodes have been experimentally realized in photonic, electronic, and phononic crystals. However, magnonic Weyl nodes are yet to be seen experimentally. In this paper, we propose Weyl magnon nodes in noncoplanar stacked frustrated kagome antiferromagnets, naturally available in various real materials. Most crucially, the Weyl nodes in the current system occur at the lowest excitation and possess a topological thermal Hall effect, therefore they are experimentally accessible at low temperatures due to the population effect of bosonic quasiparticles. In stark contrast to other magnetic systems, the current Weyl nodes do not rely on time-reversal symmetry breaking by the magnetic order. Rather, they result from explicit macroscopically broken time reversal symmetry by the scalar spin chirality of noncoplanar spin textures and can be generalized to chiral spin liquid states. Moreover, the scalar spin chirality gives a real space Berry curvature which is not available in previously studied magnetic Weyl systems. We show the existence of magnon arc surface states connecting projected Weyl magnon nodes on the surface Brillouin zone. We also uncover the first realization of triply-degenerate nodal magnon point in the noncollinear regime with zero scalar spin chirality.

  11. Efficiency of Polymer Electrolyte Membrane Fuel Cell Stack

    Directory of Open Access Journals (Sweden)

    Hans Bosma


    Full Text Available This paper applies a feedforward control of optimal oxygen excess ratio that maximize net power (improve efficiency of a NedStack P8.0-64 PEM fuel cell stack (FCS system. Net powers profile as a function of oxygen excess ratio for some points of operation are analyzed by using FCS model. The relationships between stack current and the corresponding control input voltage that gives an optimal oxygen excess ratio are used to design a feedforward control scheme. The results of this scheme are compared to the results of a feedforward control using a constant oxygen excess ratio. Simulation results show that optimal oxygen excess ratio improves fuel cell performance compared to the results of constant oxygen excess ratio. The same procedures are performed experimentally for the FCS system. The behaviour of the net power of the fuel cell stack with respect to the variation of oxygen excess ratio is analyzed to obtain optimal values. Data of stack current and the corresponding voltage input to the compressor that gives optimal values of oxygen excess ratio are used to develop a feedforward control. Feedforward control based on constant and optimal oxygen excess ratio control, are implemented in the NedStack P8.0-64 PEM fuel cell stack system by using LabVIEW. Implementation results shows that optimal oxygen excess ratio control improves the fuel cell performance compared to the constant oxygen excess ratio control.

  12. Pi-pi Stacking Mediated Cooperative Mechanism for Human Cytochrome P450 3A4

    Directory of Open Access Journals (Sweden)

    Botao Fa


    Full Text Available Human Cytochrome P450 3A4 (CYP3A4 is an important member of the cytochrome P450 superfamily with responsibility for metabolizing ~50% of clinical drugs. Experimental evidence showed that CYP3A4 can adopt multiple substrates in its active site to form a cooperative binding model, accelerating substrate metabolism efficiency. In the current study, we constructed both normal and cooperative binding models of human CYP3A4 with antifungal drug ketoconazoles (KLN. Molecular dynamics simulation and free energy calculation were then carried out to study the cooperative binding mechanism. Our simulation showed that the second KLN in the cooperative binding model had a positive impact on the first one binding in the active site by two significant pi-pi stacking interactions. The first one was formed by Phe215, functioning to position the first KLN in a favorable orientation in the active site for further metabolism reactions. The second one was contributed by Phe304. This pi-pi stacking was enhanced in the cooperative binding model by the parallel conformation between the aromatic rings in Phe304 and the dioxolan moiety of the first KLN. These findings can provide an atomic insight into the cooperative binding in CYP3A4, revealing a novel pi-pi stacking mechanism for drug-drug interactions.

  13. How Secondary and Tertiary Amide Moieties are Molecular Stations for Dibenzo-24-crown-8 in [2]Rotaxane Molecular Shuttles?

    Directory of Open Access Journals (Sweden)

    Benjamin Riss-Yaw


    Full Text Available Interlocked molecular machines like [2]rotaxanes are intriguing aesthetic molecules. The control of the localization of the macrocycle, which surrounds a molecular axle, along the thread leads to translational isomers of very different properties. Although many moieties have been used as sites of interactions for crown ethers, the very straightforwardly obtained amide motif has more rarely been envisaged as molecular station. In this article, we report the use of secondary and tertiary amide moieties as efficient secondary molecular station in pH-sensitive molecular shuttles. Depending on the N-substitution of the amide station, and on deprotonation or deprotonation-carbamoylation, the actuation of the molecular machinery differs accordingly to very distinct interactions between the axle and the DB24C8.

  14. How Secondary and Tertiary Amide Moieties are Molecular Stations for Dibenzo-24-crown-8 in [2]Rotaxane Molecular Shuttles? (United States)

    Riss-Yaw, Benjamin; Morin, Justine; Clavel, Caroline; Coutrot, Frédéric


    Interlocked molecular machines like [2]rotaxanes are intriguing aesthetic molecules. The control of the localization of the macrocycle, which surrounds a molecular axle, along the thread leads to translational isomers of very different properties. Although many moieties have been used as sites of interactions for crown ethers, the very straightforwardly obtained amide motif has more rarely been envisaged as molecular station. In this article, we report the use of secondary and tertiary amide moieties as efficient secondary molecular station in pH-sensitive molecular shuttles. Depending on the N -substitution of the amide station, and on deprotonation or deprotonation-carbamoylation, the actuation of the molecular machinery differs accordingly to very distinct interactions between the axle and the DB24C8.

  15. Consolidity: Stack-based systems change pathway theory elaborated

    Directory of Open Access Journals (Sweden)

    Hassen Taher Dorrah


    Full Text Available This paper presents an elaborated analysis for investigating the stack-based layering processes during the systems change pathway. The system change pathway is defined as the path resulting from the combinations of all successive changes induced on the system when subjected to varying environments, activities, events, or any excessive internal or external influences and happenings “on and above” its normal stands, situations or set-points during its course of life. The analysis is essentially based on the important overall system paradigm of “Time driven-event driven-parameters change”. Based on this paradigm, it is considered that any affected activity, event or varying environment is intelligently self-recorded inside the system through an incremental consolidity-scaled change in system parameters of the stack-based layering types. Various joint stack-based mathematical and graphical approaches supported by representable case studies are suggested for the identification, extraction, and processing of various stack-based systems changes layering of different classifications and categorizations. Moreover, some selected real life illustrative applications are provided to demonstrate the (infinite stack-based identification and recognition of the change pathway process in the areas of geology, archeology, life sciences, ecology, environmental science, engineering, materials, medicine, biology, sociology, humanities, and other important fields. These case studies and selected applications revealed that there are general similarities of the stack-based layering structures and formations among all the various research fields. Such general similarities clearly demonstrate the global concept of the “fractals-general stacking behavior” of real life systems during their change pathways. Therefore, it is recommended that concentrated efforts should be expedited toward building generic modular stack-based systems or blocks for the mathematical

  16. Loop Entropy Assists Tertiary Order: Loopy Stabilization of Stacking Motifs

    Directory of Open Access Journals (Sweden)

    Daniel P. Aalberts


    Full Text Available The free energy of an RNA fold is a combination of favorable base pairing and stacking interactions competing with entropic costs of forming loops. Here we show how loop entropy, surprisingly, can promote tertiary order. A general formula for the free energy of forming multibranch and other RNA loops is derived with a polymer-physics based theory. We also derive a formula for the free energy of coaxial stacking in the context of a loop. Simulations support the analytic formulas. The effects of stacking of unpaired bases are also studied with simulations.

  17. On $k$-stellated and $k$-stacked spheres


    Bagchi, Bhaskar; Datta, Basudeb


    We introduce the class $\\Sigma_k(d)$ of $k$-stellated (combinatorial) spheres of dimension $d$ ($0 \\leq k \\leq d + 1$) and compare and contrast it with the class ${\\cal S}_k(d)$ ($0 \\leq k \\leq d$) of $k$-stacked homology $d$-spheres. We have $\\Sigma_1(d) = {\\cal S}_1(d)$, and $\\Sigma_k(d) \\subseteq {\\cal S}_k(d)$ for $d \\geq 2k - 1$. However, for each $k \\geq 2$ there are $k$-stacked spheres which are not $k$-stellated. The existence of $k$-stellated spheres which are not $k$-stacked remains...

  18. Stacking by electroinjection with discontinuous buffers in capillary zone electrophoresis. (United States)

    Shihabi, Zak K


    The work presented here demonstrates that electroinjection can be performed using discontinuous buffers, which can result in better stacking than that obtained by hydrodynamic injection. The sample can be concentrated at the tip of the capillary leaving practically the whole capillary for sample separation. This results in several advantages, such as better sample concentration, higher plate number and shorter time of stacking. However, sample introduction by electromigration is suited for samples free or low in salt content. Samples, which are high in salt content, are better introduced by the hydrodynamic injection for stacking by the discontinuous buffers. Different simple methods to introduce the discontinuity in the buffer for electroinjection are discussed.

  19. Optimized stacked RADFETs for milli-rad dose measurement

    International Nuclear Information System (INIS)

    O'Connell, B.; Lane, B.; Mohammadzadeh, A.


    This paper details the improvements in the design of stacked RADFETs for increased radiation sensitivity. The issues of high read-out voltage has been shown to be a draw-back. It is the body (bulk)effect factor that is responsible for the increased overall stack Threshold voltage (V T ), which is greater than the sum of the individual devices V T . From extensive process and device simulation and resultant circuit simulation, modified stack structures have been proposed and designed. New and exciting result of lower initial (pre-irradiation) output voltage as well as increased radiation sensitivity will be presented. (author)

  20. Influence of macrocyclic chelators on the targeting properties of (68Ga-labeled synthetic affibody molecules: comparison with (111In-labeled counterparts.

    Directory of Open Access Journals (Sweden)

    Joanna Strand

    Full Text Available Affibody molecules are a class of small (7 kDa non-immunoglobulin scaffold-based affinity proteins, which have demonstrated substantial potential as probes for radionuclide molecular imaging. The use of positron emission tomography (PET would further increase the resolution and quantification accuracy of Affibody-based imaging. The rapid in vivo kinetics of Affibody molecules permit the use of the generator-produced radionuclide (68Ga (T1/2=67.6 min. Earlier studies have demonstrated that the chemical nature of chelators has a substantial influence on the biodistribution properties of Affibody molecules. To determine an optimal labeling approach, the macrocyclic chelators 1,4,7,10-tetraazacylododecane-1,4,7,10-tetraacetic acid (DOTA, 1,4,7-triazacyclononane-N,N,N-triacetic acid (NOTA and 1-(1,3-carboxypropyl-1,4,7- triazacyclononane-4,7-diacetic acid (NODAGA were conjugated to the N-terminus of the synthetic Affibody molecule ZHER2:S1 targeting HER2. Affibody molecules were labeled with (68Ga, and their binding specificity and cellular processing were evaluated. The biodistribution of (68Ga-DOTA-ZHER2:S1, (68Ga-NOTA-ZHER2:S1 and (68Ga-NODAGA-ZHER2:S1, as well as that of their (111In-labeled counterparts, was evaluated in BALB/C nu/nu mice bearing HER2-expressing SKOV3 xenografts. The tumor uptake for (68Ga-DOTA-ZHER2:S1 (17.9 ± 0.7%IA/g was significantly higher than for both (68Ga-NODAGA-ZHER2:S1 (16.13 ± 0.67%IA/g and (68Ga-NOTA-ZHER2:S1 (13 ± 3%IA/g at 2 h after injection. (68Ga-NODAGA-ZHER2:S1 had the highest tumor-to-blood ratio (60 ± 10 in comparison with both (68Ga-DOTA-ZHER2:S1 (28 ± 4 and (68Ga-NOTA-ZHER2:S1 (42 ± 11. The tumor-to-liver ratio was also higher for (68Ga-NODAGA-ZHER2:S1 (7 ± 2 than the DOTA and NOTA conjugates (5.5 ± 0.6 vs.3.3 ± 0.6. The influence of chelator on the biodistribution and targeting properties was less pronounced for (68Ga than for (111In. The results of this study demonstrate that macrocyclic

  1. “One Ring to Bind Them All”—Part I: The Efficiency of the Macrocyclic Scaffold for G-Quadruplex DNA Recognition

    Directory of Open Access Journals (Sweden)

    David Monchaud


    Full Text Available Macrocyclic scaffolds are particularly attractive for designing selective G-quadruplex ligands essentially because, on one hand, they show a poor affinity for the “standard” B-DNA conformation and, on the other hand, they fit nicely with the external G-quartets of quadruplexes. Stimulated by the pioneering studies on the cationic porphyrin TMPyP4 and the natural product telomestatin, follow-up studies have developed, rapidly leading to a large diversity of macrocyclic structures with remarkable-quadruplex binding properties and biological activities. In this review we summarize the current state of the art in detailing the three main categories of quadruplex-binding macrocycles described so far (telomestatin-like polyheteroarenes, porphyrins and derivatives, polyammonium cyclophanes, and in addressing both synthetic issues and biological aspects.

  2. Catalytic Silylation of N2and Synthesis of NH3and N2H4by Net Hydrogen Atom Transfer Reactions Using a Chromium P4Macrocycle. (United States)

    Kendall, Alexander J; Johnson, Samantha I; Bullock, R Morris; Mock, Michael T


    We report the first discrete molecular Cr-based catalysts for the reduction of N 2 . This study is focused on the reactivity of the Cr-N 2 complex, trans-[Cr(N 2 ) 2 (P Ph 4 N Bn 4 )] (P 4 Cr(N 2 ) 2 ), bearing a 16-membered tetraphosphine macrocycle. The architecture of the [16]-P Ph 4 N Bn 4 ligand is critical to preserve the structural integrity of the catalyst. P 4 Cr(N 2 ) 2 was found to mediate the reduction of N 2 at room temperature and 1 atm pressure by three complementary reaction pathways: (1) Cr-catalyzed reduction of N 2 to N(SiMe 3 ) 3 by Na and Me 3 SiCl, affording up to 34 equiv N(SiMe 3 ) 3 ; (2) stoichiometric reduction of N 2 by protons and electrons (for example, the reaction of cobaltocene and collidinium triflate at room temperature afforded 1.9 equiv of NH 3 , or at -78 °C afforded a mixture of NH 3 and N 2 H 4 ); and (3) the first example of NH 3 formation from the reaction of a terminally bound N 2 ligand with a traditional H atom source, TEMPOH (2,2,6,6-tetramethylpiperidine-1-ol). We found that trans-[Cr( 15 N 2 ) 2 (P Ph 4 N Bn 4 )] reacts with excess TEMPOH to afford 1.4 equiv of 15 NH 3 . Isotopic labeling studies using TEMPOD afforded ND 3 as the product of N 2 reduction, confirming that the H atoms are provided by TEMPOH.

  3. Thermodynamic studies of the complexation of plutonium(IV) by linear and macrocyclic poly-amino-carboxylate ligands

    International Nuclear Information System (INIS)

    Burgat, Romain


    In the framework of a collaboration between the CEA (Commissariat a l Energie Atomique) of Valduc and the ICMUB (Institut de Chimie Moleculaire de l Universite de Bourgogne), a study platform of the structural and physico-chemical properties of the radioelements U, Pu and Am complexes has been implemented. The plutonium(IV) complexation has been studied in a molar nitrate medium. The affinity of three linear poly-amino-carboxylates (EDTA, CDTA and DTPA) towards plutonium(IV) has then been estimated. For the three ligands, the formation constants of the monoleptic complexes Pu(EDTA), Pu(CDTA) and [Pu(DTPA)] - have been determined in a (H,K)NO 3 1 M medium and then extrapolated at a zero ionic force with the specific interactions theory (SIT). For the three complexes, mono-hydroxylated monoleptic species have been observed. With the EDTA and the CDTA, protonated dileptic complexes of a general formula [Pu(L) 2 H h ] (4-h)- have been revealed too. Nevertheless, the steric hindrance around the metallic center is too important to allow to a second molecule of DTPA to coordinate the Pu 4+ cation. The exclusive formation of the species [Pu(DTPA)] - and [Pu(DTPA)(OH)] 2- has been confirmed by capillary electrophoresis (EC-ICP-MS). On account of the preliminary results obtained during the titration of the cyclame tetraacetic product (TETRA) in presence of plutonium(IV), the adding of a competitive ligand such as EDTA has been considered for the study of the complexation of this radioelement by macrocyclic ligands. At last, the affinity of different macrocyclic ligands containing either four amide functions (TETAMMe 2 and TETAMMEt 2 ) or carboxylate groups (TETA, DOTPr and TETPr) towards lanthanides(III) has been estimated too. Although the complexation reaction be fast with the two first ligands, these complexes are less stable than those formed with the carboxylic macrocycles. (O.M.)

  4. Fuel flow distribution in SOFC stacks revealed by impedance spectroscopy

    DEFF Research Database (Denmark)

    Mosbæk, Rasmus Rode; Hjelm, Johan; Barfod, Rasmus


    . An operating stack is subject to compositional gradients in the gaseous reactant streams, and temperature gradients across each cell and across the stack, which complicates detailed analysis. An experimental stack with low ohmic resistance from Topsoe Fuel Cell A/S was characterized using Electrochemical...... Impedance Spectroscopy (EIS). The stack measurement geometry was optimized for EIS by careful selection of the placement of current feeds and voltage probes in order to minimize measurement errors. It was demonstrated that with the improved placement of current feeds and voltage probes it is possible...... to separate the loss contributions in an ohmic and a polarization part and that the low frequency response is useful in detecting mass transfer limitations. This methodology can be used to detect possible minor changes in the supply of gas to the individual cells, which is important when going to high fuel...

  5. Simulation of magnetization and levitation characteristics of HTS tape stacks (United States)

    Anischenko, I. V.; Pokrovskii, S. V.; Mineev, N. A.


    In this work it is presented a computational model of a magnetic levitation system based on stacks of high-temperature second generation superconducting tapes (HTS) GdBa2Cu3O7-x. Calculated magnetic field and the current distributions in the system for different stacks geometries in the zero-field cooling mode are also presented. The magnetization curves of the stacks in the external field of a permanent NdFeB magnet and the levitation force dependence on the gap between the magnet and the HTS tapes stack were obtained. A model of the magnetic system, oriented to levitation application, is given. Results of modeling were compared with the experimental data.

  6. Fast principal component analysis for stacking seismic data (United States)

    Wu, Juan; Bai, Min


    Stacking seismic data plays an indispensable role in many steps of the seismic data processing and imaging workflow. Optimal stacking of seismic data can help mitigate seismic noise and enhance the principal components to a great extent. Traditional average-based seismic stacking methods cannot obtain optimal performance when the ambient noise is extremely strong. We propose a principal component analysis (PCA) algorithm for stacking seismic data without being sensitive to noise level. Considering the computational bottleneck of the classic PCA algorithm in processing massive seismic data, we propose an efficient PCA algorithm to make the proposed method readily applicable for industrial applications. Two numerically designed examples and one real seismic data are used to demonstrate the performance of the presented method.

  7. Static analysis of worst-case stack cache behavior

    DEFF Research Database (Denmark)

    Jordan, Alexander; Brandner, Florian; Schoeberl, Martin


    Utilizing a stack cache in a real-time system can aid predictability by avoiding interference that heap memory traffic causes on the data cache. While loads and stores are guaranteed cache hits, explicit operations are responsible for managing the stack cache. The behavior of these operations can......-graph, the worst-case bounds can be efficiently yet precisely determined. Our evaluation using the MiBench benchmark suite shows that only 37% and 21% of potential stack cache operations actually store to and load from memory, respectively. Analysis times are modest, on average running between 0.46s and 1.30s per...... be analyzed statically. We present algorithms that derive worst-case bounds on the latency-inducing operations of the stack cache. Their results can be used by a static WCET tool. By breaking the analysis down into subproblems that solve intra-procedural data-flow analysis and path searches on the call...

  8. A Stack Cache for Real-Time Systems

    DEFF Research Database (Denmark)

    Schoeberl, Martin; Nielsen, Carsten


    Real-time systems need time-predictable computing platforms to allowfor static analysis of the worst-case execution time. Caches are important for good performance, but data caches arehard to analyze for the worst-case execution time. Stack allocated data has different properties related to local......Real-time systems need time-predictable computing platforms to allowfor static analysis of the worst-case execution time. Caches are important for good performance, but data caches arehard to analyze for the worst-case execution time. Stack allocated data has different properties related...... to locality, lifetime, and static analyzability of access addresses comparedto static or heap allocated data. Therefore, caching of stack allocateddata benefits from having its own cache. In this paper we present a cache architecture optimized for stack allocateddata. This cache is additional to the normal...

  9. DBaaS with OpenStack Trove

    CERN Document Server

    Giardini, Andrea


    The purpose of the project was to evaluate the Trove component for OpenStack, understand if it can be used with the CERN infrastructure and report the benefits and disadvantages of this software. Currently, databases for CERN projects are provided by a DbaaS software developed inside the IT-DB group. This solution works well with the actual infrastructure but it is not easy to maintain. With the migration of the CERN infrastructure to OpenStack the Database group started to evaluate the Trove component. Instead of mantaining an own DbaaS service it can be interesting to migrate everything to OpenStack and replace the actual DbaaS software with Trove. This way both virtual machines and databases will be managed by OpenStack itself.

  10. Stacking dependence of carrier transport properties in multilayered black phosphorous. (United States)

    Sengupta, A; Audiffred, M; Heine, T; Niehaus, T A


    We present the effect of different stacking orders on carrier transport properties of multi-layer black phosphorous. We consider three different stacking orders AAA, ABA and ACA, with increasing number of layers (from 2 to 6 layers). We employ a hierarchical approach in density functional theory (DFT), with structural simulations performed with generalized gradient approximation (GGA) and the bandstructure, carrier effective masses and optical properties evaluated with the meta-generalized gradient approximation (MGGA). The carrier transmission in the various black phosphorous sheets was carried out with the non-equilibrium green's function (NEGF) approach. The results show that ACA stacking has the highest electron and hole transmission probabilities. The results show tunability for a wide range of band-gaps, carrier effective masses and transmission with a great promise for lattice engineering (stacking order and layers) in black phosphorous.

  11. SEE on Different Layers of Stacked-SRAMs

    CERN Document Server

    Gupta, V; Tsiligiannis, G; Rousselet, M; Mohammadzadeh, A; Javanainen, A; Virtanen, A; Puchner, H; Saigné, F; Wrobel, F; Dilillo, L


    This paper presents heavy-ion and proton radiation test results of a 90 nm COTS SRAM with stacked structure. Radiation tests were made using high penetration heavy-ion cocktails at the HIF (Belgium) and at RADEF (Finland) as well as low energy protons at RADEF. The heavy-ion SEU cross-section showed an unusual profile with a peak at the lowest LET (heavy-ion with the highest penetration range). The discrepancy is due to the fact that the SRAM is constituted of two vertically stacked dice. The impact of proton testing on the response of both stacked dice is presented. The results are discussed and the SEU cross-sections of the upper and lower layers are compared. The impact of the stacked structure on the proton SEE rate is investigated.

  12. Synthesis of Cycloveratrylene Macrocycles and Benzyl Oligomers Catalysed by Bentonite under Microwave/Infrared and Solvent-Free Conditions

    Directory of Open Access Journals (Sweden)

    Manuel Salmón


    Full Text Available Tonsil Actisil FF, which is a commercial bentonitic clay, promotes the formation of cycloveratrylene macrocycles and benzyl oligomers from the corresponding benzyl alcohols in good yields under microwave heating and infrared irradiation in the absence of solvent in both cases. The catalytic reaction is sensitive to the type of substituent on the aromatic ring. Thus, when benzyl alcohol was substituted with a methylenedioxy, two methoxy or three methoxy groups, a cyclooligomerisation process was induced. Unsubstituted, methyl and methoxy benzyl alcohols yielded linear oligomers. In addition, computational chemistry calculations were performed to establish a validated mechanistic pathway to explain the growth of the obtained linear oligomers.

  13. Dysprosium complexes with the tetraphenylporphyrin macrocyclic ligand; Complejos de disprosio con el ligante macrociclico tetrafenilporfirina

    Energy Technology Data Exchange (ETDEWEB)

    Martinez M, V.; Padilla, J.; Ramirez, F.M


    In this report, the results obtained on the synthesis, characterization and study of the chemical behavior of dysprosium complex with the acetylacetone chelating agent (Hacac) and the tetraphenylporphyrin macrocyclic ligand (H{sub 2}TFP) are given. Based on the literature but according to our necessities and interest, the appropriate methodology settled down from the synthesis of prime matters until the obtaining and characterization of the products. The acetyl acetonate complex was obtained of mono hydrated dysprosium [Dy(acac){sub 3}. H{sub 2}0] and trihydrated [Dy(acac){sub 3} .3 H{sub 2}0], the mono tetra phenyl porphyrinate [Dy(TFP)(acac). 2 ac] the double sandwich of the dysprosium porphyrinate [Dy(TFP){sub 2}] and the triple sandwich of the dysprosium porphyrinate [Dy(TFP){sub 3}. 2 TCB] (TCB = trichlorobenzene). Its were characterized by their melting points, solubility, IR, UV, TGA and DTA both first and besides the techniques already mentioned for NMR'H, RPE and Magnetic susceptibility the three last complexes. From the spectroscopic point of view, IR and RPE its suggested the existence of a complex of inverse mixed valence [Dy(TFP){sup 2-} (TFP) {sup 1-}] for the Dy(TFP){sub 2} as a result of the existence of the free radical (TFP' {sup 1-} and that it was not in none of the other porphyrin compounds. In the NMR'H spectra of the compounds were not observed signals in the region from 0 to 10 ppm that which shows that the dysprosium complexes in special those of the porphyrin type are highly paramagnetic and its could be used as displacement reagents, creators of images and contrast agents of great utility in these days in studies of NMR, technique today by today used in medical diagnoses. (Author)

  14. Anti-influenza activity of marchantins, macrocyclic bisbibenzyls contained in liverworts.

    Directory of Open Access Journals (Sweden)

    Yuma Iwai

    Full Text Available The H1N1 influenza A virus of swine-origin caused pandemics throughout the world in 2009 and the highly pathogenic H5N1 avian influenza virus has also caused epidemics in Southeast Asia in recent years. The threat of influenza A thus remains a serious global health issue and novel drugs that target these viruses are highly desirable. Influenza A possesses an endonuclease within its RNA polymerase which comprises PA, PB1 and PB2 subunits. To identify potential new anti-influenza compounds in our current study, we screened 33 different types of phytochemicals using a PA endonuclease inhibition assay in vitro and an anti-influenza A virus assay. The marchantins are macrocyclic bisbibenzyls found in liverworts, and plagiochin A and perrottetin F are marchantin-related phytochemicals. We found from our screen that marchantin A, B, E, plagiochin A and perrottetin F inhibit influenza PA endonuclease activity in vitro. These compounds have a 3,4-dihydroxyphenethyl group in common, indicating the importance of this moiety for the inhibition of PA endonuclease. Docking simulations of marchantin E with PA endonuclease suggest a putative "fitting and chelating model" as the mechanism underlying PA endonuclease inhibition. The docking amino acids are well conserved between influenza A and B. In a cultured cell system, marchantin E was further found to inhibit the growth of both H3N2 and H1N1 influenza A viruses, and marchantin A, E and perrotein F showed inhibitory properties towards the growth of influenza B. These marchantins also decreased the viral infectivity titer, with marchantin E showing the strongest activity in this assay. We additionally identified a chemical group that is conserved among different anti-influenza chemicals including marchantins, green tea catechins and dihydroxy phenethylphenylphthalimides. Our present results indicate that marchantins are candidate anti-influenza drugs and demonstrate the utility of the PA endonuclease assay in

  15. Modeling of a Stacked Power Module for Parasitic Inductance Extraction (United States)


    ARL-TR-8138 ● SEP 2017 US Army Research Laboratory Modeling of a Stacked Power Module for Parasitic Inductance Extraction by...not return it to the originator. ARL-TR-8138 ● SEP 2017 US Army Research Laboratory Modeling of a Stacked Power Module for...aware that notwithstanding any other provision of law , no person shall be subject to any penalty for failing to comply with a collection of information if

  16. National Spherical Torus Experiment (NSTX) Center Stack Upgrade

    International Nuclear Information System (INIS)

    Neumeyer, C.; Avasarala, S.; Chrzanowski, J.; Dudek, L.; Fan, H.; Hatcher, H.; Heitzenroeder, P.; Menard, J.; Ono, M.; Ramakrishnan, S.; Titus, P.; Woolley, R.; Zhan, H.


    The purpose of the NSTX Center Stack Upgrade project is to expand the NSTX operational space and thereby the physics basis for next-step ST facilities. The plasma aspect ratio (ratio of plasma major to minor radius) of the upgrade is increased to 1.5 from the original value of 1.26, which increases the cross sectional area of the center stack by a factor of ∼ 3 and makes possible higher levels of performance and pulse duration.

  17. A new method for beam stacking in storage rings

    Energy Technology Data Exchange (ETDEWEB)

    Bhat, C.M.; /Fermilab


    Recently, I developed a new beam stacking scheme for synchrotron storage rings called 'longitudinal phase-space coating' (LPSC). This scheme has been convincingly validated by multi-particle beam dynamics simulations and has been demonstrated with beam experiments at the Fermilab Recycler. Here, I present the results from both simulations and experiments. The beam stacking scheme presented here is the first of its kind.

  18. Stacking faults and phase transformations in silicon nitride (United States)

    Milhet, X.; Demenet, J.-L.; Rabier, J.


    From observations of extended dislocation nodes in β silicon nitride, possible stacking fault structures in the basal plane of this compound have been investigated. It has been found that stacking fault structure is locally analogous to α silicon nitride. A phase transformation α to β or β to α can also be achieved by cooperative shear of partial dislocations with 1/3<~ngle1bar{1}00rangle Burgers vectors.

  19. LOFT diesel generator ''A'' exhaust stack seismic analysis

    International Nuclear Information System (INIS)

    Blandford, R.K.


    A stress analysis of the LOFT Diesel Generator ''A'' Exhaust Stack was performed to determine its reaction to Safe-Shutdown Earthquake loads. The exhaust stack silencer and supporting foundation was found to be inadequate for the postulated seismic accelerations. Lateral support is required to prevent overturning of the silencer pedestal and reinforcement of the 4'' x 0.5'' silencer base straps is necessary. Basic requirements for this additional support are discussed

  20. A Focus on Triazolium as a Multipurpose Molecular Station for pH-Sensitive Interlocked Crown-Ether-Based Molecular Machines. (United States)

    Coutrot, Frédéric


    The control of motion of one element with respect to others in an interlocked architecture allows for different co-conformational states of a molecule. This can result in variations of physical or chemical properties. The increase of knowledge in the field of molecular interactions led to the design, the synthesis, and the study of various systems of molecular machinery in a wide range of interlocked architectures. In this field, the discovery of new molecular stations for macrocycles is an attractive way to conceive original molecular machines. In the very recent past, the triazolium moiety proved to interact with crown ethers in interlocked molecules, so that it could be used as an ideal molecular station. It also served as a molecular barrier in order to lock interlaced structures or to compartmentalize interlocked molecular machines. This review describes the recently reported examples of pH-sensitive triazolium-containing molecular machines and their peculiar features.

  1. Size filtering effect in vertical stacks of In(Ga)As/GaAs self-assembled quantum rings

    International Nuclear Information System (INIS)

    Ouerghui, W.; Melliti, A.; Maaref, M.A.; Martinez-Pastor, J.; Gomis, J.; Granados, D.; Garcia, J.M.


    We present a systematic study of closely In(Ga)As/InAs quantum rings (QRs) grown by molecular beam epitaxy (MBE). Photoluminescence (PL) experiments show a strong filtering effect in the ring being stacked and simultaneous linewidth narrowing for the appropriate layer thickness (thinner thickness). If the spacer thickness is further reduced, a strong coupling between the nanostructures is produced and the signal shifts to low energy

  2. Measurements of proton energy spectra using a radiochromic film stack (United States)

    Filkins, T. M.; Steidle, Jessica; Ellison, D. M.; Steidle, Jeffrey; Freeman, C. G.; Padalino, S. J.; Fiksel, G.; Regan, S. P.; Sangster, T. C.


    The energy spectrum of protons accelerated from the rear-side of a thin foil illuminated with ultra-intense laser light from the OMEGA EP laser system at the University of Rochester's Laboratory for Laser Energetics (LLE) was measured using a stack of radiochromic film (RCF). The film stack consisted of four layers of Gafchromic HD-V2 film and four layers of Gafchromic MD-V2-55 film. Aluminum foils of various thicknesses were placed between each piece of RCF in the stack. This arrangement allowed protons with energies of 30 MeV to reach the back layer of RCF in the stack. The stack was placed in the detector plane of a Thomson parabola ion energy (TPIE) spectrometer. Each piece of film in the stack was scanned using a commercially available flat-bed scanner (Epson 10000XL). The resulting optical density was converted into proton fluence using an absolute calibration of the RCF obtained at the SUNY Geneseo 1.7 MV Pelletron accelerator laboratory. In these calibration measurements, the sensitivity of the radiochromic film was measured using monoenergetic protons produced by the accelerator. Details of the analysis procedure and the resulting proton energy spectra will be presented. Funded in part by a grant from the DOE through the Laboratory for Laser Energetics.

  3. Contorted Organic Semiconductors for Molecular Electronics (United States)

    Zhong, Yu

    Chapter 4, I discuss helical molecular semiconductors as electron acceptors that are on par with fullerene derivatives in efficient solar cells. We achieved an 8.3% power conversion efficiency in a solar cell, which is a record high for non-fullerene bulk heterojunctions. Femtosecond transient absorption spectroscopy revealed both electron and hole transfer processes at the donor-acceptor interfaces. Atomic force microscopy reveals a mesh-like network of acceptors with pores that are tens of nanometers in diameter for efficient exciton separation and charge transport. This study describes a new motif for designing highly efficient acceptors for organic solar cells. In Chapter 5, I compare analogous cyclic and acyclic pi-conjugated molecules as n-type electronic materials and find that the cyclic molecules have numerous benefits in organic photovoltaics. We designed two conjugated cycles for this study. Each comprises four subunits; one combines four electron-accepting, redox-active, diphenyl-perylenediimide subunits, and the other alternates two electron-donating bithiophene units with two diphenyl-perylenediimide units. We compare the macrocycles to acyclic versions of these molecules and find that, relative to the acyclic analogs, the conjugated macrocycles have bathochromically shifted UV-vis absorbances and are more easily reduced. In blended films, macrocycle-based devices show higher electron mobility and good morphology. All of these factors contribute to the more than doubling of the power conversion efficiency observed in organic photovoltaic devices with these macrocycles as the n-type, electron transporting material. This study highlights the importance of geometric design in creating new molecular semiconductors. In Chapter 6, I describe a new molecular design that enables high performance organic photodetectors. We use a rigid, conjugated macrocycle as the electron acceptor in devices to obtain high photocurrent and low dark current. We directly compare the

  4. Synthesis and Biological Activities of Some New (Nα-Dinicotinoyl- bis-L-Leucyl Linear and Macrocyclic Peptides

    Directory of Open Access Journals (Sweden)

    Suzan Khayyat


    Full Text Available A series of linear and macrocyclic peptides 3–12 were synthesized using 3,5-pyridinedicarboxylic acid (1 as starting material and screened for their antimicrobial, anti-inflammatory and anticancer activities. Bis-ester 3 was prepared from 1 and L-leucine methyl ester. Hydrazinolysis and hydrolysis of dipeptide methyl ester 3 with hydrazine hydrate or 1 N sodium hydroxide afforded compounds 4 and 5, respectively. Cyclization of the dipeptide 5 with L-lysine methyl ester afforded cyclic pentapeptide ester 6. Compounds 7–9 were synthesized by reacting hydrazide 4 with phthalic anhydride, 1,8-naphthalene anhydride or acetophenone derivatives. Treatment of acid hydrazide 4 with aromatic aldehydes or tetraacid dianhydrides afforded the corresponding bis-dipeptide hydrazones 10a–e and macrocyclic peptides 11 and 12, respectively. The structures of newly synthesized compounds were confirmed by IR, 1H-NMR, MS spectral data and elemental analysis. The detailed synthesis, spectroscopic data, biological and pharmacological activities of the synthesized compounds was reported.

  5. The Eponymous Cofactors in Cytochrome P460s from Ammonia-Oxidizing Bacteria Are Iron Porphyrinoids Whose Macrocycles Are Dibasic. (United States)

    Smith, Meghan A; Lancaster, Kyle M


    The enzymes hydroxylamine oxidoreductase and cytochrome (cyt) P460 contain related unconventional "heme P460" cofactors. These cofactors are unusual in their inclusion of nonstandard cross-links between amino acid side chains and the heme macrocycle. Mutagenesis studies performed on the Nitrosomonas europaea cyt P460 that remove its lysine-heme cross-link show that the cross-link is key to defining the spectroscopic properties and kinetic competence of the enzyme. However, exactly how this cross-link confers these features remains unclear. Here we report the 1.45 Å crystal structure of cyt P460 from Nitrosomonas sp. AL212 and conclude that the cross-link does not lead to a change in hybridization of the heme carbon participating in the cross-link but rather enforces structural distortions to the macrocycle away from planarity. Time-dependent density functional theory coupled to experimental structural and spectroscopic analysis suggest that this geometric distortion is sufficient to define the spectroscopic properties of the heme P460 cofactor and provide clues toward establishing a relationship between heme P460 electronic structure and function.

  6. Hydrophobic, Hydrophilic, and Amphiphilic Polyglycocarbonates with Linear and Macrocyclic Architectures from Bicyclic Glycocarbonates Derived from CO2 and Glucoside

    KAUST Repository

    Pati, Debasis


    Two bicyclic glycocarbonates were synthesized in five steps from α-methyl-d-glucoside without resorting to phosgene or to its derivatives for the first time. The 4- and 6-positions of glucose were modified to introduce a six-membered carbonate ring, using CO as the carbonylating reagent; the 2- and 3-positions of the same glucoside substrate were first transformed into either methyl or triethylene glycol monomethyl ether groups to protect these positions from undesirable reactions and also to impart hydrophobicity in the first case and hydrophilicity in the second. The polymerization behavior of these bicyclic glycocarbonates was then investigated under different conditions. On the one hand, through ring-opening polymerization of the above monomers, linear polyglycocarbonate homopolymers and diblock copolymers were obtained initiated by p-methylbenzyl alcohol using 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) as catalyst; on the other hand, macrocyclic polyglycocarbonate homopolymers and diblock copolymers were grown using 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) which served as zwitterionic initiator. The various architectures derived were all thoroughly characterized by NMR, GPC, and MALDI-tof and shown to exhibit the expected structure. Finally, the self-assembly of linear and macrocyclic amphiphilic copolyglycocarbonates in water was investigated and characterized by cryo-TEM.

  7. Synthesis, characterization and biological studies of homo and hetero-binuclear 13-membered pentaaza bis (macrocyclic) complexes (United States)

    Zafar, Hina; Kareem, Abdul; Sherwani, Asif; Mohammad, Owais; Khan, Tahir Ali


    A new series of homo and hetero binuclear 13-membered pentaaza bis (macrocyclic) complexes, [MM‧LX4], [M = Cu(II), M‧ = Cu(II), Co(II), Ni(II) and Sn(II); L = ligand and X = Cl or NO3] have been synthesized by the template reaction of dichloro/dinitrato diphenyl sulphone 1,3,6,9,12-tetra hydro pentaazacyclo pantane copper (II) complexes with formaldehyde, triethylenetetraamine, and respective metal salts in 1:2:1:1 molar ratio. The complexes have been characterized by elemental analyses, molar conductance measurements, ESI-mass, 1H, 13C and 119Sn NMR, IR, electronic and EPR spectral studies. The results of elemental analyses, ESI-mass and conductivity measurements confirmed the stoichiometry of the complexes while the characteristic absorption bands and resonance peaks in IR and NMR spectra confirmed the formation of macrocyclic frameworks of the complexes. These studies showed octahedral geometry around the metal ion. The thermal stability of copper complexes was also studied by TGA and DTA analyses. Some complexes of this series were also studied for their in vitro anticancer activity against cancer cells lines: Hep3B, MCF7, and HeLa. The recorded IC50 values for the tested complexes show moderate to good cytotoxicity against these cancer cell lines.

  8. Molecular mechanics conformational analysis of tylosin (United States)

    Ivanov, Petko M.


    The conformations of the 16-membered macrolide antibiotic tylosin were studied with molecular mechanics (AMBER∗ force field) including modelling of the effect of the solvent on the conformational preferences (GB/SA). A Monte Carlo conformational search procedure was used for finding the most probable low-energy conformations. The present study provides complementary data to recently reported analysis of the conformations of tylosin based on NMR techniques. A search for the low-energy conformations of protynolide, a 16-membered lactone containing the same aglycone as tylosin, was also carried out, and the results were compared with the observed conformation in the crystal as well as with the most probable conformations of the macrocyclic ring of tylosin. The dependence of the results on force field was also studied by utilizing the MM3 force field. Some particular conformations were computed with the semiempirical molecular orbital methods AM1 and PM3.

  9. Electron and Phonon Transport in Molecular Junctions

    DEFF Research Database (Denmark)

    Li, Qian

    transmission at the Fermi energy. We propose and analyze a way of using π   stacking to design molecular junctions to control heat transport. We develop a simple model system to identify optimal parameter regimes and then use density functional theory (DFT) to extract model parameters for a number of specific......Molecular electronics provide the possibility to investigate electron and phonon transport at the smallest imaginable scale, where quantum effects can be investigated and exploited directly in the design. In this thesis, we study both electron transport and phonon transport in molecular junctions....... The system we are interested in here are π-stacked molecules connected with two semi-infinite leads. π-stacked aromatic rings, connected via π-π electronic coupling, provides a rather soft mechanical bridge while maintaining high electronic conductivity. We investigate electron transport...

  10. Synthesis, spectroscopic studies and inhibitory activity against bactria and fungi of acyclic and macrocyclic transition metal complexes containing a triamine coumarine Schiff base ligand (United States)

    Abou-Hussein, A. A.; Linert, Wolfgang


    Two series of new mono and binuclear complexes with a Schiff base ligand derived from the condensation of 3-acetylcoumarine and diethylenetriamine, in the molar ratio 2:1 have been prepared. The ligand was characterized by elemental analysis, IR, UV-visible, 1H-NMR and mass spectra. The reaction of the Schiff base ligand with cobalt(II), nickel(II), copper(II), zinc(II) and oxovanadium(IV) lead to mono or binuclear species of cyclic or macrocyclic complexes, depending on the mole ratio of metal to ligand and as well as on the method of preparation. The Schiff base ligand behaves as a cyclic bidentate, tetradendate or pentaentadentae ligand. The formation of macrocyclic complexes depends significantly on the dimension of the internal cavity, the rigidity of the macrocycles, the nature of its donor atoms and on the complexing properties of the anion involved in the coordination. Electronic spectra and magnetic moments of the complexes indicate that the geometries of the metal centers are either square pyramidal or octahedral for acyclic or macro-cyclic complexes. The structures are consistent with the IR, UV-visible, ESR, 1H-NMR, mass spectra as well as conductivity and magnetic moment measurements. The Schiff base ligand and its metal complexes were tested against two pathogenic bacteria as Gram-positive and Gram-negative bacteria as well as one kind of fungi. Most of the complexes exhibit mild antibacterial and antifungal activities against these organisms.

  11. Fabrication of reduced graphene oxide/macrocyclic cobalt complex nanocomposites as counter electrodes for Pt-free dye-sensitized solar cells (United States)

    Tsai, Chih-Hung; Shih, Chun-Jyun; Wang, Wun-Shiuan; Chi, Wen-Feng; Huang, Wei-Chih; Hu, Yu-Chung; Yu, Yuan-Hsiang


    In this study, macrocyclic Co complexes were successfully grafted onto graphene oxide (GO) to produce GO/Co nanocomposites with a large surface area, high electrical conductivity, and excellent catalytic properties. The novel GO/Co nanocomposites were applied as counter electrodes for Pt-free dye-sensitized solar cells (DSSCs). Various ratios of macrocyclic Co complexes were used as the reductant to react with the GO, with which the surface functional groups of the GO were reduced and the macrocyclic ligand of the Co complexes underwent oxidative dehydrogenation, after which the conjugated macrocyclic Co systems were grafted onto the surface of the reduced GO to form GO/Co nanocomposites. The surface morphology, material structure, and composition of the GO/Co composites and their influences on the power-conversion efficiency of DSSC devices were comprehensively investigated. The results showed that the GO/Co (1:10) counter electrode (CE) exhibited an optimal power conversion efficiency of 7.48%, which was higher than that of the Pt CE. The GO/Co (1:10) CE exhibited superior electric conductivity, catalytic capacity, and redox capacity. Because GO/Co (1:10) CEs are more efficient and cheaper than Pt CEs, they could potentially be used as a replacement for Pt electrodes.

  12. Grafting of benzylic amide macrocycles onto acid-terminated self-assembled monolayers studied by XPS, RAIRS, and contact angle measurements

    NARCIS (Netherlands)

    Cecchet, F; Pilling, M; Hevesi, L; Schergna, S; Wong, JKY; Clarkson, GJ; Leigh, DA; Rudolf, P; Wong, Jenny K.Y.; Clarkson, Guy J.


    The grafting of benzylic amide macrocycles, the basic units of more complex mechanically interlocked architectures such as catenanes and rotaxanes, was performed via the functionalization of an acid-terminated self-assembled monolayer (SAM) of 11-mercaptoundecanoic acid (11-MUA). Both chemical and

  13. Microscale Synthesis, Reactions, and (Super 1)H NMR Spectroscopic Investigations of Square Planar Macrocyclic, Tetramido-N Co(III) Complexes Relevant to Green Chemistry (United States)

    Watson, Tanya T.; Uffelman, Erich S.; Lee, Daniel W., III; Doherty, Jonathan R.; Schulze, Carl; Burke, Amy L.; Bonnema, Kristen, R.


    The microscale preparation, characterization, and reactivity of a square planar Co(III) complex that has grown out of a program to introduce experiments of relevance to green chemistry into the undergraduate curriculum is presented. The given experiments illustrate the remarkable redox and aqueous acid-base stability that make the macrocycles very…

  14. Base-induced self-assembly for one-dimensional coordination polymers via chiral pendant-armed Schiff base mononuclear Pb(II) macrocycles. (United States)

    Zhang, Kun; Jin, Chao; Sun, Yuchen; Chang, Feifan; Huang, Wei


    A pair of 18-membered [1 + 1] chiral pendant-armed Schiff base macrocyclic mononuclear Pb(II) complexes with an unusual N1O2 coordination mode, synthesized from two chiral isomeric dialdehyde components, can be further self-assembled to one-dimensional ribbon coordination polymers by adding NaOH as a base to remove two phenolic protons.

  15. Three-Dimensional Modeling of the Detonation of a Munitions Stack and the Loading on an Adjacent Stack Protected by a Water Barricade

    National Research Council Canada - National Science Library

    Lottero, Richard


    This report describes the results of three-dimensional (3-D) hydrocode computations modeling the detonation of a donor munitions stack and the loading on and response of a protective water barricade and a nearby acceptor munitions stack...

  16. Genetic profiles of ten Dirofilaria immitis isolates susceptible or resistant to macrocyclic lactone heartworm preventives

    Directory of Open Access Journals (Sweden)

    Catherine Bourguinat


    Full Text Available Abstract Background For dogs and cats, chemoprophylaxis with macrocyclic lactone (ML preventives for heartworm disease is widely used in the United States and other countries. Since 2005, cases of loss of efficacy (LOE of heartworm preventives have been reported in the U.S. More recently, ML-resistant D. immitis isolates were confirmed. Previous work identified 42 genetic markers that could predict ML response in individual samples. For field surveillance, it would be more appropriate to work on microfilarial pools from individual dogs with a smaller subset of genetic markers. Methods MiSeq technology was used to identify allele frequencies with the 42 genetic markers previously reported. Microfilaria from ten well-characterized new isolates called ZoeKY, ZoeMI, ZoeGCFL, ZoeAL, ZoeMP3, ZoeMO, ZoeAMAL, ZoeLA, ZoeJYD-34, and Metairie were extracted from fresh blood from dogs. DNA were extracted and sequenced with MiSeq technology. Allele frequencies were calculated and compared with the previously reported susceptible, LOE, and resistant D. immitis populations. Results The allele frequencies identified in the current resistant and susceptible isolates were in accordance with the allele frequencies previously reported in related phenotypes. The ZoeMO population, a subset of the ZoeJYD-34 population, showed a genetic profile that was consistent with some reversion towards susceptibility compared with the parental ZoeJYD-34 population. The Random Forest algorithm was used to create a predictive model using different SNPs. The model with a combination of three SNPs (NODE_42411_RC, NODE_21554_RC, and NODE_45689 appears to be suitable for future monitoring. Conclusions MiSeq technology provided a suitable methodology to work with the microfilarial samples. The list of SNPs that showed good predictability for ML resistance was narrowed. Additional phenotypically well characterized D. immitis isolates are required to finalize the best set of SNPs to be

  17. Crystal and molecular simulation of high-performance polymers. (United States)

    Colquhoun, H M; Williams, D J


    Single-crystal X-ray analyses of oligomeric models for high-performance aromatic polymers, interfaced to computer-based molecular modeling and diffraction simulation, have enabled the determination of a range of previously unknown polymer crystal structures from X-ray powder data. Materials which have been successfully analyzed using this approach include aromatic polyesters, polyetherketones, polythioetherketones, polyphenylenes, and polycarboranes. Pure macrocyclic homologues of noncrystalline polyethersulfones afford high-quality single crystals-even at very large ring sizes-and have provided the first examples of a "protein crystallographic" approach to the structures of conventionally amorphous synthetic polymers.

  18. Generalized diffraction-stack migration and filtering of coherent noise

    KAUST Repository

    Zhan, Ge


    We reformulate the equation of reverse-time migration so that it can be interpreted as summing data along a series of hyperbola-like curves, each one representing a different type of event such as a reflection or multiple. This is a generalization of the familiar diffraction-stack migration algorithm where the migration image at a point is computed by the sum of trace amplitudes along an appropriate hyperbola-like curve. Instead of summing along the curve associated with the primary reflection, the sum is over all scattering events and so this method is named generalized diffraction-stack migration. This formulation leads to filters that can be applied to the generalized diffraction-stack migration operator to mitigate coherent migration artefacts due to, e.g., crosstalk and aliasing. Results with both synthetic and field data show that generalized diffraction-stack migration images have fewer artefacts than those computed by the standard reverse-time migration algorithm. The main drawback is that generalized diffraction-stack migration is much more memory intensive and I/O limited than the standard reverse-time migration method. © 2014 European Association of Geoscientists & Engineers.

  19. Effect of flow parameters on flare stack generator noise

    International Nuclear Information System (INIS)

    Dinn, T.S.


    The SoundPLAN Computer Noise Model was used to determine the general effect of flare noise in a community adjacent to a petrochemical plant. Tests were conducted to determine the effect of process flow conditions and the pulsating flame on the flare stack generator noise from both a refinery flare and process flare. Flaring under normal plant operations, the flaring of fuel gas and the flaring of hydrogen were the three conditions that were tested. It was shown that the steam flow rate was the determining factor in the flare stack generated noise. Variations in the water seal level in the flare line surge tank increased or decreased the gas flowrate, which resulted in a pulsating flame. The period and amplitude of the pulsating noise from the flare stacks was determined by measuring several parameters. Flare stack noise oscillations were found to be greater for the process flare than for the refinery flare stack. It was suggested that minimizing the amount of steam fed to the flare and improving the burner design would minimize noise. 2 tabs., 6 figs

  20. Estimation of stacking fault and twin energies in transition metals

    International Nuclear Information System (INIS)

    Papon, Anne-Marie


    As twins and stacking faults play an important role in the plastic deformation of metals, the objective of this research thesis is, by using an as correct as possible description of band d state density, to assess the internal energy of twins and stacking faults in metals with a CFC, HC or CC crystal structure. If, in transition metals, cohesion mainly results from d electron attraction, other terms intervening in crystal equilibrium must also be taken into account. Thus, the author proposes a decomposition of cohesion energy. The geometry of twins and stacking faults in compact phases is defined, and energy calculations are presented and discussed. Alloying effects are then addressed, as well as a general comparison with available experimental results. After a geometric description of twins and stacking faults in CC structures, their energies are calculated for a Gaussian distribution of state density. For higher order moments, defect energy due to d orbital anisotropy is assessed, and then applied to energy and stability calculations in twins and stacking faults for various relaxed atomic configurations

  1. Communication: Thermodynamics of stacking disorder in ice nuclei (United States)

    Quigley, D.


    A simple Ising-like model for the stacking thermodynamics of ice 1 is constructed for nuclei in supercooled water, and combined with classical nucleation theory. For relative stabilities of cubic and hexagonal ice I within the range of experimental estimates, this predicts critical nuclei are stacking disordered at strong sub-cooling, consistent with recent experiments. At higher temperatures nucleation of pure hexagonal ice is recovered. Lattice-switching Monte-Carlo is applied to accurately compute the relative stability of cubic and hexagonal ice for the popular mW model of water. Results demonstrate that this model fails to adequately capture the relative energetics of the two polytypes, leading to stacking disorder at all temperatures.

  2. Reliability assessment of germanium gate stacks with promising initial characteristics (United States)

    Lu, Cimang; Lee, Choong Hyun; Nishimura, Tomonori; Nagashio, Kosuke; Toriumi, Akira


    This work reports on the reliability assessment of germanium (Ge) gate stacks with promising initial electrical properties, with focus on trap generation under a constant electric stress field (Estress). Initial Ge gate stack properties do not necessarily mean highly robust reliability when it is considered that traps are newly generated under high Estress. A small amount of yttrium- or scandium oxide-doped GeO2 (Y-GeO2 or Sc-GeO2, respectively) significantly reduces trap generation in Ge gate stacks without deterioration of the interface. This is explained by the increase in the average coordination number (Nav) of the modified GeO2 network that results from the doping.

  3. Edge-edge interactions in stacked graphene nanoplatelets

    Energy Technology Data Exchange (ETDEWEB)

    Cruz Silva, Eduardo [ORNL; Terrones Maldonado, Humberto [ORNL; Terrones Maldonado, Mauricio [ORNL; Jia, Xiaoting [Massachusetts Institute of Technology (MIT); Sumpter, Bobby G [ORNL; Dresselhaus, M [Massachusetts Institute of Technology (MIT); Meunier, V. [Rensselaer Polytechnic Institute (RPI)


    High-resolution transmission electron microscopy (HRTEM) studies show the dynamics of small graphene platelets on larger graphene layers. The platelets move nearly freely to eventually lock in at well-defined positions close to the edges of the larger underlying graphene sheet. While such movement is driven by a shallow potential energy surface described by an interplane interaction, the lock-in position occurs by via edge-edge interactions of the platelet and the graphene surface located underneath. Here we quantitatively study this behavior using van der Waals density functional calculations. Local interactions at the open edges are found to dictate stacking configurations that are different from Bernal (AB) stacking. These stacking configurations are known to be otherwise absent in edge-free two-dimensional (2D) graphene. The results explain the experimentally observed platelet dynamics and provide a detailed account of the new electronic properties of these combined systems.

  4. Magneto-optical properties of ABC-stacked trilayer graphene. (United States)

    Lin, Yi-Ping; Lin, Chiun-Yan; Ho, Yen-Hung; Do, Thi-Nga; Lin, Ming-Fa


    The generalized tight-binding model is developed to investigate the magneto-optical absorption spectra of ABC-stacked trilayer graphene. The absorption peaks can be classified into nine categories of inter-Landau-level optical excitations, including three intra-group and six inter-group ones. Most of them belong to the twin-peak structures because of the asymmetric Landau level spectrum. The threshold absorption peak alone comes from a certain excitation channel, and its frequency is associated with a specific interlayer atomic interaction. The Landau-level anticrossings cause extra absorption peaks. Moreover, a simple relationship between the absorption frequency and the field strength is absent. The magneto-optical properties of ABC-stacked trilayer graphene are totally different from those of AAA- and ABA-stacked ones, such as the number, intensity and frequency of absorption peaks.

  5. Thermoacoustic design using stem of goose down stack (United States)

    Farikhah, Irna; Ristanto, Sigit; Idrus, Hadiyati; Kaltsum, Ummi; Faisal, Affandi; Setiawan, Ihsan; Setio Utomo, Agung Bambang


    Many refrigerators using CFC as a refrigerant are seen as the cause of the depletion of ozone. Hence, thermoacoustic was chosen as an alternative refrigerator that safe for environment. There are many variable that influenced the optimization of thermoacoustic design. One of them is thermal conductivity of material of stack. The Stack material must have a low thermal conductivity. In this research we used organic stack made of stem of goose down. It has superior thermal insulating. It means that they have the lowest thermal conductivity. The system uses no refrigerant or compressor, and the only mechanical moving part is the loudspeaker connected to a signal generator that produces the acoustic. The working fluid is air and the material of resonator is stainless steel. A series test on the laboratory found that there is a decrease of 5°C in temperature for about 2 minutes.

  6. The measurement of power reactor stack releases under accident conditions

    International Nuclear Information System (INIS)

    Stroem, L.


    The performance of a typical Swedish monitor for ventilation stack radioactivity releases is examined critically with respect to accident generated radioactive particles. The conditions in the stack, particle character, and the monitor design are considered. A large LOCA outside the containment leads to high relative humidity, and high temperature, or mist in the stack. A small external LOCA results in a moderate increase in temperature and humidity, and condensing conditions only with reduced ventilation. Particle size and stickiness are estimated for different types of accident. A particle is sticky if it adheres after contact with a solid, smooth, dry, and clean surface. The monitor performance is concluded to be poor for large, sticky particles, like mist droplets. Dense aerosols, like fire smoke, will plug the sampling filter. Non-sticky particles are generally sampled with acceptable accuracy. (au)

  7. Electric toy vehicle powered by a PEMFC stack

    Energy Technology Data Exchange (ETDEWEB)

    Beneito, Ruben; Vilaplana, Joaquin; Gisbert, Santiago [Technological Institute for Toy (AIJU), 03440 Ibi (Spain)


    The article describes the design and development of an electric toy vehicle powered by a fuel cell stack. The system consisted of a 150 W PEMFC stack powered by hydrogen/air, a tank of metal hydrides of AB (TiFe) alloy type with a capacity of 300 standard litres, for storing hydrogen, and an electronic power device based on electrolytic capacitors, to supply peak power demands during acceleration and start up of the vehicle. The air supply was provided by a fan preceded by a filter, and in a similar manner the stack was cooled by an air ventilation system. An electrovalve was used to supply H{sub 2} in dead-ended mode. All the components were integrated in the vehicle, and the prototype was tested in real working conditions, in a test bench and by children. (author)

  8. Piezoelectric stack actuator parameter extraction with hysteresis compensation

    DEFF Research Database (Denmark)

    Zsurzsan, Tiberiu-Gabriel; Mangeot, Charles; Andersen, Michael A. E.


    The Piezoelectric Actuator Drive (PAD) is a type of rotary motor that transforms the linear motion of piezoelectric stack actuators into a precise rotational motion. The very high stiffness of the actuators employed make this type of motor suited for open-loop control, but the inherent hysteresis...... exhibited by piezoelectric ceramics causes losses. Therefore, this paper presents a straightforward method to measure piezoelectric stack actuator equiv- alent parameters that includes nonlinearities. By folding the nonlinearities into a newly-defined cou- pling coefficient, the inherent hysteretic behavior...... of piezoelectric stack actuators can be greatly reduced through precompensation. Experimental results show a fitting accuracy of 98.8 % between the model and measurements and a peak absolute error reduction by a factor of 10 compared to the manufacturer- provided parameter. This method improves both the static...

  9. Stacking and discontinuous buffers in capillary zone electrophoresis. (United States)

    Shihabi, Z K


    Discontinuous buffers for capillary zone electrophoresis (CZE) can be used under less rigid conditions compared to those for isotachophoresis for stacking. They can be prepared simply by modifying the sample itself, either by addition of small inorganic ions, low conductivity diluents, or both, and also by adjusting its pH, meanwhile injecting a large volume on the capillary. Zwitterionic and organic-based buffers such as triethanolamine and tris(hydroxymethyl)aminomethane (Tris) are well suited for stacking due to their low conductivity, provided the buffer is discontinuous as demonstrated here. A simple mechanism based on discontinuous buffers is described to explain many of the observed stacking types in CZE, pointing out the many similarities to transient isotachophoresis.

  10. Salt Concentration Differences Alter Membrane Resistance in Reverse Electrodialysis Stacks

    KAUST Repository

    Geise, Geoffrey M.


    Membrane ionic resistance is usually measured by immersing the membrane in a salt solution at a single, fixed concentration. While salt concentration is known to affect membrane resistance when the same concentration is used on both sides of the membrane, little is known about membrane resistance when the membrane is placed between solutions of different concentrations, such as in a reverse electrodialysis (RED) stack. Ionic resistance measurements obtained using Selemion CMV and AMV that separated sodium chloride and ammonium bicarbonate solutions of different concentrations were greater than those measured using only the high-concentration solution. Measured RED stack resistances showed good agreement with resistances calculated using an equivalent series resistance model, where the membranes accounted for 46% of the total stack resistance. The high area resistance of the membranes separating different salt concentration solutions has implications for modeling and optimizing membranes used in RED systems.

  11. Continued SOFC cell and stack technology and improved production methods

    Energy Technology Data Exchange (ETDEWEB)

    Wandel, M.; Brodersen, K.; Phair, J. (and others)


    Within this project significant results are obtained on a number of very diverse areas ranging from development of cell production, metallic creep in interconnect to assembling and test of stacks with foot print larger than 500 cm2. Out of 38 milestones 28 have been fulfilled and 10 have been partly fulfilled. This project has focused on three main areas: 1) The continued cell development and optimization of manufacturing processes aiming at production of large foot-print cells, improving cell performance and development environmentally more benign production methods. 2) Stack technology - especially stacks with large foot print and improving the stack design with respect to flow geometry and gas leakages. 3) Development of stack components with emphasis on sealing (for 2G as well as 3G), interconnect (coat, architecture and creep) and test development. Production of cells with a foot print larger than 500 cm2 is very difficult due to the brittleness of the cells and great effort has been put into this topic. Eight cells were successfully produced making it possible to assemble and test a real stack thereby giving valuable results on the prospects of stacks with large foot print. However, the yield rate is very low and a significant development to increase this yield lies ahead. Several lessons were learned on the stack level regarding 'large foot print' stacks. Modelling studies showed that the width of the cell primarily is limited by production and handling of the cell whereas the length (in the flow direction) is limited by e.g. pressure drop and necessary manifolding. The optimal cell size in the flow direction was calculated to be between approx20 cm and < 30 cm. From an economical point of view the production yield is crucial and stacks with large foot print cell area are only feasible if the cell production yield is significantly enhanced. Co-casting has been pursued as a production technique due to the possibilities in large scale production

  12. Electrically Conductive and Protective Coating for Planar SOFC Stacks

    Energy Technology Data Exchange (ETDEWEB)

    Choi, Jung-Pyung; Stevenson, Jeffry W.


    Ferritic stainless steels are preferred interconnect materials for intermediate temperature SOFCs because of their resistance to oxidation, high formability and low cost. However, their protective oxide layer produces Cr-containing volatile species at SOFC operating temperatures and conditions, which can cause cathode poisoning. Electrically conducting spinel coatings have been developed to prevent cathode poisoning and to maintain an electrically conductive pathway through SOFC stacks. However, this coating is not compatible with the formation of stable, hermetic seals between the interconnect frame component and the ceramic cell. Thus, a new aluminizing process has been developed by PNNL to enable durable sealing, prevent Cr evaporation, and maintain electrical insulation between stack repeat units. Hence, two different types of coating need to have stable operation of SOFC stacks. This paper will focus on the electrically conductive coating process. Moreover, an advanced coating process, compatible with a non-electrically conductive coating will be

  13. Multipole Stack for the 800 MeV PS Booster

    CERN Multimedia


    The 800 MeV PS Booster had seen first beam in its 4 superposed rings in 1972, routine operation began in 1973. In the strive for ever higher beam intensities, the need for additional multipole lenses became evident. After detailed studies, the manufacture of 8 stacks of multipoles was launched in 1974. Each stack consists of 4 superposed multipoles and each multipole has 4 concentric shells. From the innermost to the outermost shell, Type A contains octupole, skew-octupole, sextupole, skew-sextupole. Type B contains skew-octupole, skew-sextupole, vertical dipole, horizontal dipole. Completion of installation in 1976 opened the way to higher beam intensities. M. Battiaz is seen here with a multipole stack and its many electrical connections.

  14. Nuclear fuel rod with retainer for pellet stack

    International Nuclear Information System (INIS)

    Cloue, J.M.


    The rod, usable in pressurized water reactors, comprises a stack of fuel pellets and means holding the stack against an end plug of the fuel can during handling operations. These means include a radially expansive element (retainer) of which the shape is so that when it is free at ambient temperature it is gripping the inside of the casing, and a temperature sensitive spacer which contracts the retainer to release it from the casing at a temperature between the ambient and the operating temperature of a reactor [fr

  15. Implementing cloud storage with OpenStack Swift

    CERN Document Server

    Rajana, Kris; Varma, Sreedhar


    This tutorial-based book has a step-by-step approach for each topic, ensuring it is thoroughly covered and easy to follow. If you are an IT administrator who wants to enter the world of cloud storage using OpenStack Swift, then this book is ideal for you. Whether your job is to build, manage, or use OpenStack Swift, this book is an ideal way to move your career ahead. Only basic Linux and server technology skills are expected, to take advantage of this book.

  16. Exact Solutions to the Double TSP with Multiple Stacks

    DEFF Research Database (Denmark)

    Petersen, Hanne Løhmann; Archetti, Claudia; Madsen, Oli B.G.

    In the Double Travelling Salesman Problem with Multiple Stacks (DTSPMS) a set of orders is given, each one requiring transportation of one item from a customer in a pickup region to a customer in a delivery region. The vehicle available for the transportation in each region carries a container......, which is organised in rows of given length. Each row is handled independently from the others according to a LIFO stack policy. The DTSPMS consists in determining the pickup tour, the loading plan of the container and the delivery tour in such a way that the total length of the two tours is minimised...

  17. Hardware Evaluation of the Horizontal Exercise Fixture with Weight Stack (United States)

    Newby, Nate; Leach, Mark; Fincke, Renita; Sharp, Carwyn


    HEF with weight stack seems to be a very sturdy and reliable exercise device that should function well in a bed rest training setting. A few improvements should be made to both the hardware and software to improve usage efficiency, but largely, this evaluation has demonstrated HEF's robustness. The hardware offers loading to muscles, bones, and joints, potentially sufficient to mitigate the loss of muscle mass and bone mineral density during long-duration bed rest campaigns. With some minor modifications, the HEF with weight stack equipment provides the best currently available means of performing squat, heel raise, prone row, bench press, and hip flexion/extension exercise in a supine orientation.

  18. Experimental 1 kW 20 cell PEFC stack

    Energy Technology Data Exchange (ETDEWEB)

    Buechi, F.N.; Marmy, C.A.; Scherer, G.G. [Paul Scherrer Inst. (PSI), Villigen (Switzerland); Ruge, M. [Swiss Federal Inst. of Technology (ETH), Zuerich (Switzerland)


    A 20-cell PEFC stack was designed and built. Resin impregnated graphite was used as bipolar plate material. The air cooling of the stack was optimized by introducing high surface structures into the open space of the cooling plates. At {eta} (H{sub 2} LHV) = 0.5 a power of 880 W was obtained under conditions of low gas-pressures of 1.15 bar{sub a}. The auxiliary power for process air supply and cooling at 880 W power is less than 7% of the power output, indicating that the described system may be operated at a high efficiency. (author) 5 figs., 2 refs.

  19. Second Generation Small Pixel Technology Using Hybrid Bond Stacking (United States)

    Venezia, Vincent C.; Hsiung, Alan Chih-Wei; Yang, Wu-Zang; Zhang, Yuying; Zhao, Cheng; Lin, Zhiqiang; Grant, Lindsay A.


    In this work, OmniVision’s second generation (Gen2) of small-pixel BSI stacking technologies is reviewed. The key features of this technology are hybrid-bond stacking, deeper back-side, deep-trench isolation, new back-side composite metal-oxide grid, and improved gate oxide quality. This Gen2 technology achieves state-of-the-art low-light image-sensor performance for 1.1, 1.0, and 0.9 µm pixel products. Additional improvements on this technology include less than 100 ppm white-pixel process and a high near-infrared (NIR) QE technology. PMID:29495272

  20. Second Generation Small Pixel Technology Using Hybrid Bond Stacking


    Vincent C. Venezia; Alan Chih-Wei Hsiung; Wu-Zang Yang; Yuying Zhang; Cheng Zhao; Zhiqiang Lin; Lindsay A. Grant


    In this work, OmniVision’s second generation (Gen2) of small-pixel BSI stacking technologies is reviewed. The key features of this technology are hybrid-bond stacking, deeper back-side, deep-trench isolation, new back-side composite metal-oxide grid, and improved gate oxide quality. This Gen2 technology achieves state-of-the-art low-light image-sensor performance for 1.1, 1.0, and 0.9 µm pixel products. Additional improvements on this technology include less than 100 ppm white-pixel process a...

  1. Second Generation Small Pixel Technology Using Hybrid Bond Stacking

    Directory of Open Access Journals (Sweden)

    Vincent C. Venezia


    Full Text Available In this work, OmniVision’s second generation (Gen2 of small-pixel BSI stacking technologies is reviewed. The key features of this technology are hybrid-bond stacking, deeper back-side, deep-trench isolation, new back-side composite metal-oxide grid, and improved gate oxide quality. This Gen2 technology achieves state-of-the-art low-light image-sensor performance for 1.1, 1.0, and 0.9 µm pixel products. Additional improvements on this technology include less than 100 ppm white-pixel process and a high near-infrared (NIR QE technology.

  2. Second Generation Small Pixel Technology Using Hybrid Bond Stacking. (United States)

    Venezia, Vincent C; Hsiung, Alan Chih-Wei; Yang, Wu-Zang; Zhang, Yuying; Zhao, Cheng; Lin, Zhiqiang; Grant, Lindsay A


    In this work, OmniVision's second generation (Gen2) of small-pixel BSI stacking technologies is reviewed. The key features of this technology are hybrid-bond stacking, deeper back-side, deep-trench isolation, new back-side composite metal-oxide grid, and improved gate oxide quality. This Gen2 technology achieves state-of-the-art low-light image-sensor performance for 1.1, 1.0, and 0.9 µm pixel products. Additional improvements on this technology include less than 100 ppm white-pixel process and a high near-infrared (NIR) QE technology.

  3. Band engineering in transition metal dichalcogenides: Stacked versus lateral heterostructures

    International Nuclear Information System (INIS)

    Guo, Yuzheng; Robertson, John


    We calculate a large difference in the band alignments for transition metal dichalcogenide (TMD) heterojunctions when arranged in the stacked layer or lateral (in-plane) geometries, using direct supercell calculations. The stacked case follows the unpinned limit of the electron affinity rule, whereas the lateral geometry follows the strongly pinned limit of alignment of charge neutrality levels. TMDs therefore provide one of the few clear tests of band alignment models, whereas three-dimensional semiconductors give less stringent tests because of accidental chemical trends in their properties.

  4. Simulation of Collective Excitations in Long Josephson Junction Stacks (United States)

    Rahmonov, Ilhom; Shukrinov, Yury; Atanasova, Pavlina; Zemlyanaya, Elena; Streltsova, Oksana; Zuev, Maxim; Plecenik, Andrej; Irie, Akinobu


    The phase dynamics of a stack of long Josephson junctions has been studied. Both inductive and capacitive couplings between Josephson junctions have been taken into account in the calculations. The IV-curve, the dependence on the bias current of the radiation power and dynamics of each JJs of the stack have been investigated. The coexistence of the charge traveling wave and fluxon states has been observed. This state can be considered as a new collective excitation in the system of coupled Josephson junctions. We demonstrate that the observed collective excitation leads to the decrease of radiation power from the system.

  5. Spectrally tunable linear polarization rotation using stacked metallic metamaterials (United States)

    Romain, Xavier; Baida, Fadi I.; Boyer, Philippe


    We make a theoretical study of the transmission properties of a stack of metallic metamaterials and show that is able to achieve a perfect transmission selectively exhibiting broadband (Q {10}5) polarization rotation. We especially highlight how the arrangement of the stacked structure, as well as the metamaterial unit cell geometry, has a large influence on transmission in the spectral domain. For this purpose, we use an extended analytical Jones formalism that allows us to obtain a rigorous and analytical expression of the transmission. Such versatile structures could find potential applications in polarimetry or in the control of light polarization for THz waves.

  6. Mononuclear and binuclear lanthanide complexes of the macrocyclic polyamine polycarboxylic ligands H8OTEC and H8OHEC

    International Nuclear Information System (INIS)

    Schumann, H.; Boettger, U.; Zschunke, A; Weisshoff, H.


    Full text: In recent years there is a growing interest in design and synthesis of macrocyclic ligands and of their dinuclear complexes, owing to their relevance in basic and applied chemistry.1 Our studies are aimed to synthesize ligands based on the DOTA or DTPA backbone which can at least bind two trivalent lanthanide ions, to study their stereochemical properties and to determine the stability of such complexes in aqueous solution. We have recently reported the successful synthesis and characterization of two new hexadecadentate macrocyclic polyaza polycarboxylate ligands OTEC (1,4,7,10,13,16,19,22 - octaazacyclotetracosane - 1,4,7,10,13,16,19,22-octaacetic acid) and OHEC (1,4,7,10,14,17,20,-23 - octaazacyclohexacosane - 1,4,7,10,14,17,20,23 - octaacetic acid) and some of their mono- and dinuclear lanthanide(III) chelate complexes which are highly stable and watersoluble. The acid-base properties of these ligands were characterized by using potentiometry and NMR titration techniques. The determination of the thermodynamic stability constants governing the formation of the complexes with Ca(II), Mg(II) and Gd(III) are in progress. The solid structure of four homodinuclear lanthanide(III)chelates (La(III), Eu(III), Gd(III) and Y(III)) of the ligand OHEC was investigated by X-ray crystal structure analysis. In the isostructural complexes the lanthanide ions are nine coordinated by eight donors provided by the ligand and one oxygen of a water molecule. This results in an unusual coordination polyhedron different from that found in the lanthanide complexes of the ligand DOTA and TETA. The conformation of the macrocycles in these complexes was compared to those of the parent compound 1,4,7,10,14,17,20,23-octaazacyclohex-acosane and its dinuclear copper complex. Due to NMR investigations the environment of the lanthanide cation is probably identical in solution and in the solid state. There is nearly a quantitative fit between the crystal structure and the major

  7. From the components to the stack. Developing and designing 5kW HT-PEFC stacks; Von der Komponente zum Stack. Entwicklung und Auslegung von HT-PEFC-Stacks der 5 kW-Klasse

    Energy Technology Data Exchange (ETDEWEB)

    Bendzulla, Anne


    The aim of the present project is to develop a stack design for a 5-kW HTPEFC system. First, the state of the art of potential materials and process designs will be discussed for each component. Then, using this as a basis, three potential stack designs with typical attributes will be developed and assessed in terms of practicality with the aid of a specially derived evaluation method. Two stack designs classified as promising will be discussed in detail, constructed and then characterized using short stack tests. Comparing the stack designs reveals that both designs are fundamentally suitable for application in a HT-PEFC system with on-board supply. However, some of the performance data differ significantly for the two stack designs. The preferred stack design for application in a HT-PEFC system is characterized by robust operating behaviour and reproducible high-level performance data. Moreover, in compact constructions (120 W/l at 60 W/kg), the stack design allows flexible cooling with thermal oil or air, which can be adapted to suit specific applications. Furthermore, a defined temperature gradient can be set during operation, allowing the CO tolerance to be increased by up to 10 mV. The short stack design developed within the scope of the present work therefore represents an ideal basis for developing a 5-kW HT-PEFC system. Topics for further research activities include improving the performance by reducing weight and/or volume, as well as optimizing the heat management. The results achieved within the framework of this work clearly show that HTPEFC stacks have the potential to play a decisive role in increasing efficiency in the future, particularly when combined with an on-board supply system. (orig.) [German] Ziel der vorliegenden Arbeit ist die Entwicklung eines Stackkonzeptes fuer ein 5 kW-HT-PEFC System. Dazu wird zunaechst fuer jede Komponente der Stand der Technik moeglicher Materialien und Prozesskonzepte diskutiert. Darauf aufbauend werden drei

  8. Stress-induced formation mechanism of stacking fault tetrahedra in nano-cutting of single crystal copper

    International Nuclear Information System (INIS)

    Wang, Quanlong; Bai, Qingshun; Chen, Jiaxuan; Guo, Yongbo; Xie, Wenkun


    Graphical abstract: In this paper, molecular dynamics simulation is performed to study the distribution of dislocation defects and local atomic crystal structure of single crystal copper. The stress distribution is investigated which is calculated by virial stress and analyzed by static pressure. The results are shown in (a)–(d). It is indicated that the compressive stress mainly spreads over the shear-slip zone, and the tensile stress is consisted in flank friction zone, shown in (a). The high tensile stress in subsurface is the source of stress, shown in (b). By the driven action of the stress source, the initial stair-rod dislocation nucleates. Then the dislocation climbs along four {1 1 1} planes under the stress driven action, shown in (d). Finally, the SFT is formed by the interaction of the compressive stress and the tensile stress which come from the shear-slip zone and friction zone, respectively. Besides, stair-rod dislocation, stacking faults and dislocation loop are also nucleated in the subsurface, shown in (c). Dislocation distribution, local atomic crystal structure state and stress-induced formation process of SFT by atomic. - Highlights: • A novel defect structure “stress-induced stacking fault tetrahedra” is revealed. • Atomic structural evolution and stress state distribution of the SFT are studied. • The stress-induced formation mechanism of the SFT is proposed. - Abstract: Stacking fault tetrahedra commonly existed in subsurface of deformed face center cubic metals, has great influence on machining precision and surface roughness in nano-cutting. Here we report, a stacking fault tetrahedra is formed in subsurface of workpiece during nano-cutting. The variation of cutting force and subsurface defects distribution are studied by using molecular dynamics simulation. The stress distribution is investigated which is calculated by virial stress and analyzed by static compression. The result shows that the cutting force has a rapidly

  9. Magneto-electroluminescence effects in the single-layer organic light-emitting devices with macrocyclic aromatic hydrocarbons

    Directory of Open Access Journals (Sweden)

    S.-T. Pham


    Full Text Available Magneto-electroluminescence (MEL effects are observed in single-layer organic light-emitting devices (OLEDs comprising only macrocyclic aromatic hydrocarbons (MAHs. The fluorescence devices were prepared using synthesized MAHs, namely, [n]cyclo-meta-phenylene ([n]CMP, n = 5, 6. The MEL ratio of the resulting OLED is 1%–2% in the spectral wavelength range of 400-500 nm, whereas it becomes negative (−1.5% to −2% in the range from 650 to 700 nm. The possible physical origins of the sign change in the MEL are discussed. This wavelength-dependent sign change in the MEL ratio could be a unique function for future single-layer OLEDs capable of magnetic-field-induced color changes.

  10. Cyclic and Macrocyclic Organic Compounds - a Personal Review in Honor of Professor Leopold Ružička

    Directory of Open Access Journals (Sweden)

    Höcker¸, H.


    Full Text Available Ružička opened the field of cyclic molecules such as cyclic terpenes and cyclic ketones with up to 17 ring atoms. This work until now was extended in many directions such as cyclic paraffins, crown ethers and cryptands and cyclic ester amides. Cyclic molecules are formed upon electron transfer and intramolecular association of polymers with two active ends and they are synthesized by directed cyclization of bifunctional macromolecules. In the course of step growth polymerization and ring opening polymerization, ring chain equilibria may be established; the larger the monomer unit the easier is the separation of pure oligomers such as the heptamer of cyclododecene with 84 carbon atoms in the ring. Still many questions remain open, in particular whether there are macrocyclic catenanes in commercial polycondensates.

  11. A review on the toxicity and non-target effects of macrocyclic lactones in terrestrial and aquatic environments. (United States)

    Lumaret, Jean-Pierre; Errouissi, Faiek; Floate, Kevin; Römbke, Jörg; Wardhaugh, Keith


    The avermectins, milbemycins and spinosyns are collectively referred to as macrocyclic lactones (MLs) which comprise several classes of chemicals derived from cultures of soil micro-organisms. These compounds are extensively and increasingly used in veterinary medicine and agriculture. Due to their potential effects on non-target organisms, large amounts of information on their impact in the environment has been compiled in recent years, mainly caused by legal requirements related to their marketing authorization or registration. The main objective of this paper is to critically review the present knowledge about the acute and chronic ecotoxicological effects of MLs on organisms, mainly invertebrates, in the terrestrial and aquatic environment. Detailed information is presented on the mode-of-action as well as the ecotoxicity of the most important compounds representing the three groups of MLs. This information, based on more than 360 references, is mainly provided in nine tables, presenting the effects of abamectin, ivermectin, eprinomectin, doramectin, emamectin, moxidectin, and spinosad on individual species of terrestrial and aquatic invertebrates as well as plants and algae. Since dung dwelling organisms are particularly important non-targets, as they are exposed via dung from treated animals over their whole life-cycle, the information on the effects of MLs on dung communities is compiled in an additional table. The results of this review clearly demonstrate that regarding environmental impacts many macrocyclic lactones are substances of high concern particularly with larval instars of invertebrates. Recent studies have also shown that susceptibility varies with life cycle stage and impacts can be mitigated by using MLs when these stages are not present. However information on the environmental impact of the MLs is scattered across a wide range of specialised scientific journals with research focusing mainly on ivermectin and to a lesser extent on abamectin

  12. A Review on the Toxicity and Non-Target Effects of Macrocyclic Lactones in Terrestrial and Aquatic Environments (United States)

    Lumaret, Jean-Pierre; Errouissi, Faiek; Floate, Kevin; Römbke, Jörg; Wardhaugh, Keith


    The avermectins, milbemycins and spinosyns are collectively referred to as macrocyclic lactones (MLs) which comprise several classes of chemicals derived from cultures of soil micro-organisms. These compounds are extensively and increasingly used in veterinary medicine and agriculture. Due to their potential effects on non-target organisms, large amounts of information on their impact in the environment has been compiled in recent years, mainly caused by legal requirements related to their marketing authorization or registration. The main objective of this paper is to critically review the present knowledge about the acute and chronic ecotoxicological effects of MLs on organisms, mainly invertebrates, in the terrestrial and aquatic environment. Detailed information is presented on the mode-of-action as well as the ecotoxicity of the most important compounds representing the three groups of MLs. This information, based on more than 360 references, is mainly provided in nine tables, presenting the effects of abamectin, ivermectin, eprinomectin, doramectin, emamectin, moxidectin, and spinosad on individual species of terrestrial and aquatic invertebrates as well as plants and algae. Since dung dwelling organisms are particularly important non-targets, as they are exposed via dung from treated animals over their whole life-cycle, the information on the effects of MLs on dung communities is compiled in an additional table. The results of this review clearly demonstrate that regarding environmental impacts many macrocyclic lactones are substances of high concern particularly with larval instars of invertebrates. Recent studies have also shown that susceptibility varies with life cycle stage and impacts can be mitigated by using MLs when these stages are not present. However information on the environmental impact of the MLs is scattered across a wide range of specialised scientific journals with research focusing mainly on ivermectin and to a lesser extent on abamectin

  13. Synthesis, characterization, nano-sized binuclear nickel complexes, DFT calculations and antibacterial evaluation of new macrocyclic Schiff base compounds (United States)

    Parsaee, Zohreh; Mohammadi, Khosro


    Some new macrocyclic bridged dianilines tetradentate with N4coordination sphere Schiff base ligands and their nickel(II)complexes with general formula [{Ni2LCl4} where L = (C20H14N2X)2, X = SO2, O, CH2] have been synthesized. The compounds have been characterized by FT-IR, 1H and 13C NMR, mass spectroscopy, TGA, elemental analysis, molar conductivity and magnetic moment techniques. Scanning electron microscopy (SEM) shows nano-sized structures under 100 nm for nickel (II) complexes. NiO nanoparticle was achieved via the thermal decomposition method and analyzed by FT-IR, SEM and X-ray powder diffraction which indicates closeaccordance to standard pattern of NiO nanoparticle. All the Schiff bases and their complexes have been detected in vitro both for antibacterial activity against two gram-negative and two gram-positive bacteria. The nickel(II) complexes were found to be more active than the free macrocycle Schiff bases. In addition, computational studies of three ligands have been carried out at the DFT-B3LYP/6-31G+(d,p) level of theory on the spectroscopic properties, including IR, 1HNMR and 13CNMR spectroscopy. The correlation between the theoretical and the experimental vibrational frequencies, 1H NMR and 13C NMR of the ligands were 0.999, 0.930-0.973 and 0.917-0.995, respectively. Also, the energy gap was determined and by using HOMO and LUMO energy values, chemical hardness-softness, electronegativity and electrophilic index were calculated.

  14. Adaptation of a 96-well plate larval migration inhibition test for measuring the sensitivity of cyathostomins to macrocyclic lactone anthelmintics. (United States)

    Beasley, A M; Coleman, G T; Kotze, A C


    The use of macrocyclic lactone drugs for control of equine cyathostomins is threatened by increasing levels of resistance. Detection of changes in drug sensitivity is important for effective and sustainable management of cyathostomins, however, at present such detection relies on the use of the faecal egg count reduction test, which is known to be an insensitive method. The present study therefore aimed to examine the use of a 96-well plate larval migration inhibition test for detection of resistance to macrocyclic lactone drugs in cyathostomins. We optimised conditions for migration of larvae, and examined the effects of larval storage time on drug dose responses. The modified test was able to define the sensitivity of cyathostomin isolates to ivermectin and eprinomectin in terms of dose response curves, and IC 50 and IC 95 values. The IC 95 showed much greater consistency than the IC 50 with larvae that had been stored for different periods prior to the test. Comparisons between two isolates, which had both been defined previously as susceptible using faecal egg count reduction tests, showed more variation at the IC 50 compared to the IC 95 . Limitations of the test included the degree of variation in control-well migration despite optimisation of migration incubation conditions, and the need to incorporate a method to determine the species composition of the larval populations to account for possible species differences in drug sensitivity among cyathostomins. Validation of the technique on reference susceptible and resistant isolates of known species composition is still required. Copyright © 2017 Elsevier B.V. All rights reserved.

  15. An Exact Method for the Double TSP with Multiple Stacks

    DEFF Research Database (Denmark)

    Larsen, Jesper; Lusby, Richard Martin; Ehrgott, Matthias

    The double travelling salesman problem with multiple stacks (DTSPMS) is a pickup and delivery problem in which all pickups must be completed before any deliveries can be made. The problem originates from a real-life application where a 40 foot container (configured as 3 columns of 11 rows) is used...

  16. An Exact Method for the Double TSP with Multiple Stacks

    DEFF Research Database (Denmark)

    Lusby, Richard Martin; Larsen, Jesper; Ehrgott, Matthias


    The double travelling salesman problem with multiple stacks (DTSPMS) is a pickup and delivery problem in which all pickups must be completed before any deliveries can be made. The problem originates from a real-life application where a 40 foot container (configured as 3 columns of 11 rows) is used...

  17. Hydrothermal synthesis and photoluminescent properties of stacked indium sulfide superstructures. (United States)

    Xing, Yan; Zhang, Hongjie; Song, Shuyan; Feng, Jing; Lei, Yongqian; Zhao, Lijun; Li, Meiye


    Unusual hierarchical stacked superstructures of cubic beta-In2S3 were fabricated via a facile hydrothermal process in the presence of a surfactant cetyltrimethylammonium bromide CTAB; the 3D superstructures were developed by helical propagation of surface steps from microflakes of 10-20 nm thickness.

  18. Phase locked fluxon-antifluxon states in stacked Josephson junctions

    DEFF Research Database (Denmark)

    Carapella, Giovanni; Constabile, Giovanni; Petraglia, Antonio


    Measurements were made on a two-stack long Josephson junction with very similar parameters and electrical access to the thin middle electrode. Mutually phase-locked fluxon-antifluxon states were observed. The observed propagation velocity is in agreement with the theoretical prediction. The I-V c...... in the junctions coexist with fluxons. (C) 1996 American Institute of Physics....

  19. Compactifications of reductive groups as moduli stacks of bundles

    DEFF Research Database (Denmark)

    Martens, Johan; Thaddeus, Michael

    Let G be a reductive group. We introduce the moduli problem of "bundle chains" parametrizing framed principal G-bundles on chains of lines. Any fan supported in a Weyl chamber determines a stability condition on bundle chains. Its moduli stack provides an equivariant toroidal compactification of G...

  20. Stacking faults and microstructural parameters in non-mulberry silk ...

    Indian Academy of Sciences (India)

    Then the whole pattern fitting was done by introducing weight factors for the individual profiles and also taking into account the average stacking faults derived using eqs (4) and (5) in the final stage of refinement with the whole experimental diffraction data of the sample. Computational procedure is given in the flow chart ...

  1. Rhythmic ring–ring stacking drives the circadian oscillator clockwise (United States)

    Chang, Yong-Gang; Tseng, Roger; Kuo, Nai-Wei; LiWang, Andy


    The oscillator of the circadian clock of cyanobacteria is composed of three proteins, KaiA, KaiB, and KaiC, which together generate a self-sustained ∼24-h rhythm of phosphorylation of KaiC. The mechanism propelling this oscillator has remained elusive, however. We show that stacking interactions between the CI and CII rings of KaiC drive the transition from the phosphorylation-specific KaiC–KaiA interaction to the dephosphorylation-specific KaiC–KaiB interaction. We have identified the KaiB-binding site, which is on the CI domain. This site is hidden when CI domains are associated as a hexameric ring. However, stacking of the CI and CII rings exposes the KaiB-binding site. Because the clock output protein SasA also binds to CI and competes with KaiB for binding, ring stacking likely regulates clock output. We demonstrate that ADP can expose the KaiB-binding site in the absence of ring stacking, providing an explanation for how it can reset the clock. PMID:22967510

  2. Rhythmic ring-ring stacking drives the circadian oscillator clockwise. (United States)

    Chang, Yong-Gang; Tseng, Roger; Kuo, Nai-Wei; LiWang, Andy


    The oscillator of the circadian clock of cyanobacteria is composed of three proteins, KaiA, KaiB, and KaiC, which together generate a self-sustained ∼24-h rhythm of phosphorylation of KaiC. The mechanism propelling this oscillator has remained elusive, however. We show that stacking interactions between the CI and CII rings of KaiC drive the transition from the phosphorylation-specific KaiC-KaiA interaction to the dephosphorylation-specific KaiC-KaiB interaction. We have identified the KaiB-binding site, which is on the CI domain. This site is hidden when CI domains are associated as a hexameric ring. However, stacking of the CI and CII rings exposes the KaiB-binding site. Because the clock output protein SasA also binds to CI and competes with KaiB for binding, ring stacking likely regulates clock output. We demonstrate that ADP can expose the KaiB-binding site in the absence of ring stacking, providing an explanation for how it can reset the clock.

  3. Revisiting the Fundamentals and Capabilities of the Stack Compression Test

    DEFF Research Database (Denmark)

    Alves, L.M.; Nielsen, Chris Valentin; Martin, P.A.F.


    performance by comparing the flow curves obtained from its utilisation with those determined by means of compressive testing carried out on solid cylinder specimens of the same material. Results show that mechanical testing of materials by means of the stack compression test is capable of meeting...... the increasing demand of accurate and reliable flow curves for sheet metals....

  4. Tunable infrared plasmonic devices using graphene/insulator stacks (United States)

    Yan, Hugen; Li, Xuesong; Chandra, Bhupesh; Tulevski, George; Wu, Yanqing; Freitag, Marcus; Zhu, Wenjuan; Avouris, Phaedon; Xia, Fengnian


    The collective oscillation of carriers--the plasmon--in graphene has many desirable properties, including tunability and low loss. However, in single-layer graphene, the dependence on carrier concentration of both the plasmonic resonance frequency and magnitude is relatively weak, limiting its applications in photonics. Here, we demonstrate transparent photonic devices based on graphene/insulator stacks, which are formed by depositing alternating wafer-scale graphene sheets and thin insulating layers, then patterning them together into photonic-crystal-like structures. We show experimentally that the plasmon in such stacks is unambiguously non-classical. Compared with doping in single-layer graphene, distributing carriers into multiple graphene layers effectively enhances the plasmonic resonance frequency and magnitude, which is different from the effect in a conventional semiconductor superlattice and is a direct consequence of the unique carrier density scaling law of the plasmonic resonance of Dirac fermions. Using patterned graphene/insulator stacks, we demonstrate widely tunable far-infrared notch filters with 8.2 dB rejection ratios and terahertz linear polarizers with 9.5 dB extinction ratios. An unpatterned stack consisting of five graphene layers shields 97.5% of electromagnetic radiation at frequencies below 1.2 THz. This work could lead to the development of transparent mid- and far-infrared photonic devices such as detectors, modulators and three-dimensional metamaterial systems.

  5. Stacked-Bloch-wave electron diffraction simulations using GPU acceleration

    International Nuclear Information System (INIS)

    Pennington, Robert S.; Wang, Feng; Koch, Christoph T.


    In this paper, we discuss the advantages for Bloch-wave simulations performed using graphics processing units (GPUs), based on approximating the matrix exponential directly instead of performing a matrix diagonalization. Our direct matrix-exponential algorithm yields a functionally identical electron scattering matrix to that generated with matrix diagonalization. Using the matrix-exponential scaling-and-squaring method with a Padé approximation, direct GPU-based matrix-exponential double-precision calculations are up to 20× faster than CPU-based calculations and up to approximately 70× faster than matrix diagonalization. We compare precision and runtime of scaling and squaring methods with either the Padé approximation or a Taylor expansion. We also discuss the stacked-Bloch-wave method, and show that our stacked-Bloch-wave implementation yields the same electron scattering matrix as traditional Bloch-wave matrix diagonalization. - Highlights: • Bloch-wave and stacked-Bloch-wave calculations can be accelerated with GPUs. • Direct approximation of the matrix exponential can be faster than diagonalization. • GPU-based direct approximation can be ≈70× faster than CPU diagonalization. • Larger matrices benefit more from this approach than smaller ones. • Stacked-Bloch-wave scattering results are functionally identical to diagonalization

  6. Do Identical Polar Diatomic Molecules Form Stacked or Linear ...

    Indian Academy of Sciences (India)

    Home; Journals; Resonance – Journal of Science Education; Volume 19; Issue 8. Do Identical Polar Diatomic Molecules Form Stacked or Linear Dimers?: Hydrogen Bonding is Not Just Dipole-Dipole Interactions. C W Williams Richard N Zare E Arunan. General Article Volume 19 Issue 8 August 2014 pp 704-712 ...

  7. 7. Data Structures: Lists, Queues, Stacks and Arrays

    Indian Academy of Sciences (India)

    Home; Journals; Resonance – Journal of Science Education; Volume 2; Issue 6. Algorithms - Data Structures: Lists, Queues, Stacks and Arrays. R K Shyamasundar ... Author Affiliations. R K Shyamasundar1. Computer Science Group, Tata Institute of Fundamental Research, Homi Bhabha Road, Mumbai 400 005, India ...

  8. Seismic fragility of ventilation stack of nuclear power plant

    International Nuclear Information System (INIS)

    Nefedov, S.S.; Yugai, T.Z.; Kalinkin, I.V.; Vizir, P.L.


    Fragility study of safety related elements is necessary step in seismic PSA of nuclear power plant (NPP). In present work fragility was analyzed after the example of the ventilation stack of NPP. Ventilation stack, considered in present work, is a separately erected construction with height of 100 m made of cast-in-place reinforced concrete. In accordance with IAEA terminology fragility of element is defined as conditional probability of its failure at given level of seismic loading. Failure of a ventilation stack was considered as development of the plastic hinge in some section of a shaft. Seismic ground acceleration a, which corresponds to failure, could be defined as limit seismic acceleration of ventilation stack [a]. Limit seismic acceleration [a] was considered as random value. Sources of its variation are connected with stochastic nature of factors determining it (properties of construction materials, soils etc.), and also with uncertainties of existing analytical techniques. Random value [a] was assumed to be distributed lognormally. Median m[a] and logarithmically standard deviation β of this distribution were defined by 'scaling method' developed by R.P. Kennedy et al. Using this values fragility curves were plotted for different levels of confidence probability. (author)

  9. Thermal entrance effects in a thermoacoustic stacked screen regenerator

    NARCIS (Netherlands)

    Bühler, Simon; wilcox, D; Oosterhuis, Joris; van der Meer, Theodorus H.


    Thermoacoustic cryocoolers are of raising interest because they are cost effective and reliable. The underlying heat pumping process occurs in the regenerator, where a sound wave interacts with a solid matrix material. Stacked screens are frequently used to build regenerators for thermoacoustic

  10. Proposal of stack Effect technology for predicted future years (United States)

    Teddy Badai Samodra, FX; Adi Indrawan, Iwan


    Recently, stack effect is a general problem solver in providing vertical ventilation for urban environmental issues. However, study on resilient technology of stack effect for future years as predicted by climate trend should be conducted. Therefore, this research proposes a design of new technology on operable and adaptable vertical ventilation to the environmental change. The research method is conducted by comprehensive simulation of Ecotect Analysis, ANSYS Fluent and Matlab. Urban environment of Surabaya, as the research location, is the representative of tropical region. The results showed that the stack effect height and area could be modified instantly adjusting the environmental condition time by time in the future years. With 1.8 m of stack width, the proposed technology could capture 40 m3 of vertical air flow which is useful for physiological cooling and its dimension could be modified depending on the environmental condition. By providing resilient technology, predictable and sustainable ventilation method is offered to anticipate an unpredicted global warming and environmental change.

  11. Multipole stack for the 4 rings of the PS Booster

    CERN Multimedia

    CERN PhotoLab


    The PS Booster (originally 800 MeV, now 1.4 GeV) saw first beam in 1972, routine operation began in 1973. The strive for ever higher intensities required the addition of multipoles. Manufacture of 8 stacks of multipoles was launched in 1974, for installation in 1976. For details, see 7511120X.

  12. Consolidation process model for film stacking glass/PPS laminates

    NARCIS (Netherlands)

    Grouve, Wouter Johannes Bernardus; Akkerman, Remko


    A model is proposed to optimise the processing parameters for the consolidation of glass/polyphenylene sulphide (PPS) laminates using a film stacking procedure. In a split approach, the heating and consolidation phase are treated separately. The heating phase is modelled using the one-dimensional

  13. 7. Data Structures: Lists, Queues, Stacks and Arrays

    Indian Academy of Sciences (India)

    Home; Journals; Resonance – Journal of Science Education; Volume 2; Issue 6. Algorithms - Data Structures: Lists, Queues, Stacks and Arrays. R K Shyamasundar. Series Article Volume 2 Issue 6 June 1997 pp 39-46. Fulltext. Click here to view fulltext PDF. Permanent link:

  14. Calculating the output distribution of stack filters that are erosion ...

    African Journals Online (AJOL)

    Two procedures to compute the output distribution ϕs of certain stack filters S (so called erosion-dilation cascades) are given. One rests on the disjunctive normal form of S and also yields the rank selection probabilities. The other is based on inclusion-exclusion and e.g. yields ϕs for some important LULU-operators S.

  15. Precise stacking and bonding technology for RDDS structure

    International Nuclear Information System (INIS)

    Higo, T; Toge, N.; Suzuki, T.


    The X-band accelerating structures called RDDS1 (Rounded Dumped Detuned Structure) for the linear collider have been developed. The main body of RDDS1 was successfully fabricated in Japan (KEK, IHI). We established basic fabrication techniques through the development of prototype structures including RDDS1. The precise stacking and bonding technologies for RDDS structure are presented in this paper. (author)

  16. Novel cross-strand three-purine stack of the highly conserved 5'-GA/AAG-5' internal loop at the 3'-end termini of Parvovirus Genomes

    International Nuclear Information System (INIS)

    Chou, S.-H.; Chin, K.-H.


    We have used two-dimensional nuclear magnetic resonance (2D-NMR), distance geometry (DG) and molecular dynamics / energy minimization (MD/EM) methods to study a 2x3 asymmetric internal loop structure of the highly conserved '5'-(GA)/(AAG)-5' bubble' present at the 3'-end hairpin of the single-stranded DNA genome of parvoviruses. This motif contains an unpaired adenosine stacked between two bracketed sheared G·A pairs. However, the phenomenal cross-strand G-G and A-A stacking in the tandem sheared G·A pairs has undergone considerable change. A novel three-purine stacking pattern is observed instead; the inserted A18 base is completely un-stacked from its neighboring G17 and A19 bases, but well stacked with the cross-strand A4 and G3 bases to form a novel A4/A18/G3 stack that is different from the double G/G, A/A or quadruple G/G/G/G stack present in the 5'-(GA)/(AG)-5' or 5'-(GGA)/(AGG)-5' motifs. Unlike the bulged purine residue that usually causes about 20 degree kink in the helical axis of the parent helix when bracketed by canonical G·C or A·T base pairs, no significant kink is observed in the present helix containing a bulged-adenine that is bracketed by sheared G ·A pairs. The phosphodiesters connecting G3-A4 and G17-A18 residues adopt unusual ζ torsional angles close to the trans domain, yet that connecting A18-A19 residues resumes the normal ζ(g - ) value. The well structured '5'-(GAA)/(AG)-5'' internal loop in the parvovirus genomes explains its resistance to single-strand specific endonuclease susceptibility

  17. Stacking multiple transgenes at a selected genomic site via repeated recombinase-mediated DNA cassette exchanges. (United States)

    Li, Zhongsen; Moon, Bryan P; Xing, Aiqiu; Liu, Zhan-Bin; McCardell, Richard P; Damude, Howard G; Falco, S Carl


    Recombinase-mediated DNA cassette exchange (RMCE) has been successfully used to insert transgenes at previously characterized genomic sites in plants. Following the same strategy, groups of transgenes can be stacked to the same site through multiple rounds of RMCE. A gene-silencing cassette, designed to simultaneously silence soybean (Glycine max) genes fatty acid ω-6 desaturase 2 (FAD2) and acyl-acyl carrier protein thioesterase 2 (FATB) to improve oleic acid content, was first inserted by RMCE at a precharacterized genomic site in soybean. Selected transgenic events were subsequently retransformed with the second DNA construct containing a Yarrowia lipolytica diacylglycerol acyltransferase gene (DGAT1) to increase oil content by the enhancement of triacylglycerol biosynthesis and three other genes, a Corynebacterium glutamicum dihydrodipicolinate synthetase gene (DHPS), a barley (Hordeum vulgare) high-lysine protein gene (BHL8), and a truncated soybean cysteine synthase gene (CGS), to improve the contents of the essential amino acids lysine and methionine. Molecular characterization confirmed that the second RMCE successfully stacked the four overexpression cassettes to the previously integrated FAD2-FATB gene-silencing cassette. Phenotypic analyses indicated that all the transgenes expressed expected phenotypes.

  18. Development and Applications of a Stage Stacking Procedure (United States)

    Kulkarni, Sameer; Celestina, Mark L.; Adamczyk, John J.


    The preliminary design of multistage axial compressors in gas turbine engines is typically accomplished with mean-line methods. These methods, which rely on empirical correlations, estimate compressor performance well near the design point, but may become less reliable off-design. For land-based applications of gas turbine engines, off-design performance estimates are becoming increasingly important, as turbine plant operators desire peaking or load-following capabilities and hot-day operability. The current work develops a one-dimensional stage stacking procedure, including a newly defined blockage term, which is used to estimate the off-design performance and operability range of a 13-stage axial compressor used in a power generating gas turbine engine. The new blockage term is defined to give mathematical closure on static pressure, and values of blockage are shown to collapse to curves as a function of stage inlet flow coefficient and corrected shaft speed. In addition to these blockage curves, the stage stacking procedure utilizes stage characteristics of ideal work coefficient and adiabatic efficiency. These curves are constructed using flow information extracted from computational fluid dynamics (CFD) simulations of groups of stages within the compressor. Performance estimates resulting from the stage stacking procedure are shown to match the results of CFD simulations of the entire compressor to within 1.6% in overall total pressure ratio and within 0.3 points in overall adiabatic efficiency. Utility of the stage stacking procedure is demonstrated by estimation of the minimum corrected speed which allows stable operation of the compressor. Further utility of the stage stacking procedure is demonstrated with a bleed sensitivity study, which estimates a bleed schedule to expand the compressors operating range.

  19. Hydrodynamic Modelling and Experimental Analysis of FE-DMFC Stacks (United States)

    Kablou, Yashar

    Direct methanol fuel cells (DMFCs) present some unique features such as having liquid fuel, quick refueling process, compact design and high energy density. These characteristics make them incredibly suitable as a promising power source for portable electronic applications, such as cell phones or laptop computers. Despite of these positive aspects, the commercial development of DMFCs has nevertheless been hindered by some important issues such as, carbon dioxide formation at the anode compartment and, methanol crossover through the membrane. Many researchers have tried to model the two-phase flow behavior inside the DMFC anode compartment using the "homogenous flow modelling" approach, which has proven to be inaccurate specially when dealing with DMFC stacks. On the other hand, several strategies to prevent methanol crossover have been suggested in the literature, including the use of a flowing electrolyte between the DMFC anode and cathode compartments. Preliminary tests on flowing electrolyte direct methanol fuel cells (FE-DMFCs) have shown promising results; however, further investigation should be carried out on the stack level. In the first part of this study, a quasi two-dimensional numerical model was developed, to predict the two-phase flow behavior within the DMFC anode compartment, both in single cell and stack levels. Various types of flow modelling approaches and void fraction correlations were utilized to estimate the pressure drop across the anode compartment. It was found that the "separated flow modelling" approach, as well as CISE correlation for void fraction (developed at the CISE labs in Milan), yield the best results. In the second part, a five-cell FE-DMFC stack unit with a parallel serpentine flow bed design and U-type manifold configuration, was developed and tested at various operating conditions. It was found that, the flowing electrolyte effectively reduced methanol crossover and, improved the stack performance.

  20. Study on the polarity, solubility, and stacking characteristics of asphaltenes

    KAUST Repository

    Zhang, Long-li


    The structure and transformation of fused aromatic ring system in asphaltenes play an important role in the character of asphaltenes, and in step affect the properties of heavy oils. Polarity, solubility and structural characteristics of asphaltenes derived from Tahe atmospheric residue (THAR) and Tuo-826 heavy crude oil (Tuo-826) were analyzed for study of their internal relationship. A fractionation method was used to separate the asphaltenes into four sub-fractions, based on their solubility in the mixed solvent, for the study of different structural and physical-chemical properties, such as polarity, solubility, morphology, stacking characteristics, and mean structural parameters. Transmission electron microscope (TEM) observation can present the intuitive morphology of asphaltene molecules, and shows that the structure of asphaltenes is in local order as well as long range disorder. The analysis results showed that n-heptane asphaltenes of THAR and Tuo-826 had larger dipole moment values, larger fused aromatic ring systems, larger mean number of stacking layers, and less interlayer spacing between stacking layers than the corresponding n-pentane asphaltenes. The sub-fractions that were inclined to precipitate from the mixture of n-heptane and tetrahydrofuran had larger polarity and less solubility. From the first sub-fraction to the fourth sub-fraction, polarity, mean stacking numbers, and average layer size from the TEM images follow a gradual decrease. The structural parameters derived from TEM images could reflect the largest fused aromatic ring system in asphaltene molecule, yet the parameters derived from 1H NMR data reflected the mean message of poly-aromatic ring systems. The structural parameters derived from TEM images were more consistent with the polarity variation of sub-fractions than those derived from 1H NMR data, which indicates that the largest fused aromatic ring system will play a more important role in the stacking characteristics of