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Sample records for nitroxyl amide dipolar

  1. Sequential backbone assignment based on dipolar amide-to-amide correlation experiments

    Energy Technology Data Exchange (ETDEWEB)

    Xiang, ShengQi; Grohe, Kristof; Rovó, Petra; Vasa, Suresh Kumar; Giller, Karin; Becker, Stefan; Linser, Rasmus, E-mail: rali@nmr.mpibpc.mpg.de [Max Planck Institute for Biophysical Chemistry, Department for NMR-Based Structural Biology (Germany)

    2015-07-15

    Proton detection in solid-state NMR has seen a tremendous increase in popularity in the last years. New experimental techniques allow to exploit protons as an additional source of information on structure, dynamics, and protein interactions with their surroundings. In addition, sensitivity is mostly improved and ambiguity in assignment experiments reduced. We show here that, in the solid state, sequential amide-to-amide correlations turn out to be an excellent, complementary way to exploit amide shifts for unambiguous backbone assignment. For a general assessment, we compare amide-to-amide experiments with the more common {sup 13}C-shift-based methods. Exploiting efficient CP magnetization transfers rather than less efficient INEPT periods, our results suggest that the approach is very feasible for solid-state NMR.

  2. Sequential backbone assignment based on dipolar amide-to-amide correlation experiments

    International Nuclear Information System (INIS)

    Xiang, ShengQi; Grohe, Kristof; Rovó, Petra; Vasa, Suresh Kumar; Giller, Karin; Becker, Stefan; Linser, Rasmus

    2015-01-01

    Proton detection in solid-state NMR has seen a tremendous increase in popularity in the last years. New experimental techniques allow to exploit protons as an additional source of information on structure, dynamics, and protein interactions with their surroundings. In addition, sensitivity is mostly improved and ambiguity in assignment experiments reduced. We show here that, in the solid state, sequential amide-to-amide correlations turn out to be an excellent, complementary way to exploit amide shifts for unambiguous backbone assignment. For a general assessment, we compare amide-to-amide experiments with the more common 13 C-shift-based methods. Exploiting efficient CP magnetization transfers rather than less efficient INEPT periods, our results suggest that the approach is very feasible for solid-state NMR

  3. Relationships between nitric oxide, nitroxyl ion, nitrosonium cation and peroxynitrite.

    Science.gov (United States)

    Hughes, M N

    1999-05-05

    This review is concerned mainly with the three redox-related, but chemically distinct, species NO-, NO. and NO+, with greatest emphasis being placed on the chemistry and biology of the nitroxyl ion. Biochemical routes for the formation of nitroxyl ion and methods for showing the intermediacy of this species are discussed, together with chemical methods for generating nitroxyl ion in solution. Reactions of nitroxyl ion with NO., thiols, iron centres in haem and with dioxygen are reviewed The significance of the reaction between NO- and dioxygen as a source of peroxynitrite is assessed, and attention drawn to the possible significance of the spin state of the nitroxyl ion in this context. The biological significance of nitrosation and the importance of S-nitrosothiols and certain metal nitrosyl complexes as carriers of NO+ at physiological pH is stressed. Some features in the chemistry of peroxynitrite are noted.

  4. Nitroxyl free radicals formed from hindered amine light stabilizers under 60Co γ-ray irradiation

    International Nuclear Information System (INIS)

    Wang Huiliang; Chen Wenxiu

    2006-01-01

    Nitroxyl free radicals formed from several low molecular weight (LMW) hindered amine light stabilizers (HALS) under 60 Co γ-ray irradiation was studied with electron spin resonance (ESR) spectroscopy. All the HALSs irradiated in air formed nitroxyl free radicals under irradiation in air. For most of the HALSs, concentration of the nitroxyl free radicals increased linearly and quickly with absorbed dose in 0-10 kGy range, but increased slowly, or even kept constant, with doses of greater than 10 kGy. Concentration of nitroxyl free radicals formed from LMW HALS was usually higher than high molecular weight HALS. Tetramethyl HALS was easier to form nitroxyl free radicals than pentamethyl HLAS. Concentration of nitroxyl free radicals formed from the samples irradiated in oxygen was about two times higher than that the samples irradiated in air. Mechanisms of the nitroxyl free radical formation from the γ-ray irradiated HALSs were was discussed. (authors)

  5. Hpa1 harpin needs nitroxyl terminus to promote vegetative growth ...

    Indian Academy of Sciences (India)

    2016-08-26

    Aug 26, 2016 ... Home; Journals; Journal of Biosciences; Volume 39; Issue 1. Hpa1 harpin needs nitroxyl terminus to ... Hansong Dong1 Chunling Zhang1. State Ministry of Education Key Laboratory of Integrated Management of Crop Pathogens and Insect Pests, Nanjing Agricultural University, Jiangsu, 210095, China ...

  6. Nitroxyl-mediated oxidation of lignin and polycarboxylated products

    Energy Technology Data Exchange (ETDEWEB)

    Stahl, Shannon S.; Rafiee, Mohammad

    2018-02-27

    Methods of selectively modifying lignin, polycarboxylated products thereof, and methods of deriving aromatic compounds therefrom. The methods comprise electrochemically oxidizing lignin using stable nitroxyl radicals to selectively oxidize primary hydroxyls on .beta.-O-4 phenylpropanoid units to corresponding carboxylic acids while leaving the secondary hydroxyls unchanged. The oxidation results in polycarboxylated lignin in the form of a polymeric .beta.-hydroxy acid. The polymeric .beta.-hydroxy acid has a high loading of carboxylic acid and can be isolated in acid form, deprotonated, and/or converted to a salt. The .beta.-hydroxy acid, anion, or salt can also be subjected to acidolysis to generate various aromatic monomers or oligomers. The initial oxidation of lignin to the polycarboxylated form renders the lignin more susceptible to acidolysis and thereby enhances the yield of aromatic monomers and oligomers obtained through acidolysis.

  7. Diffusion studies on permeable nitroxyl spin probes through bilayer lipid membranes: A low frequency ESR study

    International Nuclear Information System (INIS)

    Meenakumari, V.; Benial, A. Milton Franklin; Utsumi, Hideo; Ichikawa, Kazuhiro; Yamada, Ken-ichi; Hyodo, Fuminori; Jawahar, A.

    2015-01-01

    Electron spin resonance (ESR) studies were carried out for permeable 2mM 14 N-labeled deutrated 3 Methoxy carbonyl-2,2,5,5-tetramethyl-pyrrolidine-1-oxyl (MC-PROXYL) in pure water and 1mM, 2mM, 3mM, 4mM concentration of 14N-labeled deutrated MC-PROXYL in 400mM concentration of liposomal solution by using a 300 MHz ESR spectrometer. The ESR parameters such as linewidth, hyperfine coupling constant, g-factor, partition parameter and permeability were reported for these samples. The line broadening was observed for the nitroxyl spin probe in the liposomal solution. The line broadening indicates that the high viscous nature of the liposomal solution. The partition parameter and permeability values indicate the maximum diffusion of nitroxyl spin probes in the bilayer lipid membranes at 2 mM concentration of nitroxyl radical. This study illustrates that ESR can be used to differentiate between the intra and extra- membrane water by loading the liposome vesicles with a lipid-permeable nitroxyl spin probe. From the ESR results, the spin probe concentration was optimized as 2mM in liposomal solution for ESR phantom studies/imaging, invivo and invitro experiments

  8. Low-frequency ESR studies on permeable and impermeable deuterated nitroxyl radicals in corn oil solution.

    Science.gov (United States)

    David Jebaraj, D; Utsumi, Hideo; Milton Franklin Benial, A

    2018-04-01

    Low-frequency electron spin resonance studies were performed for 2 mM concentration of deuterated permeable and impermeable nitroxyl spin probes, 3-methoxycarbonyl-2,2,5,5-tetramethyl-pyrrolidine-1-oxyl and 3-carboxy-2,2,5,5,-tetramethyl-1-pyrrolidinyloxy in pure water and various concentrations of corn oil solution. The electron spin resonance parameters such as the line width, hyperfine coupling constant, g factor, rotational correlation time, permeability, and partition parameter were estimated. The broadening of line width was observed for nitroxyl radicals in corn oil mixture. The rotational correlation time increases with increasing concentration of corn oil, which indicates the less mobile nature of spin probe in corn oil mixture. The membrane permeability and partition parameter values were estimated as a function of corn oil concentration, which reveals that the nitroxyl radicals permeate equally into the aqueous phase and oil phase at the corn oil concentration of 50%. The electron spin resonance spectra demonstrate the permeable and impermeable nature of nitroxyl spin probes. From these results, the corn oil concentration was optimized as 50% for phantom studies. In this work, the corn oil and pure water mixture phantom models with various viscosities correspond to plasma membrane, and whole blood membrane with different hematocrit levels was studied for monitoring the biological characteristics and their interactions with permeable nitroxyl spin probe. These results will be useful for the development of electron spin resonance and Overhauser-enhanced magnetic resonance imaging modalities in biomedical applications. Copyright © 2017 John Wiley & Sons, Ltd.

  9. Dipolar and spinor bosonic systems

    Science.gov (United States)

    Yukalov, V. I.

    2018-05-01

    The main properties and methods of describing dipolar and spinor atomic systems, composed of bosonic atoms or molecules, are reviewed. The general approach for the correct treatment of Bose-condensed atomic systems with nonlocal interaction potentials is explained. The approach is applied to Bose-condensed systems with dipolar interaction potentials. The properties of systems with spinor interaction potentials are described. Trapped atoms and atoms in optical lattices are considered. Effective spin Hamiltonians for atoms in optical lattices are derived. The possibility of spintronics with cold atom is emphasized. The present review differs from the previous review articles by concentrating on a thorough presentation of basic theoretical points, helping the reader to better follow mathematical details and to make clearer physical conclusions.

  10. Dipolar quantum gases of erbium

    International Nuclear Information System (INIS)

    Frisch, A.

    2014-01-01

    Since the preparation of the first Bose-Einstein condensate about two decades ago and the first degenerate Fermi gas following four years later a plethora of fascinating quantum phenomena have been explored. The vast majority of experiments focused on quantum degenerate atomic gases with short-range contact interaction between particles. Atomic species with large magnetic dipole moments, such as chromium, dysprosium, and erbium, offer unique possibilities to investigate phenomena arising from dipolar interaction. This kind of interaction is not only long-range but also anisotropic in character and imprints qualitatively novel features on the system. Prominent examples are the d-wave collapse of a dipolar Bose-Einstein condensate of chromium atoms realized by the group in Stuttgart, the spin magnetization and demagnetization dynamics observed by groups in Stuttgart, Paris, and Stanford, and the deformation of the Fermi surface observed by our group in Innsbruck. This thesis reports on the creation and study of the first Bose-Einstein condensate and degenerate Fermi gas of erbium atoms. Erbium belongs to the lanthanide group of elements and has a large magnetic moment of seven Bohr magneton. In particular, this thesis describes the experimental apparatus and the sequence for producing a dipolar quantum gas. There is an emphasis on the production of the narrow-line magneto-optical trap of erbium since this represents a very efficient and robust laser-cooling scheme that greatly simplifies the experimental procedure. After describing the experimental setup this thesis focuses on several fundamental questions related to the dipolar character of erbium and to its lanthanide nature. A first set of studies centers on the scattering properties of ultracold erbium atoms, including the elastic and the inelastic cross section and the spectrum of Feshbach resonances. Specifically, we observe that identical dipolar fermions do collide and rethermalize even at low temperatures

  11. Iron catalyzed conversion of NO into nitrosonium (NO+) and nitroxyl (HNO/NO-) species.

    Science.gov (United States)

    Stojanović, Srdjan; Stanić, Dragana; Nikolić, Milan; Spasić, Mihailo; Niketić, Vesna

    2004-11-01

    The conversion of NO into its congeners, nitrosonium (NO+) and nitroxyl (HNO/NO-) species, has important consequences in NO metabolism. Dinitrosyl iron complex (DNIC) combined with thiol ligands was shown to catalyze the conversion of NO into NO+, resulting in the synthesis of S-nitrosothiols (RSNO) both in vitro and in vivo. The formation mechanism of DNIC was proposed to involve the intermediate release of nitroxyl. Since the detection of hydroxylamine (as the product of a rapid reaction of HNO/NO- with thiols) is taken as the evidence for nitroxyl generation, we examined the formation of hydroxylamine, RSNO, and nitrite (the product of a rapid reaction of NO+ with water) in neutral solutions containing iron ions and thiols exposed to NO under anaerobic conditions. Hydroxylamine was detected in NO treated solutions of iron ions in the presence of cysteine, but not glutathione (GSH). The addition of urate, a major "free" iron-binding agent in humans, to solutions of GSH and iron ions, and the subsequent treatment of these solutions with NO increased the synthesis of GSNO and resulted in the formation of hydroxylamine. This caused a loss of urate and yielded a novel nitrosative/nitration product. GSH attenuated the urate decomposition to such a degree that it could be reflected as the function of GSH:urate. Results described here contribute to the understanding of the role of iron ions in catalyzing the conversion of NO into HNO/NO- and point to the role of uric acid not previously described.

  12. Backbone amide linker strategy

    DEFF Research Database (Denmark)

    Shelton, Anne Pernille Tofteng; Jensen, Knud Jørgen

    2013-01-01

    In the backbone amide linker (BAL) strategy, the peptide is anchored not at the C-terminus but through a backbone amide, which leaves the C-terminal available for various modifications. This is thus a very general strategy for the introduction of C-terminal modifications. The BAL strategy...

  13. Thermodynamics of Dipolar Chain Systems

    DEFF Research Database (Denmark)

    R. Armstrong, J.; Zinner, Nikolaj Thomas; V. Fedorov, D.

    2012-01-01

    The thermodynamics of a quantum system of layers containing perpendicularly oriented dipolar molecules is studied within an oscillator approximation for both bosonic and fermionic species. The system is assumed to be built from chains with one molecule in each layer. We consider the effects...... numerically. Our findings indicate that thermodynamic observables, such as the heat capacity, can be used to probe the signatures of the intralayer interaction between chains. This should be relevant for near future experiments on polar molecules with strong dipole moments....

  14. Dipolarization Fronts from Reconnection Onset

    Science.gov (United States)

    Sitnov, M. I.; Swisdak, M. M.; Merkin, V. G.; Buzulukova, N.; Moore, T. E.

    2012-12-01

    Dipolarization fronts observed in the magnetotail are often viewed as signatures of bursty magnetic reconnection. However, until recently spontaneous reconnection was considered to be fully prohibited in the magnetotail geometry because of the linear stability of the ion tearing mode. Recent theoretical studies showed that spontaneous reconnection could be possible in the magnetotail geometries with the accumulation of magnetic flux at the tailward end of the thin current sheet, a distinctive feature of the magnetotail prior to substorm onset. That result was confirmed by open-boundary full-particle simulations of 2D current sheet equilibria, where two magnetotails were separated by an equilibrium X-line and weak external electric field was imposed to nudge the system toward the instability threshold. To investigate the roles of the equilibrium X-line, driving electric field and other parameters in the reconnection onset process we performed a set of 2D PIC runs with different initial settings. The investigated parameter space includes the critical current sheet thickness, flux tube volume per unit magnetic flux and the north-south component of the magnetic field. Such an investigation is critically important for the implementation of kinetic reconnection onset criteria into global MHD codes. The results are compared with Geotail visualization of the magnetotail during substorms, as well as Cluster and THEMIS observations of dipolarization fronts.

  15. Designing Hysteresis with Dipolar Chains

    Science.gov (United States)

    Concha, Andrés; Aguayo, David; Mellado, Paula

    2018-04-01

    Materials that have hysteretic response to an external field are essential in modern information storage and processing technologies. A myriad of magnetization curves of several natural and artificial materials have previously been measured and each has found a particular mechanism that accounts for it. However, a phenomenological model that captures all the hysteresis loops and at the same time provides a simple way to design the magnetic response of a material while remaining minimal is missing. Here, we propose and experimentally demonstrate an elementary method to engineer hysteresis loops in metamaterials built out of dipolar chains. We show that by tuning the interactions of the system and its geometry we can shape the hysteresis loop which allows for the design of the softness of a magnetic material at will. Additionally, this mechanism allows for the control of the number of loops aimed to realize multiple-valued logic technologies. Our findings pave the way for the rational design of hysteretical responses in a variety of physical systems such as dipolar cold atoms, ferroelectrics, or artificial magnetic lattices, among others.

  16. Independent EEG sources are dipolar.

    Directory of Open Access Journals (Sweden)

    Arnaud Delorme

    Full Text Available Independent component analysis (ICA and blind source separation (BSS methods are increasingly used to separate individual brain and non-brain source signals mixed by volume conduction in electroencephalographic (EEG and other electrophysiological recordings. We compared results of decomposing thirteen 71-channel human scalp EEG datasets by 22 ICA and BSS algorithms, assessing the pairwise mutual information (PMI in scalp channel pairs, the remaining PMI in component pairs, the overall mutual information reduction (MIR effected by each decomposition, and decomposition 'dipolarity' defined as the number of component scalp maps matching the projection of a single equivalent dipole with less than a given residual variance. The least well-performing algorithm was principal component analysis (PCA; best performing were AMICA and other likelihood/mutual information based ICA methods. Though these and other commonly-used decomposition methods returned many similar components, across 18 ICA/BSS algorithms mean dipolarity varied linearly with both MIR and with PMI remaining between the resulting component time courses, a result compatible with an interpretation of many maximally independent EEG components as being volume-conducted projections of partially-synchronous local cortical field activity within single compact cortical domains. To encourage further method comparisons, the data and software used to prepare the results have been made available (http://sccn.ucsd.edu/wiki/BSSComparison.

  17. Thermodynamics of Dipolar Chain Systems

    International Nuclear Information System (INIS)

    Armstrong, J.R.; Zinner, N.T.; Fedorov, D.V.; Jensen, A.S.

    2013-01-01

    The thermodynamics of a quantum system of layers containing perpendicularly oriented dipolar molecules is studied within an oscillator approximation for both bosonic and fermionic species. The system is assumed to be built from chains with one molecule in each layer. We consider the effects of the intralayer repulsion and quantum statistical requirements in systems with more than one chain. Specifically, we consider the case of two chains and solve the problem analytically within the harmonic Hamiltonian approach which is accurate for large dipole moments. The case of three chains is calculated numerically. Our findings indicate that thermodynamic observables, such as the heat capacity, can be used to probe the signatures of the intralayer interaction between chains. This should be relevant for near future experiments on polar molecules with strong dipole moments. (author)

  18. Moessbauer effect study of iron(III)-inidazolidine nitroxyl-free radical ligand complex

    Energy Technology Data Exchange (ETDEWEB)

    Mulaba, A. [Technikon Witwatersrand, Metallurgy Department (South Africa); Kiremire, E. [University of the Witwatersrand, Chemistry Department (South Africa); Pollak, H. [University of the Witwatersrand, Physics Department (South Africa); Boeyens, J. [University of the Witwatersrand, Chemistry Department (South Africa)

    1999-09-15

    A new complex, [Fe(acac)L{sub 2}], bearing inidazolidine nitroxyl-free radical ligand (L{sup -}) was recently synthesised for biological studies. It proved to be biologically active against African sleeping sickness, plasmodium falciparum (malaria), leishmaniasis and chaga disease causative agents. Three ESR well resolved peaks indicated the presence of a free (unpaired) and chemically active electron in the complex. The structural complex ferric iron was found at the centre of two electric gradient whose the biggest is suggested to be initiated by the unpaired charge. No distinction between different cis isomers could be made.

  19. Moessbauer effect study of iron(III)-inidazolidine nitroxyl-free radical ligand complex

    International Nuclear Information System (INIS)

    Mulaba, A.; Kiremire, E.; Pollak, H.; Boeyens, J.

    1999-01-01

    A new complex, [Fe(acac)L 2 ], bearing inidazolidine nitroxyl-free radical ligand (L - ) was recently synthesised for biological studies. It proved to be biologically active against African sleeping sickness, plasmodium falciparum (malaria), leishmaniasis and chaga disease causative agents. Three ESR well resolved peaks indicated the presence of a free (unpaired) and chemically active electron in the complex. The structural complex ferric iron was found at the centre of two electric gradient whose the biggest is suggested to be initiated by the unpaired charge. No distinction between different cis isomers could be made

  20. Evaluation of magnetic dipolar terms in molecules

    International Nuclear Information System (INIS)

    Muniz, R.B.; Brandi, H.S.; Maffeo, B.

    1977-01-01

    The magnetic dipolar parameter b for several values of the internuclear distance in the molecule F 2 - is evaluated. The difficulties appearing in the calculations are discussed and a manner to overcome them is presented [pt

  1. Imaging using long range dipolar field effects

    International Nuclear Information System (INIS)

    Gutteridge, Sarah

    2002-01-01

    The work in this thesis has been undertaken by the author, except where indicated in reference, within the Magnetic Resonance Centre, at the University of Nottingham during the period from October 1998 to March 2001. This thesis details the different characteristics of the long range dipolar field and its application to magnetic resonance imaging. The long range dipolar field is usually neglected in nuclear magnetic resonance experiments, as molecular tumbling decouples its effect at short distances. However, in highly polarised samples residual long range components have a significant effect on the evolution of the magnetisation, giving rise to multiple spin echoes and unexpected quantum coherences. Three applications utilising these dipolar field effects are documented in this thesis. The first demonstrates the spatial sensitivity of the signal generated via dipolar field effects in structured liquid state samples. The second utilises the signal produced by the dipolar field to create proton spin density maps. These maps directly yield an absolute value for the water content of the sample that is unaffected by relaxation and any RF inhomogeneity or calibration errors in the radio frequency pulses applied. It has also been suggested that the signal generated by dipolar field effects may provide novel contrast in functional magnetic resonance imaging. In the third application, the effects of microscopic susceptibility variation on the signal are studied and the relaxation rate of the signal is compared to that of a conventional spin echo. (author)

  2. Liquid-crystalline polyesters with end nitroxyl radical and their use in living free-radical polymerization

    Czech Academy of Sciences Publication Activity Database

    Razina, A B.; Sedláková, Zdeňka; Bouchal, Karel; Tenkovtsev, A. V.; Ilavský, Michal

    2002-01-01

    Roč. 44, č. 9 (2002), s. 924-930 ISSN 0965-545X R&D Projects: GA AV ČR KSK4050111 Institutional research plan: CEZ:AV0Z4050913 Keywords : liquid crystal * polyesters * nitroxyl radical Subject RIV: CD - Macromolecular Chemistry Impact factor: 0.627, year: 2002

  3. Utility decay rates of T1-weighted magnetic resonance imaging contrast based on redox-sensitive paramagnetic nitroxyl contrast agents

    International Nuclear Information System (INIS)

    Matsumoto, Ken-ichiro

    2009-01-01

    The availability and applicability of the combination of paramagnetic nitroxyl contrast agent and T 1 -weighted gradient echo (GE)-based dynamic magnetic resonance imaging (MRI) measurement for redox imaging are described. The time courses of T 1 -weighted GE MRI signal intensities according to first-order paramagnetic loss of a nitroxyl contrast agent were simulated for several experimental conditions. The apparent decay rate calculated based on decreasing T 1 -weighted MRI contrast (k MRI ) can show an approximate value of the original decay rate (k true ) discretionarily given for simulation with suitable experimental parameters. The difference between k MRI and k true can be sufficiently small under T 1 -weighted spoiled gradient echo (SPGR) scan conditions (repetition time=75 ms, echo time=3 ms, and flip angle=45deg), with a conventional redox-sensitive nitroxyl contrast agent, such as 4-hydroxy-2,2,6,6,-tetramethylpiperidine-N-oxyl (TEMPOL) and/or 3-carbamoyl-2,2,5,5-tetramethylpyrrolidine-N-oxyl (carbamoyl-PROXYL), and with intravenous (i.v.) doses of below 1.5 γmol/g body weight (b.w.) for mice. The results of this simulation suggest that the k MRI of nitroxyl contrast agents can be the primary index of redox status under biological conditions. (author)

  4. Hpa1 harpin needs nitroxyl terminus to promote vegetative growth and leaf photosynthesis in Arabidopsis.

    Science.gov (United States)

    Li, Xiaojie; Han, Liping; Zhao, Yanying; You, Zhenzhen; Dong, Hansong; Zhang, Chunling

    2014-03-01

    Hpa1 is a harpin protein produced by Xanthomonas oryzae, an important bacterial pathogen of rice, and has the growth-promoting activity in plants. To understand the molecular basis for the function of Hpa1, we generated an inactive variant protein, Hpa1 delta NT, by deleting the nitroxyl-terminal region of the Hpa1 sequence and compared Hpa1 delta NT with the full-length protein in terms of the effects on vegetative growth and related physiological responses in Arabidopsis. When Hpa1 was applied to plants, it acted to enhance the vegetative growth but did not affect the floral development. Enhanced plant growth was accompanied by induced expression of growth-promoting genes in plant leaves. The growth-promoting activity of Hpa1 was further correlated with a physiological consequence shown as promoted leaf photosynthesis as a result of facilitated CO2 conduction through leaf stomata and mesophyll cells. On the contrary, plant growth, growth-promoting gene expression, and the physiological consequence changed little in response to the Hpa1 delta NT treatment. These analyses suggest that Hpa1 requires the nitroxyl-terminus to facilitate CO2 transport inside leaf cells and promote leaf photosynthesis and vegetative growth of the plant.

  5. Longitudinal expansion of field line dipolarization

    Science.gov (United States)

    Saka, O.; Hayashi, K.

    2017-11-01

    We examine the substorm expansions that started at 1155 UT 10 August 1994 in the midnight sector focusing on the longitudinal (eastward) expansion of field line dipolarization in the auroral zone. Eastward expansion of the dipolarization region was observed in all of the H, D, and Z components. The dipolarization that started at 1155 UT (0027 MLT) from 260° of geomagnetic longitude (CMO) expanded to 351°(PBQ) in about 48 min. The expansion velocity was 0.03-0.04°/s, or 1.9 km/s at 62°N of geomagnetic latitude. The dipolarization region expanding to the east was accompanied by a bipolar event at the leading edge of the expansion in latitudes equatorward of the westward electrojet (WEJ). In the midnight sector at the onset meridian, the Magnetospheric Plasma Analyzer (MAP) on board geosynchronous satellite L9 measured electrons and ions between 10 eV and 40 keV. We conclude from the satellite observations that this dipolarization was characterized by the evolution of temperature anisotropies, an increase of the electron and ion temperatures, and a rapid change in the symmetry axis of the temperature tensor. The field line dipolarization and its longitudinal expansion were interpreted in terms of the slow MHD mode triggered by the current disruption. We propose a new magnetosphere-ionosphere coupling (MI-coupling) mechanism based on the scenario that transmitted westward electric fields from the magnetosphere in association with expanding dipolarization produced electrostatic potential (negative) in the ionosphere through differences in the mobility of collisional ions and collisionless electrons. The field-aligned currents that emerged from the negative potential region are arranged in a concentric pattern around the negative potential region, upward toward the center and downward on the peripheral.

  6. Dipolar ferromagnets and glasses (invited)

    International Nuclear Information System (INIS)

    Rosenbaum, T.F.; Wu, W.; Ellman, B.; Yang, J.; Aeppli, G.; Reich, D.H.

    1991-01-01

    What is the ground state and what are the dynamics of 10 23 randomly distributed Ising spins? We have attempted to answer these questions through magnetic susceptibility, calorimetric, and neutron scattering studies of the randomly diluted dipolar-coupled Ising magnet LiHo x Y 1-x F 4 . The material is ferromagnetic for dipole concentrations at least as low as x=0.46, with a Curie temperature obeying mean-field scaling relative to that of pure LiHoF 4 . In the dilute spin limit, an x=0.045 crystal shows very unusual glassy properties characterized by decreasing barriers to relaxation as T→0. Its properties are consistent with a single low degeneracy ground state with a large gap for excitations. A slightly more concentrated x=0.167 sample, however, supports a complex ground state with no appreciable gap, in accordance with prevailing theories of spin glasses. The underlying causes of such disparate behavior are discussed in terms of random clusters as probed by neutron studies of the x=0.167 sample. In addition to tracing the evolution of the glassy and ferromagnetic states with dipole concentration, we investigate the effects of a transverse magnetic field on the Ising spin glass, LiHo 0.167 Y 0.833 F 4 . The transverse field mixes the eigenfunctions of the ground-state Ising doublet with the otherwise inaccessible excited-state levels. We observe a rapid decrease in the characteristic relaxation times, large changes in the spectral form of the relaxation, and a depression of the spin-glass transition temperature with the addition of quantum fluctuations

  7. Dipolar modulation of Large-Scale Structure

    Science.gov (United States)

    Yoon, Mijin

    For the last two decades, we have seen a drastic development of modern cosmology based on various observations such as the cosmic microwave background (CMB), type Ia supernovae, and baryonic acoustic oscillations (BAO). These observational evidences have led us to a great deal of consensus on the cosmological model so-called LambdaCDM and tight constraints on cosmological parameters consisting the model. On the other hand, the advancement in cosmology relies on the cosmological principle: the universe is isotropic and homogeneous on large scales. Testing these fundamental assumptions is crucial and will soon become possible given the planned observations ahead. Dipolar modulation is the largest angular anisotropy of the sky, which is quantified by its direction and amplitude. We measured a huge dipolar modulation in CMB, which mainly originated from our solar system's motion relative to CMB rest frame. However, we have not yet acquired consistent measurements of dipolar modulations in large-scale structure (LSS), as they require large sky coverage and a number of well-identified objects. In this thesis, we explore measurement of dipolar modulation in number counts of LSS objects as a test of statistical isotropy. This thesis is based on two papers that were published in peer-reviewed journals. In Chapter 2 [Yoon et al., 2014], we measured a dipolar modulation in number counts of WISE matched with 2MASS sources. In Chapter 3 [Yoon & Huterer, 2015], we investigated requirements for detection of kinematic dipole in future surveys.

  8. Ultracold Dipolar Gases in Optical Lattices

    OpenAIRE

    Trefzger, C.; Menotti, C.; Capogrosso-Sansone, B.; Lewenstein, M.

    2011-01-01

    This tutorial is a theoretical work, in which we study the physics of ultra-cold dipolar bosonic gases in optical lattices. Such gases consist of bosonic atoms or molecules that interact via dipolar forces, and that are cooled below the quantum degeneracy temperature, typically in the nK range. When such a degenerate quantum gas is loaded into an optical lattice produced by standing waves of laser light, new kinds of physical phenomena occur. These systems realize then extended Hubbard-type m...

  9. A Recent History of HNO (Nitroxyl) Chemistry, Pharmacology and Therapeutic Potential.

    Science.gov (United States)

    Fukuto, Jon M

    2018-06-02

    Due to the excitement surrounding the discovery of nitric oxide (NO) as an endogenously generated signaling molecule, numerous other nitrogen oxides were also investigated as possible physiological mediators. Among these was nitroxyl (HNO). Over the past 25 years or so, a significant amount of work by this lab and many others has discovered that HNO possesses unique chemical properties and important pharmacological utility. Indeed, the pharmacological potential for HNO as a treatment for heart failure, among other uses, has garnered this curious molecule tremendous recent attention. This review thus summarizes the events that led to this recent attention as well as pose remaining questions that are important to answer with regards to understanding the chemistry and biology of HNO. This article is protected by copyright. All rights reserved.

  10. Amides in Nature and Biocatalysis.

    Science.gov (United States)

    Pitzer, Julia; Steiner, Kerstin

    2016-10-10

    Amides are widespread in biologically active compounds with a broad range of applications in biotechnology, agriculture and medicine. Therefore, as alternative to chemical synthesis the biocatalytic amide synthesis is a very interesting field of research. As usual, Nature can serve as guide in the quest for novel biocatalysts. Several mechanisms for carboxylate activation involving mainly acyl-adenylate, acyl-phosphate or acyl-enzyme intermediates have been discovered, but also completely different pathways to amides are found. In addition to ribosomes, selected enzymes of almost all main enzyme classes are able to synthesize amides. In this review we give an overview about amide synthesis in Nature, as well as biotechnological applications of these enzymes. Moreover, several examples of biocatalytic amide synthesis are given. Copyright © 2016 Elsevier B.V. All rights reserved.

  11. The Effects of Nitroxyl (HNO) on H2O2 Metabolism and Possible Mechanisms of HNO Signaling

    OpenAIRE

    Jackson, Matthew I.; Fields, Hannah F.; Lujan, Timothy S.; Cantrell, Megan M.; Lin, Joseph; Fukuto, Jon M.

    2013-01-01

    Nitroxyl (HNO) possesses unique and potentially important biological/physiological activity that is currently mechanistically ill-defined. Previous work has shown that the likely biological targets for HNO are thiol proteins, oxidized metalloproteins (i.e. ferric heme proteins) and, most likely, selenoproteins. Interestingly, these are the same classes of proteins that interact with H2O2. In fact, these classes of proteins not only react with H2O2, and thus potentially responsible for the sig...

  12. Development and testing of a CW-EPR apparatus for imaging of short-lifetime nitroxyl radicals in mouse head

    Science.gov (United States)

    Sato-Akaba, Hideo; Fujii, Hirotada; Hirata, Hiroshi

    2008-08-01

    This article describes a method for reducing the acquisition time in three-dimensional (3D) continuous-wave electron paramagnetic resonance (CW-EPR) imaging. To visualize nitroxyl spin probes, which have a short lifetime in living organisms, the acquisition time for a data set of spectral projections should be shorter than the lifetime of the spin probes. To decrease the total time required for data acquisition, the duration of magnetic field scanning was reduced to 0.5 s. Moreover, the number of projections was decreased by using the concept of a uniform distribution. To demonstrate this faster data acquisition, two kinds of nitroxyl radicals with different decay rates were measured in mice. 3D EPR imaging of 4-hydroxy-2,2,6,6-tetramethylpiperidine-d 17-1- 15N-1-oxyl in mouse head was successfully carried out. 3D EPR imaging of nitroxyl spin probes with a half-life of a few minutes was achieved for the first time in live animals.

  13. Permeability studies of redox-sensitive nitroxyl spin probes in corn oil using an L-band ESR spectrometer

    Energy Technology Data Exchange (ETDEWEB)

    Jebaraj, D. David [Department of Physics, The American College, Madurai-625 002, Tamilnadu (India); Utsumi, Hideo [Innovation Center for Medical Redox Navigation, Kyushu University, Fukuoka 812-8582 (Japan); Asath, R. Mohamed; Benial, A. Milton Franklin, E-mail: miltonfranklin@yahoo.com [Department of Physics, NMSSVN College, Madurai-625 019, Tamilnadu (India)

    2016-05-23

    Electron spin resonance (ESR) studies were carried out for 2mM {sup 14}N labeled {sup 2}H enriched 3-methoxycarbonyl-2,2,5,5-tetramethyl-pyrrolidine-1-oxyl (MC-PROXYL) and 3–carboxy-2,2,5,5,-tetramethyl-1-pyrrolidinyloxy (carboxy-PROXYL) in pure water and various concentrations of corn oil. The ESR parameters, such as the line width, hyperfine coupling constant, g-factor, rotational correlation time, partition parameter and permeability were reported for the samples. The line width broadening was observed for both nitroxyl radicals in corn oil solutions. The partition parameter for permeable MC-PROXYL in corn oil increases with increasing concentration of corn oil, which reveals that the nitroxyl spin probe permeates into the oil phase. From the results, the corn oil concentration was optimized as 50 % for phantom studies. The rotational correlation time also increases with increasing concentration of corn oil. The permeable and impermeable nature of nitroxyl spin probes was demonstrated. These results will be useful for the development of ESR/OMR imaging modalities in in vivo and in vitro studies.

  14. Permeability studies of redox-sensitive nitroxyl spin probes in corn oil using an L-band ESR spectrometer

    International Nuclear Information System (INIS)

    Jebaraj, D. David; Utsumi, Hideo; Asath, R. Mohamed; Benial, A. Milton Franklin

    2016-01-01

    Electron spin resonance (ESR) studies were carried out for 2mM 14 N labeled 2 H enriched 3-methoxycarbonyl-2,2,5,5-tetramethyl-pyrrolidine-1-oxyl (MC-PROXYL) and 3–carboxy-2,2,5,5,-tetramethyl-1-pyrrolidinyloxy (carboxy-PROXYL) in pure water and various concentrations of corn oil. The ESR parameters, such as the line width, hyperfine coupling constant, g-factor, rotational correlation time, partition parameter and permeability were reported for the samples. The line width broadening was observed for both nitroxyl radicals in corn oil solutions. The partition parameter for permeable MC-PROXYL in corn oil increases with increasing concentration of corn oil, which reveals that the nitroxyl spin probe permeates into the oil phase. From the results, the corn oil concentration was optimized as 50 % for phantom studies. The rotational correlation time also increases with increasing concentration of corn oil. The permeable and impermeable nature of nitroxyl spin probes was demonstrated. These results will be useful for the development of ESR/OMR imaging modalities in in vivo and in vitro studies.

  15. Amides in Nature and Biocatalysis

    NARCIS (Netherlands)

    Pitzer, J.; Steiner, K.

    2016-01-01

    Amides are widespread in biologically active compounds with a broad range of applications in biotechnology, agriculture and medicine. Therefore, as alternative to chemical synthesis the biocatalytic amide synthesis is a very interesting field of research. As usual, Nature can serve as guide in the

  16. Artifact suppression in electron paramagnetic resonance imaging of 14N- and 15N-labeled nitroxyl radicals with asymmetric absorption spectra

    Science.gov (United States)

    Takahashi, Wataru; Miyake, Yusuke; Hirata, Hiroshi

    2014-10-01

    This article describes an improved method for suppressing image artifacts in the visualization of 14N- and 15N-labeled nitroxyl radicals in a single image scan using electron paramagnetic resonance (EPR). The purpose of this work was to solve the problem of asymmetric EPR absorption spectra in spectral processing. A hybrid function of Gaussian and Lorentzian lineshapes was used to perform spectral line-fitting to successfully separate the two kinds of nitroxyl radicals. This approach can process the asymmetric EPR absorption spectra of the nitroxyl radicals being measured, and can suppress image artifacts due to spectral asymmetry. With this improved visualization method and a 750-MHz continuous-wave EPR imager, a temporal change in the distributions of a two-phase paraffin oil and water/glycerin solution system was visualized using lipophilic and hydrophilic nitroxyl radicals, i.e., 2-(14-carboxytetradecyl)-2-ethyl-4,4-dimethyl-3-oxazolidinyloxy (16-DOXYL stearic acid) and 4-hydroxyl-2,2,6,6-tetramethylpiperidine-d17-1-15N-1-oxyl (TEMPOL-d17-15N). The results of the two-phase separation experiment verified that reasonable artifact suppression could be achieved by the present method that deals with asymmetric absorption spectra in the EPR imaging of 14N- and 15N-labeled nitroxyl radicals.

  17. Heterogeneous dipolar theory of the exponential pile

    International Nuclear Information System (INIS)

    Mastrangelo, P.V.

    1981-01-01

    We present a heterogeneous theory of the exponential pile, closely related to NORDHEIM-SCALETTAR's. It is well adapted to lattice whose pitch is relatively large (D-2O, grahpite) and the dimensions of whose channels are not negligible. The anisotropy of neutron diffusion is taken into account by the introduction of dipolar parameters. We express the contribution of each channel to the total flux in the moderator by means of multipolar coefficients. In order to be able to apply conditions of continuity between the flux and their derivatives, on the side of the moderator, we develop in a Fourier series the fluxes found at the periphery of each channel. Using Wronski's relations of Bessel's functions, we express the multipolar coefficients of the surfaces of each channel, on the side of the moderator, by means of the harmonics of each flux and their derivatives. We retain only monopolar (A 0 sub(g)) and dipolar (A 1 sub(g)) coefficients; those of a higher order are ignored. We deduce from these coefficients the systems of homogeneous equations of the exponential pile with monopoles on their own and monopoles plus dipoles. It should be noted that the systems of homogeneous equations of the critical pile are contained in those of the exponential pile. In another article, we develop the calculation of monopolar and dipolar heterogeneous parameters. (orig.)

  18. Diffusion studies on permeable nitroxyl spin probe through lipid bilayer membrane

    International Nuclear Information System (INIS)

    Benial, A. Milton Franklin; Meenakumari, V.; Ichikawa, Kazuhiro; Yamada, Ken-ichi; Utsumi, Hideo; Hyodo, Fuminori; Jawahar, A.

    2014-01-01

    Electron spin resonance (ESR) studies were carried out for 2mM 14 N labeled deutrated permeable 3- methoxycarbonyl-2,2,5,5-tetramethyl-pyrrolidine-1-oxyl (MC-PROXYL) in pure water, 1 mM, 2 mM, 3 mM and 4 mM concentration of MC-PROXYL in 300 mM concentration of liposomal solution by using a L-band ESR spectrometer. The ESR parameters such as linewidth, hyperfine coupling constant, g-factor, partition parameter and permeability were reported. The partition parameter and permeability values indicate the maximum spin distribution in the lipid phase at 2 mM concentration. This study illustrates that ESR can be used to differentiate between the intra and extra-membrane water by loading the liposome vesicles with a lipid-permeable nitroxyl spin probe. From the ESR results, the radical concentration was optimized as 2 mM in liposomal solution for ESR phantom studies and experiments

  19. Quantitative detection of nitroxyl upon trapping with glutathione and labeling with a specific fluorogenic reagent.

    Science.gov (United States)

    Johnson, Gail M; Chozinski, Tyler J; Salmon, Debra J; Moghaddam, Alan D; Chen, Hsin Chih; Miranda, Katrina M

    2013-10-01

    Donors of nitroxyl (HNO) have shown promise for treatment of stroke, heart failure, alcoholism and cancer. However, comparing the pharmacological capacities of various donors is difficult without first quantifying the amount of HNO released from each donor. Detection and quantitation of HNO has been complicated by the rapid self-consumption of HNO through irreversible dimerization, poor selectivity of trapping agents against other nitrogen oxides, and/or low sensitivity towards HNO. Here, an assay is described for the trapping of HNO by glutathione (GSH) followed by labeling of GSH with the fluorogenic agent, naphthalene-2,3-dicarboxaldehyde (NDA), and subsequent quantitation by fluorescence difference. The newly developed assay was used to validate the pH-dependence of HNO release from isopropylamine NONOate (IPA/NO), which is a dual donor of HNO and NO at physiological pH. Furthermore, varied assay conditions were utilized to suggest the ratios of the products of the reaction of GSH with HNO. At intracellular concentrations of GSH, the disulfide (GSSG) was the major product, but significant concentrations of glutathione sulfinamide (GS(O)NH₂) were also detected. This suggests that GS(O)NH₂, which is a selective biomarker of HNO, may be produced in concentrations that are amenable to in vivo analysis. Copyright © 2013 Elsevier Inc. All rights reserved.

  20. Tissue Prx I in the protection against Fe-NTA and the reduction of nitroxyl radicals

    International Nuclear Information System (INIS)

    Uwayama, Junya; Hirayama, Aki; Yanagawa, Toru; Warabi, Eiji; Sugimoto, Rika; Itoh, Ken; Yamamoto, Masayuki; Yoshida, Hiroshi; Koyama, Akio; Ishii, Tetsuro

    2006-01-01

    Peroxiredoxin I (Prx I) is a key cytoplasmic peroxidase that reduces intracellular hydroperoxides in concert with thioredoxin. To study the role of tissue Prx I in protection from oxidative stress, we generated Prx I -/- mice by gene trapping. We then evaluated the acute-phase tissue damage caused by ferric-nitrilotriacetate (Fe-NTA). Increases in serum aspartate aminotransferase and alanine aminotransferase levels were significantly greater in Prx I -/- than wild-type mice, 4 and 12 h after the injection of Fe-NTA. Using real-time EPR imaging, we examined the reduction of the stable paramagnetic nitroxyl radical 3-carbamoyl-2,2,5,5-tetramethylpyrrolidine-1-oxyl in vivo, and found that the half-life of this spin probe in the liver and kidney was significantly prolonged in the Prx I -/- mice. These results demonstrate that Prx I -/- mice have less reducing activity and are more susceptible to the damage mediated by reactive oxygen species in vivo than wild-type mice

  1. Existence of solitary waves in dipolar quantum gases

    KAUST Repository

    Antonelli, Paolo; Sparber, Christof

    2011-01-01

    We study a nonlinear Schrdinger equation arising in the mean field description of dipolar quantum gases. Under the assumption of sufficiently strong dipolar interactions, the existence of standing waves, and hence solitons, is proved together with some of their properties. This gives a rigorous argument for the possible existence of solitary waves in BoseEinstein condensates, which originate solely due to the dipolar interaction between the particles. © 2010 Elsevier B.V. All rights reserved.

  2. Existence of solitary waves in dipolar quantum gases

    KAUST Repository

    Antonelli, Paolo

    2011-02-01

    We study a nonlinear Schrdinger equation arising in the mean field description of dipolar quantum gases. Under the assumption of sufficiently strong dipolar interactions, the existence of standing waves, and hence solitons, is proved together with some of their properties. This gives a rigorous argument for the possible existence of solitary waves in BoseEinstein condensates, which originate solely due to the dipolar interaction between the particles. © 2010 Elsevier B.V. All rights reserved.

  3. Ultracold chromium: a dipolar quantum gas

    International Nuclear Information System (INIS)

    Pfau, T.; Stuhler, J.; Griesmaier, A.; Fattori, M.; Koch, T.

    2005-01-01

    We report on our recent achievement of a Bose-Einstein condensate in a gas of chromium atoms. Peculiar electronic and magnetic properties of chromium require the implementation of novel cooling strategies. We observe up to ∼ 10 5 condensed 52 Cr atoms after forced evaporation within a crossed optical dipole trap. Due to its large magnetic moment (6μ B ), the dipole-dipole interaction strength in chromium is comparable with the one of the van der Waals interaction. We prove the anisotropic nature of the dipolar interaction by releasing the condensate from a cigar shaped trap and observe, in time of flight measurements, the change of the aspect-ratio for different in-trap orientations of the atomic dipoles. We also report on the recent observation of 14 Feshbach resonances in elastic collisions between polarized ultra-cold 52 Cr atoms. This is the first Ballistic expansion of a dipolar quantum gas: The anisotropic interaction leads to a different expansion dynamics for the case of the magnetic dipoles aligned with the symmetry axis of the cigar shaped trap as compared with the dipoles oriented perpendicular to the axis of the cigar. The straight lines correspond to the theoretical expectation according to mean field theory without free parameters. observation of collisional Feshbach resonances in an atomic species with more than one valence electron. Moreover, such resonances constitute an important tool towards the realization of a purely dipolar interacting gas because they can be used to change strength and sign of the van der Waals interaction. (author)

  4. Improvement of hydrogen bond geometry in protein NMR structures by residual dipolar couplings - an assessment of the interrelation of NMR restraints

    Energy Technology Data Exchange (ETDEWEB)

    Jensen, Pernille Rose; Axelsen, Jacob Bock [University of Copenhagen, Institute of Molecular Biology (Denmark); Lerche, Mathilde Hauge [Amersham Health (Sweden); Poulsen, Flemming M. [University of Copenhagen, Institute of Molecular Biology (Denmark)], E-mail: fmp@apk.molbio.ku.dk

    2004-01-15

    We have examined how the hydrogen bond geometry in three different proteins is affected when structural restraints based on measurements of residual dipolar couplings are included in the structure calculations. The study shows, that including restraints based solely on {sup 1}H{sup N}-{sup 15}N residual dipolar couplings has pronounced impact on the backbone rmsd and Ramachandran plot but does not improve the hydrogen bond geometry. In the case of chymotrypsin inhibitor 2 the addition of {sup 13}CO-{sup 13}C{sup {alpha}} and {sup 15}N-{sup 13}CO one bond dipolar couplings as restraints in the structure calculations improved the hydrogen bond geometry to a quality comparable to that obtained in the 1.8 A resolution X-ray structure of this protein. A systematic restraint study was performed, in which four types of restraints, residual dipolar couplings, hydrogen bonds, TALOS angles and NOEs, were allowed in two states. This study revealed the importance of using several types of residual dipolar couplings to get good hydrogen bond geometry. The study also showed that using a small set of NOEs derived only from the amide protons, together with a full set of residual dipolar couplings resulted in structures of very high quality. When reducing the NOE set, it is mainly the side-chain to side-chain NOEs that are removed. Despite of this the effect on the side-chain packing is very small when a reduced NOE set is used, which implies that the over all fold of a protein structure is mainly determined by correct folding of the backbone.

  5. The effect of noncollinearity of 15N-1H dipolar and 15N CSA tensors and rotational anisotropy on 15N relaxation, CSA/dipolar cross correlation, and TROSY

    International Nuclear Information System (INIS)

    Fushman, David; Cowburn, David

    1999-01-01

    Current approaches to 15N relaxation in proteins assume that the 15N-1H dipolar and 15N CSA tensors are collinear. We show theoretically that, when there is significant anisotropy of molecular rotation, different orientations of the two tensors, experimentally observed in proteins, nucleic acids, and small peptides, will result in differences in site- specific correlation functions and spectral densities. The standard treatments of the rates of longitudinal and transverse relaxation of amide 15N nuclei, of the 15N CSA/15N-1H dipolar cross correlation, and of the TROSY experiment are extended to account for the effect of noncollinearity of the 15N-1H dipolar and 15N CSA (chemical shift anisotropy) tensors. This effect, proportional to the degree of anisotropy of the overall motion, (D-parallel /D-perpendicular -1), is sensitive to the relative orientation of the two tensors and to the orientation of the peptide plane with respect to the diffusion coordinate frame. The effect is negligible at small degrees of anisotropy, but is predicted to become significant for D-parallel /D-perpendicular ≥1.5, and at high magnetic fields. The effect of noncollinearity of 15N CSA and 15N-1H dipolar interaction is sensitive to both gross (hydrodynamic) properties and atomic-level details of protein structure. Incorporation of this effect into relaxation data analysis is likely to improve both precision and accuracy of the derived characteristics of protein dynamics, especially at high magnetic fields and for molecules with a high degree of anisotropy of the overall motion. The effect will also make TROSY efficiency dependent on local orientation in moderately anisotropic systems

  6. Redox properties of the nitronyl nitroxide antioxidants studied via their reactions with nitroxyl and ferrocyanide.

    Science.gov (United States)

    Bobko, A A; Khramtsov, V V

    2015-01-01

    Nitronyl nitroxides (NNs) are the paramagnetic probes that are capable of scavenging physiologically relevant reactive oxygen (ROS) and nitrogen (RNS) species, namely superoxide, nitric oxide (NO), and nitroxyl (HNO). NNs are increasingly considered as potent antioxidants and potential therapeutic agents. Understanding redox chemistry of the NNs is important for their use as antioxidants and as paramagnetic probes for discriminative detection of NO and HNO by electron paramagnetic resonance (EPR) spectroscopy. Here we investigated the redox properties of the two most commonly used NNs, including determination of the equilibrium and rate constants of their reduction by HNO and ferrocyanide, and reduction potential of the couple NN/hydroxylamine of nitronyl nitroxide (hNN). The rate constants of the reaction of the NNs with HNO were found to be equal to (1-2) × 10(4) M(-1)s(- 1) being close to the rate constants of scavenging superoxide and NO by NNs. The reduction potential of the NNs and iminonitroxides (INs, product of NNs reaction with NO) were calculated based on their reaction constants with ferrocyanide. The obtained values of the reduction potential for NN/hNN (E'0 ≈ 285 mV) and IN/hIN (E' ≈ 495 mV) are close to the corresponding values for vitamin C and vitamin E, correspondingly. The "balanced" scavenging rates of the NNs towards superoxide, NO, and HNO, and their low reduction potential being thermodynamically close to the bottom of the pecking order of oxidizing radicals, might be important factors contributing into their antioxidant activity.

  7. Hydrogen Sulfide Sensing through Reactive Sulfur Species (RSS) and Nitroxyl (HNO) in Enterococcus faecalis.

    Science.gov (United States)

    Shen, Jiangchuan; Walsh, Brenna J C; Flores-Mireles, Ana Lidia; Peng, Hui; Zhang, Yifan; Zhang, Yixiang; Trinidad, Jonathan C; Hultgren, Scott J; Giedroc, David P

    2018-05-17

    Recent studies of hydrogen sulfide (H 2 S) signaling implicate low molecular weight (LMW) thiol persulfides and other reactive sulfur species (RSS) as signaling effectors. Here, we show that a CstR protein from the human pathogen Enterococcus faecalis ( E. faecalis), previously identified in Staphylococcus aureus ( S. aureus), is an RSS-sensing repressor that transcriptionally regulates a cst-like operon in response to both exogenous sulfide stress and Angeli's salt, a precursor of nitroxyl (HNO). E. faecalis CstR reacts with coenzyme A persulfide (CoASSH) to form interprotomer disulfide and trisulfide bridges between C32 and C61', which negatively regulate DNA binding to a consensus CstR DNA operator. A Δ cstR strain exhibits deficiency in catheter colonization in a catheter-associated urinary tract infection (CAUTI) mouse model, suggesting sulfide regulation and homeostasis is critical for pathogenicity. Cellular polysulfide metabolite profiling of sodium sulfide-stressed E. faecalis confirms an increase in both inorganic polysulfides and LMW thiols and persulfides sensed by CstR. The cst-like operon encodes two authentic thiosulfate sulfurtransferases and an enzyme we characterize here as an NADH and FAD-dependent coenzyme A (CoA) persulfide reductase (CoAPR) that harbors an N-terminal CoA disulfide reductase (CDR) domain and a C-terminal rhodanese homology domain (RHD). Both cysteines in the CDR (C42) and RHD (C508) domains are required for CoAPR activity and complementation of a sulfide-induced growth phenotype of a S. aureus strain lacking cstB, encoding a nonheme Fe II persulfide dioxygenase. We propose that S. aureus CstB and E. faecalis CoAPR employ orthogonal chemistries to lower CoASSH that accumulates under conditions of cellular sulfide toxicity and signaling.

  8. Mechanism and regioselectivity of 1,3-dipolar cycloaddition ...

    Indian Academy of Sciences (India)

    1,3-Dipolar cycloaddition; sulphur-centred 1,3-dipoles; regioselectivity; DFT reactivity indices;. FMO theory. 1. Introduction. Five-membered heterocyclic compounds can be gene- rated by addition of a 1,3-dipole to a dipolarophile under a 1,3-dipolar cycloaddition (1,3-DC) reaction which is well known as pericyclic reaction.

  9. Critical Time Crystals in Dipolar Systems.

    Science.gov (United States)

    Ho, Wen Wei; Choi, Soonwon; Lukin, Mikhail D; Abanin, Dmitry A

    2017-07-07

    We analyze the quantum dynamics of periodically driven, disordered systems in the presence of long-range interactions. Focusing on the stability of discrete time crystalline (DTC) order in such systems, we use a perturbative procedure to evaluate its lifetime. For 3D systems with dipolar interactions, we show that the corresponding decay is parametrically slow, implying that robust, long-lived DTC order can be obtained. We further predict a sharp crossover from the stable DTC regime into a regime where DTC order is lost, reminiscent of a phase transition. These results are in good agreement with the recent experiments utilizing a dense, dipolar spin ensemble in diamond [Nature (London) 543, 221 (2017)NATUAS0028-083610.1038/nature21426]. They demonstrate the existence of a novel, critical DTC regime that is stabilized not by many-body localization but rather by slow, critical dynamics. Our analysis shows that the DTC response can be used as a sensitive probe of nonequilibrium quantum matter.

  10. Cluster and Double Star observations of dipolarization

    Directory of Open Access Journals (Sweden)

    R. Nakamura

    2005-11-01

    Full Text Available We studied two types of dipolarization events with different IMF conditions when Cluster and Double Star (TC-1 were located in the same local time sector: 7 August 2004, 18:00-24:00 UT, during a disturbed southward/northward IMF interval, and 14 August 2004, 21:00-24:00 UT, when the IMF was stably northward. Cluster observed dipolarization as well as fast flows during both intervals, but this was not the case for TC-1. For both events the satellites crossed near the conjugate location of the MIRACLE stations. By using multi-point analysis techniques, the direction/speed of the propagation is determined using Cluster and is then compared with the disturbances at TC-1 to discuss its spatial/temporal scale. The propagation direction of the BZ disturbance at Cluster was mainly dawnward with a tailward component for 7 August and with a significant Earthward component for 14 August associated with fast flows. We suggest that the role of the midtail fast flows can be quite different in the dissipation process depending on the condition of the IMF and resultant configuration of the tail.

  11. Perturbation theories for the dipolar fluids

    International Nuclear Information System (INIS)

    Lee, L.L.; Chung, T.H.

    1983-01-01

    We derive here four different perturbation equations for the calculation of the angular pair correlation functions of dipolar fluids; namely, the first order y-expansion, the modified Percus--Yevik (MPY) expansion, the modified hypernetted chain (MHNC) expansion, and the modified linearized hypernetted chain (MLHNC) equation. Both the method of the functional expansion and the method of the cluster integrals are utilized. Comparison with other perturbation theories (e.g., the Melnyk--Smith equation) is made. While none of the theories is exact, as shown by the cluster diagrams, the MLHNC and the MHNC contain more diagrams than, say, the MPY and y-expansion. The y-expansion equation can be improved by including the correction terms to the Kirkwood superposition approximation for the triplet correlation function. For example, the inclusion of the correction term rho∫d4h(14)h(24)h(34) in a formula given by Henderson, is shown to improve substantially the y-expansion equation. We examine the performance of two of the theories: the y-expansion and the MLHNC equation for a Stockmayer (dipolar) fluid with a reduced dipole moment μ/sup asterisk2/ [ = μ 2 /(epsilonsigma 3 )] = 1.0. Comparison with Monte Carlo simulation results of Adams et al. and with other theories (e.g., the QHNC equation) shows that our results are reasonable. Further improvements of the equations are also pointed out

  12. Dipolar vortex structures in magnetized rotating plasma

    International Nuclear Information System (INIS)

    Liu Jixing

    1990-01-01

    Dipolar solitary vortices of both electrostatic and electromagnetic character in low-β, in homogeneous rotating plasma confined in a constant external magnetic field were systematically presented. The main stimulus to this investigation is the expectation to apply this coherent structure as a candidate constituent of plasma turbulance to understand the anomalous transport phenomena in confined plasma. The electrostatic vortices have similar structure and properties as the Rossby vortices in rotating fluids, the electromagnetic vortices obtained here have no analogy in hydrodynamics and hence are intrinsic to magnetized plasma. It is valuably remarked that the intrinsic electromagnetic vortices presented here have no discontinuity of perturbed magnetic field δB and parallel current j(parallel) on the border of vortex core. The existence region of the new type of vortex is found much narrower than the Rossby type one. (M.T.)

  13. Poly(ether ester amide)s for tissue engineering

    NARCIS (Netherlands)

    Deschamps, A.A.; van Apeldoorn, Aart A.; de Bruijn, Joost Dick; Grijpma, Dirk W.; Feijen, Jan

    2003-01-01

    Poly(ether ester amide) (PEEA) copolymers based on poly(ethylene glycol) (PEG), 1,4-butanediol and dimethyl-7,12-diaza-6,13-dione-1,18-octadecanedioate were evaluated as scaffold materials for tissue engineering. A PEEA copolymer based on PEG with a molecular weight of 300 g/mol and 25 wt% of soft

  14. Characterizing Ion Flows Across a Dipolarization Front

    Science.gov (United States)

    Arnold, H.; Drake, J. F.; Swisdak, M.

    2017-12-01

    In light of the Magnetospheric Multiscale Mission (MMS) moving to study predominately symmetric magnetic reconnection in the Earth's magnetotail, it is of interest to investigate various methods for determining the relative location of the satellites with respect to the x line or a dipolarization front. We use a 2.5 dimensional PIC simulation to explore the dependence of various characteristics of a front, or flux bundle, on the width of the front in the dawn-dusk direction. In particular, we characterize the ion flow in the x-GSM direction across the front. We find a linear relationship between the width of a front, w, and the maximum velocity of the ion flow in the x-GSM direction, Vxi, for small widths: Vxi/VA=w/di*1/2*(mVA2)/Ti*Bz/Bxwhere m, VA, di, Ti, Bz, and Bx are the ion mass, upstream Alfven speed, ion inertial length, ion temperature, and magnetic fields in the z-GSM and x-GSM directions respectively. However, once the width reaches around 5 di, the relationship gradually approaches the well-known theoretical limit for ion flows, the upstream Alfven speed. Furthermore, we note that there is a reversal in the Hall magnetic field near the current sheet on the positive y-GSM side of the front. This reversal is most likely due to conservation of momentum in the y-GSM direction as the ions accelerate towards the x-GSM direction. This indicates that while the ions are primarily energized in the x-GSM direction by the front, they transfer energy to the electromagnetic fields in the y-GSM direction. The former energy transfer is greater than the latter, but the reversal of the Hall magnetic field drags the frozen-in electrons along with it outside of the front. These simulations should better able researchers to determine the relative location of a satellite crossing a dipolarization front.

  15. 40 CFR 721.3720 - Fatty amide.

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Fatty amide. 721.3720 Section 721.3720... Fatty amide. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as a fatty amide (PMN P-91-87) is subject to reporting under this section...

  16. 40 CFR 721.2120 - Cyclic amide.

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Cyclic amide. 721.2120 Section 721... Cyclic amide. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as a cyclic amide (PMN P-92-131) is subject to reporting under this section for the...

  17. Exact solutions for chemical bond orientations from residual dipolar couplings

    International Nuclear Information System (INIS)

    Wedemeyer, William J.; Rohl, Carol A.; Scheraga, Harold A.

    2002-01-01

    New methods for determining chemical structures from residual dipolar couplings are presented. The fundamental dipolar coupling equation is converted to an elliptical equation in the principal alignment frame. This elliptical equation is then combined with other angular or dipolar coupling constraints to form simple polynomial equations that define discrete solutions for the unit vector(s). The methods are illustrated with residual dipolar coupling data on ubiquitin taken in a single anisotropic medium. The protein backbone is divided into its rigid groups (namely, its peptide planes and C α frames), which may be solved for independently. A simple procedure for recombining these independent solutions results in backbone dihedral angles φ and ψ that resemble those of the known native structure. Subsequent refinement of these φ-ψ angles by the ROSETTA program produces a structure of ubiquitin that agrees with the known native structure to 1.1 A C α rmsd

  18. Asymptotic behavior of local dipolar fields in thin films

    Energy Technology Data Exchange (ETDEWEB)

    Bowden, G.J., E-mail: gjb@phys.soton.ac.uk [School of Physics and Astronomy, University of Southampton, SO17 1BJ (United Kingdom); Stenning, G.B.G., E-mail: Gerrit.vanderlaan@diamond.ac.uk [Magnetic Spectroscopy Group, Diamond Light Source, Didcot OX11 0DE (United Kingdom); Laan, G. van der, E-mail: gavin.stenning@stfc.ac.uk [ISIS Neutron and Muon Source, Rutherford Appleton Laboratory, Didcot OX11 0QX (United Kingdom)

    2016-10-15

    A simple method, based on layer by layer direct summation, is used to determine the local dipolar fields in uniformly magnetized thin films. The results show that the dipolar constants converge ~1/m where the number of spins in a square film is given by (2m+1){sup 2}. Dipolar field results for sc, bcc, fcc, and hexagonal lattices are presented and discussed. The results can be used to calculate local dipolar fields in films with either ferromagnetic, antiferromagnetic, spiral, exponential decay behavior, provided the magnetic order only changes normal to the film. Differences between the atomistic (local fields) and macroscopic fields (Maxwellian) are also examined. For the latter, the macro B-field inside the film is uniform and falls to zero sharply outside, in accord with Maxwell boundary conditions. In contrast, the local field for the atomistic point dipole model is highly non-linear inside and falls to zero at about three lattice spacing outside the film. Finally, it is argued that the continuum field B (used by the micromagnetic community) and the local field B{sub loc}(r) (used by the FMR community) will lead to differing values for the overall demagnetization energy. - Highlights: • Point-dipolar fields in uniformly magnetized thin films are characterized by just three numbers. • Maxwell's boundary condition is partially violated in the point-dipole approximation. • Asymptotic values of point dipolar fields in circular monolayers scale as π/r.

  19. The quantum coherence of disordered dipolar bosonic gas

    International Nuclear Information System (INIS)

    Wang Jiguo; Zhang Aixia; Tang Rongan; Gao Jimin; Xue Jukui

    2013-01-01

    We investigate the coherence of correlated dipolar gas in the presence of disorder within a three-site Bose–Hubbard model. We show that the interplay between the on-site interaction, the inter-site dipole–dipole interactions (DDI) and the disorder exhibits new and interesting coherence characters that cannot take place in a non-dipolar system. The ratio between the on-site interaction and DDI plays a dominant role in the phase coherence. The resonance character of the coherence against both disorder and interactions emerges. DDI can enhance the coherence at certain values of the disorder and on-site interaction. In the coherence region, the enhancement of the coherence by disorder in a dipolar system is more significant than that in a non-dipolar system. In particular, the on-site interaction and DDI together can enhance the coherence even in the clean dipolar system (i.e. a dipolar system without disorder). However, without the on-site interaction, disorder, DDI or both together suppress the coherence. Furthermore, the relationship between the coherence and the energy gap and the compressibility of the system is also discussed. (paper)

  20. Dipolar particles in a double-trap confinement: Response to tilting the dipolar orientation

    Science.gov (United States)

    Bjerlin, J.; Bengtsson, J.; Deuretzbacher, F.; Kristinsdóttir, L. H.; Reimann, S. M.

    2018-02-01

    We analyze the microscopic few-body properties of dipolar particles confined in two parallel quasi-one-dimensional harmonic traps. In particular, we show that an adiabatic rotation of the dipole orientation about the trap axes can drive an initially nonlocalized few-fermion state into a localized state with strong intertrap pairing. With an instant, nonadiabatic rotation, however, localization is inhibited and a highly excited state is reached. This state may be interpreted as the few-body analog of a super-Tonks-Girardeau state, known from one-dimensional systems with contact interactions.

  1. Dipolar dark matter with massive bigravity

    International Nuclear Information System (INIS)

    Blanchet, Luc; Heisenberg, Lavinia

    2015-01-01

    Massive gravity theories have been developed as viable IR modifications of gravity motivated by dark energy and the problem of the cosmological constant. On the other hand, modified gravity and modified dark matter theories were developed with the aim of solving the problems of standard cold dark matter at galactic scales. Here we propose to adapt the framework of ghost-free massive bigravity theories to reformulate the problem of dark matter at galactic scales. We investigate a promising alternative to dark matter called dipolar dark matter (DDM) in which two different species of dark matter are separately coupled to the two metrics of bigravity and are linked together by an internal vector field. We show that this model successfully reproduces the phenomenology of dark matter at galactic scales (i.e. MOND) as a result of a mechanism of gravitational polarisation. The model is safe in the gravitational sector, but because of the particular couplings of the matter fields and vector field to the metrics, a ghost in the decoupling limit is present in the dark matter sector. However, it might be possible to push the mass of the ghost beyond the strong coupling scale by an appropriate choice of the parameters of the model. Crucial questions to address in future work are the exact mass of the ghost, and the cosmological implications of the model

  2. De novo determination of internuclear vector orientations from residual dipolar couplings measured in three independent alignment media

    International Nuclear Information System (INIS)

    Ruan Ke; Briggman, Kathryn B.; Tolman, Joel R.

    2008-01-01

    The straightforward interpretation of solution state residual dipolar couplings (RDCs) in terms of internuclear vector orientations generally requires prior knowledge of the alignment tensor, which in turn is normally estimated using a structural model. We have developed a protocol which allows the requirement for prior structural knowledge to be dispensed with as long as RDC measurements can be made in three independent alignment media. This approach, called Rigid Structure from Dipolar Couplings (RSDC), allows vector orientations and alignment tensors to be determined de novo from just three independent sets of RDCs. It is shown that complications arising from the existence of multiple solutions can be overcome by careful consideration of alignment tensor magnitudes in addition to the agreement between measured and calculated RDCs. Extensive simulations as well applications to the proteins ubiquitin and Staphylococcal protein GB1 demonstrate that this method can provide robust determinations of alignment tensors and amide N-H bond orientations often with better than 10 o accuracy, even in the presence of modest levels of internal dynamics

  3. Clicked Cinnamic/Caffeic Esters and Amides as Radical Scavengers and 5-Lipoxygenase Inhibitors

    Directory of Open Access Journals (Sweden)

    Jérémie A. Doiron

    2014-01-01

    Full Text Available 5-Lipoxygenase (5-LO is the key enzyme responsible for the conversion of arachidonic acid to leukotrienes, a class of lipid mediators implicated in inflammatory disorders. In this paper, we describe the design, synthesis, and preliminary activity studies of novel clicked caffeic esters and amides as radical scavengers and 5-LO inhibitors. From known 5-LO inhibitor 3 as a lead, cinnamic esters 8a–h and amides 9a–h as well as caffeic esters 15a–h and amides 16a–h were synthesized by Cu(I-catalyzed [1,3]-dipolar cycloaddition with the appropriate azide precursors and terminal alkynes. All caffeic analogs are proved to be good radical scavengers (IC50: 10–20 μM. Esters 15g and 15f possessed excellent 5-LO inhibition activity in HEK293 cells and were equipotent with the known 5-LO inhibitor CAPE and more potent than Zileuton. Several synthesized esters possess activities rivaling Zileuton in stimulated human polymorphonuclear leukocytes.

  4. Jet Dipolarity: Top Tagging with Color Flow

    Energy Technology Data Exchange (ETDEWEB)

    Hook, Anson; Jankowiak, Martin; /SLAC /Stanford U., Phys. Dept.; Wacker, Jay G.; /SLAC

    2011-08-12

    A new jet observable, dipolarity, is introduced that can distinguish whether a pair of subjets arises from a color singlet source. This observable is incorporated into the HEPTopTagger and is shown to improve discrimination between top jets and QCD jets for moderate to high p{sub T}. The impressive resolution of the ATLAS and CMS detectors means that a typical QCD jet at the LHC deposits energy in {Omicron}(10-100) calorimeter cells. Such fine-grained calorimetry allows for jets to be studied in much greater detail than previously, with sophisticated versions of current techniques making it possible to measure more than just the bulk properties of jets (e.g. event jet multiplicities or jet masses). One goal of the LHC is to employ these techniques to extend the amount of information available from each jet, allowing for a broader probe of the properties of QCD. The past several years have seen significant progress in developing such jet substructure techniques. A number of general purpose tools have been developed, including: (i) top-tagging algorithms designed for use at both lower and higher p{sub T} as well as (ii) jet grooming techniques such as filtering, pruning, and trimming, which are designed to improve jet mass resolution. Jet substructure techniques have also been studied in the context of specific particle searches, where they have been shown to substantially extend the reach of traditional search techniques in a wide variety of scenarios, including for example boosted Higgses, neutral spin-one resonances, searches for supersymmetry, and many others. Despite these many successes, however, there is every reason to expect that there remains room for refinement of jet substructure techniques.

  5. Cluster Observations of Multiple Dipolarization Fronts

    Science.gov (United States)

    Hwang, Kyoung-Joo; Goldstein, Melvyn L.; Lee, Ensang; Pickett, Jolene S.

    2011-01-01

    We present Cluster observations of a series of dipolarization fronts (DF 1 to 6) at the central current sheet in Earth's magnetotail. The velocities of fast earthward flow following behind each DF 1-3, are comparable to the Alfven velocity, indicating that the flow bursts might have been generated by bursty reconnection that occurred tailward of the spacecraft. Based on multi-spacecraft timing analysis, DF normals are found to propagate mainly earthward at $160-335$ km/s with a thickness of 900-1500 km, which corresponds to the ion inertial length or gyroradius scale. Each DF is followed by significant fluctuations in the $x$ and $y$ components of the magnetic field whose peaks are found 1-2 minutes after the DF passage. These $(B_{x},B_{y} )$-fluctuations propagate dawnward (mainly) and earthward. Strongly enhanced field-aligned beams are observed coincidently with $(B_{x},B_{y})$ fluctuations, while an enhancement of cross-tail currents is associated with the DFs. From the observed pressure imbalance and flux-tube entropy changes between the two regions separated by the DF, we speculate that interchange instability destabilizes the DFs and causes the deformation of the mid-tail magnetic topology. This process generates significant field-aligned currents, and might power the auroral brightening in the ionosphere. However, this event is neither associated with the main substorm auroral breakup nor the poleward expansion, which might indicate that the observed multiple DFs have been dissipated before they reach the inner plasma sheet boundary.

  6. Magnetization behavior of ferrofluids with cryogenically imaged dipolar chains

    International Nuclear Information System (INIS)

    Klokkenburg, M; Erne, B H; Mendelev, V; Ivanov, A O

    2008-01-01

    Theories and simulations have demonstrated that field-induced dipolar chains affect the static magnetic properties of ferrofluids. Experimental verification, however, has been complicated by the high polydispersity of the available ferrofluids, and the morphology of the dipolar chains was left to the imagination. We now present the concentration- and field-dependent magnetization of particularly well-defined ferrofluids, with a low polydispersity, three different average particle sizes, and with dipolar chains that were imaged with and without magnetic field using cryogenic transmission electron microscopy. At low concentrations, the magnetization curves obey the Langevin equation for noninteracting dipoles. Magnetization curves for the largest particles strongly deviate from the Langevin equation but quantitatively agree with a recently developed mean-field model that incorporates the field-dependent formation and alignment of flexible dipolar chains. The combination of magnetic results and in situ electron microscopy images provides original new evidence for the effect of dipolar chains on the field-dependent magnetization of ferrofluids

  7. Scissors Mode of Dipolar Quantum Droplets of Dysprosium Atoms

    Science.gov (United States)

    Ferrier-Barbut, Igor; Wenzel, Matthias; Böttcher, Fabian; Langen, Tim; Isoard, Mathieu; Stringari, Sandro; Pfau, Tilman

    2018-04-01

    We report on the observation of the scissors mode of a single dipolar quantum droplet. The existence of this mode is due to the breaking of the rotational symmetry by the dipole-dipole interaction, which is fixed along an external homogeneous magnetic field. By modulating the orientation of this magnetic field, we introduce a new spectroscopic technique for studying dipolar quantum droplets. This provides a precise probe for interactions in the system, allowing us to extract a background scattering length for 164Dy of 69 (4 )a0 . Our results establish an analogy between quantum droplets and atomic nuclei, where the existence of the scissors mode is also only due to internal interactions. They further open the possibility to explore physics beyond the available theoretical models for strongly dipolar quantum gases.

  8. Protein backbone motions viewed by intraresidue and sequential H{sup N}-H{sup {alpha}} residual dipolar couplings

    Energy Technology Data Exchange (ETDEWEB)

    Voegeli, Beat; Yao Lishan; Bax, Ad [National Institutes of Health, Laboratory of Chemical Physics, National Institute of Diabetes and Digestive and Kidney Diseases (United States)], E-mail: bax@nih.gov

    2008-05-15

    Triple resonance E.COSY-based techniques were used to measure intra-residue and sequential H{sup N}-H{sup {alpha}} residual dipolar couplings (RDCs) for the third IgG-binding domain of protein G (GB3), aligned in Pf1 medium. Measurements closely correlate with values predicted on the basis of an NMR structure, previously determined on the basis of a large number of one-bond backbone RDCs measured in five alignment media. However, in particular the sequential H{sup N}-H{sup {alpha}} RDCs are smaller than predicted for a static structure, suggesting a degree of motion for these internuclear vectors that exceeds that of the backbone amide N-H vectors. Of all experimentally determined GB3 structures available, the best correlation between experimental {sup 1}H-{sup 1}H couplings is observed for a GB3 ensemble, previously derived to generate a realistic picture of the conformational space sampled by GB3 (Clore and Schwieters, J Mol Biol 355:879-886, 2006). However, for both NMR and X-ray-derived structures the {sup 1}H-{sup 1}H couplings are found to be systematically smaller than expected on the basis of alignment tensors derived from {sup 15}N-{sup 1}H amide RDCs, assuming librationally corrected N-H bond lengths of 1.041 A.

  9. Nonlocal and nonlinear electrostatics of a dipolar Coulomb fluid.

    Science.gov (United States)

    Sahin, Buyukdagli; Ralf, Blossey

    2014-07-16

    We study a model Coulomb fluid consisting of dipolar solvent molecules of finite extent which generalizes the point-like dipolar Poisson-Boltzmann model (DPB) previously introduced by Coalson and Duncan (1996 J. Phys. Chem. 100 2612) and Abrashkin et al (2007 Phys. Rev. Lett. 99 077801). We formulate a nonlocal Poisson-Boltzmann equation (NLPB) and study both linear and nonlinear dielectric response in this model for the case of a single plane geometry. Our results shed light on the relevance of nonlocal versus nonlinear effects in continuum models of material electrostatics.

  10. Quantum states with topological properties via dipolar interactions

    Energy Technology Data Exchange (ETDEWEB)

    Peter, David

    2015-06-25

    This thesis proposes conceptually new ways to realize materials with topological properties by using dipole-dipole interactions. First, we study a system of ultracold dipolar fermions, where the relaxation mechanism of dipolar spins can be used to reach the quantum Hall regime. Second, in a system of polar molecules in an optical lattice, dipole-dipole interactions induce spin-orbit coupling terms for the rotational excitations. In combination with time-reversal symmetry breaking this leads to topological bands with Chern numbers greater than one.

  11. Catalytic synthesis of amides via aldoximes rearrangement.

    Science.gov (United States)

    Crochet, Pascale; Cadierno, Victorio

    2015-02-14

    Amide bond formation reactions are among the most important transformations in organic chemistry because of the widespread occurrence of amides in pharmaceuticals, natural products and biologically active compounds. The Beckmann rearrangement is a well-known method to generate secondary amides from ketoximes. However, under the acidic conditions commonly employed, aldoximes RHC=NOH rarely rearrange into the corresponding primary amides RC(=O)NH2. In recent years, it was demonstrated that this atom-economical transformation can be carried out efficiently and selectively with the help of metal catalysts. Several homogeneous and heterogenous systems have been described. In addition, protocols offering the option to generate the aldoximes in situ from the corresponding aldehydes and hydroxylamine, or even from alcohols, have also been developed, as well as a series of tandem processes allowing the access to N-substituted amide products. In this Feature article a comprehensive overview of the advances achieved in this particular research area is presented.

  12. Harmonically trapped dipolar fermions in a two-dimensional square lattice

    DEFF Research Database (Denmark)

    Larsen, Anne-Louise G.; Bruun, Georg

    2012-01-01

    We consider dipolar fermions in a two-dimensional square lattice and a harmonic trapping potential. The anisotropy of the dipolar interaction combined with the lattice leads to transitions between phases with density order of different symmetries. We show that the attractive part of the dipolar...

  13. Synthesis and Chemical and Biological Comparison of Nitroxyl and Nitric Oxide Releasing Diazeniumdiolate-based Aspirin Derivatives

    Science.gov (United States)

    Basudhar, Debashree; Bharadwaj, Gaurav; Cheng, Robert Y.; Jain, Sarthak; Shi, Sa; Heinecke, Julie L.; Holland, Ryan J.; Ridnour, Lisa A.; Caceres, Viviane M.; Spadari-Bratfisch, Regina C.; Paolocci, Nazareno; Velázquez-Martínez, Carlos A.; Wink, David A.; Miranda, Katrina M.

    2013-01-01

    Structural modifications of non-steroidal anti-inflammatory drugs (NSAIDs) have successfully reduced the side effect of gastrointestinal ulceration without affecting anti-inflammatory activity, but may increase risk of myocardial infarction with chronic use. That nitroxyl (HNO) reduces platelet aggregation, preconditions against myocardial infarction and enhances contractility led us to synthesize a diazeniumdiolate-based HNO releasing aspirin and to compare it to an NO-releasing analogue. Here, the decomposition mechanisms are described for these compounds. In addition to protection against stomach ulceration, these prodrugs also exhibited significantly enhanced cytotoxcity compared to either aspirin or the parent diazeniumdiolate toward non-small cell lung carcinoma cells (A549) but were not appreciably toxic toward endothelial cells (HUVECs). The HNO-NSAID prodrug inhibited cylcooxgenase-2 and glyceraldehyde 3-phosphate dehydrogenase activity and triggered significant sarcomere shortening compared to control on murine ventricular myocytes. Together, these anti-inflammatory, anti-neoplasic and contractile properties suggest the potential of HNO-NSAIDs in the treatment of inflammation, cancer or heart failure. PMID:24102516

  14. Reversible Twisting of Primary Amides via Ground State N-C(O) Destabilization: Highly Twisted Rotationally Inverted Acyclic Amides.

    Science.gov (United States)

    Meng, Guangrong; Shi, Shicheng; Lalancette, Roger; Szostak, Roman; Szostak, Michal

    2018-01-17

    Since the seminal studies by Pauling in 1930s, planarity has become the defining characteristic of the amide bond. Planarity of amides has central implications for the reactivity and chemical properties of amides of relevance to a range of chemical disciplines. While the vast majority of amides are planar, nonplanarity has a profound effect on the properties of the amide bond, with the most common method to restrict the amide bond relying on the incorporation of the amide function into a rigid cyclic ring system. In a major departure from this concept, here, we report the first class of acyclic twisted amides that can be prepared, reversibly, from common primary amides in a single, operationally trivial step. Di-tert-butoxycarbonylation of the amide nitrogen atom yields twisted amides in which the amide bond exhibits nearly perpendicular twist. Full structural characterization of a range of electronically diverse compounds from this new class of twisted amides is reported. Through reactivity studies we demonstrate unusual properties of the amide bond, wherein selective cleavage of the amide bond can be achieved by a judicious choice of the reaction conditions. Through computational studies we evaluate structural and energetic details pertaining to the amide bond deformation. The ability to selectively twist common primary amides, in a reversible manner, has important implications for the design and application of the amide bond nonplanarity in structural chemistry, biochemistry and organic synthesis.

  15. Electron dynamics during substorm dipolarization in Mercury's magnetosphere

    Directory of Open Access Journals (Sweden)

    D. C. Delcourt

    2005-11-01

    Full Text Available We examine the nonlinear dynamics of electrons during the expansion phase of substorms at Mercury using test particle simulations. A simple model of magnetic field line dipolarization is designed by rescaling a magnetic field model of the Earth's magnetosphere. The results of the simulations demonstrate that electrons may be subjected to significant energization on the time scale (several seconds of the magnetic field reconfiguration. In a similar manner to ions in the near-Earth's magnetosphere, it is shown that low-energy (up to several tens of eV electrons may not conserve the second adiabatic invariant during dipolarization, which leads to clusters of bouncing particles in the innermost magnetotail. On the other hand, it is found that, because of the stretching of the magnetic field lines, high-energy electrons (several keVs and above do not behave adiabatically and possibly experience meandering (Speiser-type motion around the midplane. We show that dipolarization of the magnetic field lines may be responsible for significant, though transient, (a few seconds precipitation of energetic (several keVs electrons onto the planet's surface. Prominent injections of energetic trapped electrons toward the planet are also obtained as a result of dipolarization. These injections, however, do not exhibit short-lived temporal modulations, as observed by Mariner-10, which thus appear to follow from a different mechanism than a simple convection surge.

  16. Functionalization of Graphene via 1,3-Dipolar Cycloaddition

    NARCIS (Netherlands)

    Quintana, Mildred; Spyrou, Konstantinos; Grzelczak, Marek; Browne, Wesley R.; Rudolf, Petra; Prato, Maurizio

    Few-layer graphenes (FLG) produced by dispersion and exfoliation of graphite in N-methylpyrrolidone were successfully functionalized using the 1,3-dipolar cycloaddition of azomethine ylides. The amino functional groups attached to graphene sheets were quantified by the Kaiser test. These amino

  17. Dipolar fluid-wall systems. Beyond the image potential

    International Nuclear Information System (INIS)

    Boudh-hir, M.E.

    1989-02-01

    The case of dipolar fluid in front of an ideal wall is examined. The surface-fluid system is introduced as a limit case of a binary mixture Using the diagrammatic development, the expansion of the one-particle distribution function is given. 16 refs

  18. Microorganisms hydrolyse amide bonds; knowledge enabling read-across of biodegradability of fatty acid amides.

    Science.gov (United States)

    Geerts, Roy; Kuijer, Patrick; van Ginkel, Cornelis G; Plugge, Caroline M

    2014-07-01

    To get insight in the biodegradation and potential read-across of fatty acid amides, N-[3-(dimethylamino)propyl] cocoamide and N-(1-ethylpiperazine) tall oil amide were used as model compounds. Two bacteria, Pseudomonas aeruginosa PK1 and Pseudomonas putida PK2 were isolated with N-[3-(dimethylamino)propyl] cocoamide and its hydrolysis product N,N-dimethyl-1,3-propanediamine, respectively. In mixed culture, both strains accomplished complete mineralization of N-[3-(dimethylamino)propyl] cocoamide. Aeromonas hydrophila PK3 was enriched with N-(1-ethylpiperazine) tall oil amide and subsequently isolated using agar plates containing dodecanoate. N-(2-Aminoethyl)piperazine, the hydrolysis product of N-(1-ethylpiperazine) tall oil amide, was not degraded. The aerobic biodegradation pathway for primary and secondary fatty acid amides of P. aeruginosa and A. hydrophila involved initial hydrolysis of the amide bond producing ammonium, or amines, where the fatty acids formed were immediately metabolized. Complete mineralization of secondary fatty acid amides depended on the biodegradability of the released amine. Tertiary fatty acid amides were not transformed by P. aeruginosa or A. hydrophila. These strains were able to utilize all tested primary and secondary fatty acid amides independent of the amine structure and fatty acid. Read-across of previous reported ready biodegradability results of primary and secondary fatty acid amides is justified based on the broad substrate specificity and the initial hydrolytic attack of the two isolates PK1 and PK3.

  19. Acceleration and Precipitation of Electrons during Substorm Dipolarization Events

    Science.gov (United States)

    Ashour-Abdalla, Maha; Richard, Robert; Donovan, Eric; Zhou, Meng; Goldstein, Mevlyn; El-Alaoui, Mostafa; Schriver, David; Walker, Raymond

    Observations and modeling have established that during geomagnetically disturbed times the Earth’s magnetotail goes through large scale changes that result in enhanced electron precipitation into the ionosphere and earthward propagating dipolarization fronts that contain highly energized plasma. Such events originate near reconnection regions in the magnetotail at about 20-30 R_E down tail. As the dipolarization fronts propagate earthward, strong acceleration of both ions and electrons occurs due to a combination of non-adiabatic and adiabatic (betatron and Fermi) acceleration, with particle energies reaching up to 100 keV within the dipolarization front. One consequence of the plasma transport that occurs during these events is direct electron precipitation into the ionosphere, which form auroral precipitation. Using global kinetic simulations along with spacecraft and ground-based data, causes of electron precipitation are determined during well-documented, disturbed events. It is found that precipitation of keV electrons in the pre-midnight sector at latitudes around 70(°) occur due to two distinct physical processes: (1) higher latitude (≥72(°) ) precipitation due to electrons that undergo relatively rapid non-adiabatic pitch angle scattering into the loss cone just earthward of the reconnection region at around 20 R_E downtail, and (2) lower latitude (≤72(°) ) precipitation due to electrons that are more gradually accelerated primarily parallel to the geomagnetic field during its bounce motion by Fermi acceleration and enter the loss cone much closer to the Earth at 10-15 R_E, somewhat tailward of the dipolarization front. As the dipolarization fronts propagate earthward, the electron precipitation shifts to lower latitudes and occurs over a wider region in the auroral ionosphere. Our results show a direct connection between electron acceleration in the magnetotail and electron precipitation in the ionosphere during disturbed times. The electron

  20. Hydrogen abstraction reactions by amide electron adducts

    International Nuclear Information System (INIS)

    Sevilla, M.D.; Sevilla, C.L.; Swarts, S.

    1982-01-01

    Electron reactions with a number of peptide model compounds (amides and N-acetylamino acids) in aqueous glasses at low temperature have been investigated using ESR spectroscopy. The radicals produced by electron attachment to amides, RC(OD)NDR', are found to act as hydrogen abstracting agents. For example, the propionamide electron adduct is found to abstract from its parent propionamide. Electron adducts of other amides investigated show similar behavior except for acetamide electron adduct which does not abstract from its parent compound, but does abstract from other amides. The tendency toward abstraction for amide electron adducts are compared to electron adducts of several carboxylic acids, ketones, aldehydes and esters. The comparison suggests the hydrogen abstraction tendency of the various deuterated electron adducts (DEAs) to be in the following order: aldehyde DEA > acid DEA = approximately ester DEA > ketone DEA > amide DEA. In basic glasses the hydrogen abstraction ability of the amide electron adducts is maintained until the concentration of base is increased sufficiently to convert the DEA to its anionic form, RC(O - )ND 2 . In this form the hydrogen abstracting ability of the radical is greatly diminished. Similar results were found for the ester and carboxylic acid DEA's tested. (author)

  1. Metal extraction by amides of carboxylic acids

    International Nuclear Information System (INIS)

    Skorovarov, D.I.; Chumakova, G.M.; Rusin, L.I.; Ul'anov, V.S.; Sviridova, R.A.; Sviridov, A.L.

    1988-01-01

    Extraction ability of various amides was studied. Data on extraction of rare earths, vanadium, molybdenum, rhenium, uranium, niobium, tantalum by N,N-dibutyl-amides of acetic, nonanic acids and fatly synthetic acids of C 7 -C 9 fractions are presented. Effect of salting-out agents, inorganic acid concentrations on extraction process was studied. Potential ability of using amides of carboxylic acids for extractional concentration of rare earths as well as for recovery and separation of iron, rhenium, vanadium, molybdenum, uranium, niobium, and tantalum was shown

  2. Dissecting Hofmeister Effects: Direct Anion-Amide Interactions Are Weaker than Cation-Amide Binding.

    Science.gov (United States)

    Balos, Vasileios; Kim, Heejae; Bonn, Mischa; Hunger, Johannes

    2016-07-04

    Whereas there is increasing evidence for ion-induced protein destabilization through direct ion-protein interactions, the strength of the binding of anions to proteins relative to cation-protein binding has remained elusive. In this work, the rotational mobility of a model amide in aqueous solution was used as a reporter for the interactions of different anions with the amide group. Protein-stabilizing salts such as KCl and KNO3 do not affect the rotational mobility of the amide. Conversely, protein denaturants such as KSCN and KI markedly reduce the orientational freedom of the amide group. Thus these results provide evidence for a direct denaturation mechanism through ion-protein interactions. Comparing the present findings with results for cations shows that in contrast to common belief, anion-amide binding is weaker than cation-amide binding. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. CHROMIUM(II) AMIDES - SYNTHESIS AND STRUCTURES

    NARCIS (Netherlands)

    EDEMA, JJH; GAMBAROTTA, S; MEETSMA, A; SPEK, AL; SMEETS, WJJ; CHIANG, MY

    1993-01-01

    A novel class of mono- and di-meric chromium(II) amides has been prepared and characterized. Reaction of [CrCl2(thf)2] (thf = tetrahydrofuran) with 2 equivalents of M(NR2) (R = C6H11, Pr(i), Ph, or phenothiazinyl; M = Li or Na) allowed the formation of the homoleptic amides [{Cr(mu-NR2)(NR2)}2] (R =

  4. How amide hydrogens exchange in native proteins.

    Science.gov (United States)

    Persson, Filip; Halle, Bertil

    2015-08-18

    Amide hydrogen exchange (HX) is widely used in protein biophysics even though our ignorance about the HX mechanism makes data interpretation imprecise. Notably, the open exchange-competent conformational state has not been identified. Based on analysis of an ultralong molecular dynamics trajectory of the protein BPTI, we propose that the open (O) states for amides that exchange by subglobal fluctuations are locally distorted conformations with two water molecules directly coordinated to the N-H group. The HX protection factors computed from the relative O-state populations agree well with experiment. The O states of different amides show little or no temporal correlation, even if adjacent residues unfold cooperatively. The mean residence time of the O state is ∼100 ps for all examined amides, so the large variation in measured HX rate must be attributed to the opening frequency. A few amides gain solvent access via tunnels or pores penetrated by water chains including native internal water molecules, but most amides access solvent by more local structural distortions. In either case, we argue that an overcoordinated N-H group is necessary for efficient proton transfer by Grotthuss-type structural diffusion.

  5. Photochemical reduction of uranyl ion with amides

    International Nuclear Information System (INIS)

    Brar, A.S.; Chander, R.; Sandhu, S.S.

    1981-01-01

    The photochemical reduction of uranyl ion by formamide, acetamide, propionamide, butyramide, iso butyramids, n-methylformamide, N, N-dimethylformamide and N, N-diethylformamide in aqueous medium using radiation >= 380 nm from a medium pressure mercury vapour lamp has been investigated. The reduction with the said amides has been found to obey pseudo first order kinetics. The magnitude of the rate of reduction for the simple amides has been found to follow the following order formamide > isobutyramide approx. butyramide > propionamide > acetamide while the rate order for N-alkylformamides compared with that of the formamide has been found to be formamide > N-methylformamide > N,N-diethylformamide approx. N,N-dimethylformamide. The pseudo first order rate constants and quenching constants have been found from the kinetic data. It has been found that physical and chemical quenching compete with each other. Plots of reciprocal of quantum yields versus reciprocal [amide] have been found to be linear with intercepts on the ordinate axis. Absorption spectra of uranyl ion in doubly distilled water, in the presence of acid and in the presence of acid and amide reveal that there is no ground state interaction between uranyl ion and the amide. A mechanism of photoreduction of uranyl ion with amides has been proposed. (author)

  6. How amide hydrogens exchange in native proteins

    Science.gov (United States)

    Persson, Filip; Halle, Bertil

    2015-01-01

    Amide hydrogen exchange (HX) is widely used in protein biophysics even though our ignorance about the HX mechanism makes data interpretation imprecise. Notably, the open exchange-competent conformational state has not been identified. Based on analysis of an ultralong molecular dynamics trajectory of the protein BPTI, we propose that the open (O) states for amides that exchange by subglobal fluctuations are locally distorted conformations with two water molecules directly coordinated to the N–H group. The HX protection factors computed from the relative O-state populations agree well with experiment. The O states of different amides show little or no temporal correlation, even if adjacent residues unfold cooperatively. The mean residence time of the O state is ∼100 ps for all examined amides, so the large variation in measured HX rate must be attributed to the opening frequency. A few amides gain solvent access via tunnels or pores penetrated by water chains including native internal water molecules, but most amides access solvent by more local structural distortions. In either case, we argue that an overcoordinated N–H group is necessary for efficient proton transfer by Grotthuss-type structural diffusion. PMID:26195754

  7. Thermal entanglement and teleportation in a dipolar interacting system

    Energy Technology Data Exchange (ETDEWEB)

    Castro, C.S., E-mail: ccastro@if.uff.br [Instituto de Física, Universidade Federal Fluminense, Av. Gal. Milton Tavares de Souza s/n, Gragoatá, 24210-346 Niterói, RJ (Brazil); Centro de Formação de Professores, Universidade Federal do Recôncavo da Bahia, Av. Nestor de Mello Pita, n. 535, 45.300-000 Amargosa, BA (Brazil); Duarte, O.S.; Pires, D.P.; Soares-Pinto, D.O. [Instituto de Física de São Carlos, Universidade de São Paulo, P.O. Box 369, São Carlos, 13560-970 SP (Brazil); Reis, M.S. [Instituto de Física, Universidade Federal Fluminense, Av. Gal. Milton Tavares de Souza s/n, Gragoatá, 24210-346 Niterói, RJ (Brazil)

    2016-04-22

    Quantum teleportation, which depends on entangled states, is a fascinating subject and an important branch of quantum information processing. The present work reports the use of a dipolar spin thermal system as a noisy quantum channel to perform quantum teleportation. Non-locality, tested by violation of Bell's inequality and thermal entanglement, measured by negativity, shows that for the present model all entangled states, even those that do not violate Bell's inequality, are useful for teleportation. - Highlights: • The effects of a dipolar interaction between two spins on their degree of entanglement and non-locality is reported. • The model presents some degree of non-locality and entanglement at a given coupling parameters. • It is shown how the magnetic anisotropies can influence the fidelity of teleportation.

  8. Coherent manipulation of dipolar coupled spins in an anisotropic environment

    Science.gov (United States)

    Baibekov, E. I.; Gafurov, M. R.; Zverev, D. G.; Kurkin, I. N.; Malkin, B. Z.; Barbara, B.

    2014-11-01

    We study coherent dynamics in a system of dipolar coupled spin qubits diluted in a solid and subjected to a driving microwave field. In the case of rare earth ions, an anisotropic crystal background results in anisotropic g tensor and thus modifies the dipolar coupling. We develop a microscopic theory of spin relaxation in a transient regime for the frequently encountered case of axially symmetric crystal field. The calculated decoherence rate is nonlinear in the Rabi frequency. We show that the direction of a static magnetic field that corresponds to the highest spin g factor is preferable in order to obtain a higher number of coherent qubit operations. The results of calculations are in excellent agreement with our experimental data on Rabi oscillations recorded for a series of CaW O4 crystals with different concentrations of N d3 + ions.

  9. Quantum phases of dipolar rotors on two-dimensional lattices.

    Science.gov (United States)

    Abolins, B P; Zillich, R E; Whaley, K B

    2018-03-14

    The quantum phase transitions of dipoles confined to the vertices of two-dimensional lattices of square and triangular geometry is studied using path integral ground state quantum Monte Carlo. We analyze the phase diagram as a function of the strength of both the dipolar interaction and a transverse electric field. The study reveals the existence of a class of orientational phases of quantum dipolar rotors whose properties are determined by the ratios between the strength of the anisotropic dipole-dipole interaction, the strength of the applied transverse field, and the rotational constant. For the triangular lattice, the generic orientationally disordered phase found at zero and weak values of both dipolar interaction strength and applied field is found to show a transition to a phase characterized by net polarization in the lattice plane as the strength of the dipole-dipole interaction is increased, independent of the strength of the applied transverse field, in addition to the expected transition to a transverse polarized phase as the electric field strength increases. The square lattice is also found to exhibit a transition from a disordered phase to an ordered phase as the dipole-dipole interaction strength is increased, as well as the expected transition to a transverse polarized phase as the electric field strength increases. In contrast to the situation with a triangular lattice, on square lattices, the ordered phase at high dipole-dipole interaction strength possesses a striped ordering. The properties of these quantum dipolar rotor phases are dominated by the anisotropy of the interaction and provide useful models for developing quantum phases beyond the well-known paradigms of spin Hamiltonian models, implementing in particular a novel physical realization of a quantum rotor-like Hamiltonian that possesses an anisotropic long range interaction.

  10. Dipolar and quadrupolar defects in a transport line

    International Nuclear Information System (INIS)

    Leleux, G.; Nghiem, P.

    1991-01-01

    The defects on a transport line of linear accelerator are studied. A transport line where the elements are influenced by the design or position defects is analyzed. Only dipolar and quadrupolar defects are considered, and the coupling betwen transversal motions are excluded. The data from the literature and those calculated by transfer matrices are compared. The defects on a line are considered from an analytical point of view. Closed optical structures are also studied [fr

  11. Quantum phases of dipolar rotors on two-dimensional lattices

    Science.gov (United States)

    Abolins, B. P.; Zillich, R. E.; Whaley, K. B.

    2018-03-01

    The quantum phase transitions of dipoles confined to the vertices of two-dimensional lattices of square and triangular geometry is studied using path integral ground state quantum Monte Carlo. We analyze the phase diagram as a function of the strength of both the dipolar interaction and a transverse electric field. The study reveals the existence of a class of orientational phases of quantum dipolar rotors whose properties are determined by the ratios between the strength of the anisotropic dipole-dipole interaction, the strength of the applied transverse field, and the rotational constant. For the triangular lattice, the generic orientationally disordered phase found at zero and weak values of both dipolar interaction strength and applied field is found to show a transition to a phase characterized by net polarization in the lattice plane as the strength of the dipole-dipole interaction is increased, independent of the strength of the applied transverse field, in addition to the expected transition to a transverse polarized phase as the electric field strength increases. The square lattice is also found to exhibit a transition from a disordered phase to an ordered phase as the dipole-dipole interaction strength is increased, as well as the expected transition to a transverse polarized phase as the electric field strength increases. In contrast to the situation with a triangular lattice, on square lattices, the ordered phase at high dipole-dipole interaction strength possesses a striped ordering. The properties of these quantum dipolar rotor phases are dominated by the anisotropy of the interaction and provide useful models for developing quantum phases beyond the well-known paradigms of spin Hamiltonian models, implementing in particular a novel physical realization of a quantum rotor-like Hamiltonian that possesses an anisotropic long range interaction.

  12. Amide-induced phase separation of hexafluoroisopropanol-water mixtures depending on the hydrophobicity of amides.

    Science.gov (United States)

    Takamuku, Toshiyuki; Wada, Hiroshi; Kawatoko, Chiemi; Shimomura, Takuya; Kanzaki, Ryo; Takeuchi, Munetaka

    2012-06-21

    Amide-induced phase separation of hexafluoro-2-propanol (HFIP)-water mixtures has been investigated to elucidate solvation properties of the mixtures by means of small-angle neutron scattering (SANS), (1)H and (13)C NMR, and molecular dynamics (MD) simulation. The amides included N-methylformamide (NMF), N-methylacetamide (NMA), and N-methylpropionamide (NMP). The phase diagrams of amide-HFIP-water ternary systems at 298 K showed that phase separation occurs in a closed-loop area of compositions as well as an N,N-dimethylformamide (DMF) system previously reported. The phase separation area becomes wider as the hydrophobicity of amides increases in the order of NMF amides due to the hydrophobic interaction gives rise to phase separation of the mixtures. In contrast, the disruption of HFIP clusters causes the recovery of the homogeneity of the ternary systems. The present results showed that HFIP clusters are evolved with increasing amide content to the lower phase separation concentration in the same mechanism among the four amide systems. However, the disruption of HFIP clusters in the NMP and DMF systems with further increasing amide content to the upper phase separation concentration occurs in a different way from those in the NMF and NMA systems.

  13. Poly(ether amide) segmented block copolymers with adipicacid based tetra amide segments

    NARCIS (Netherlands)

    Biemond, G.J.E.; Feijen, Jan; Gaymans, R.J.

    2007-01-01

    Poly(tetramethylene oxide)-based poly(ether ester amide)s with monodisperse tetraamide segments were synthesized. The tetraamide segment was based on adipic acid, terephthalic acid, and hexamethylenediamine. The synthesis method of the copolymers and the influence of the tetraamide concentration,

  14. Microorganisms hydrolyse amide bonds; knowledge enabling read-across of biodegradability of fatty acid amides

    NARCIS (Netherlands)

    Geerts, R.; Kuijer, P.; Ginkel, van C.G.; Plugge, C.M.

    2014-01-01

    To get insight in the biodegradation and potential read-across of fatty acid amides, N-[3-(dimethylamino)propyl] cocoamide and N-(1-ethylpiperazine) tall oil amide were used as model compounds. Two bacteria, Pseudomonas aeruginosa PK1 and Pseudomonas putida PK2 were isolated with

  15. Ground state configurations in antiferromagnetic ultrathin films with dipolar anisotropy

    International Nuclear Information System (INIS)

    León, H.

    2013-01-01

    The formalism developed in a previous work to calculate the dipolar energy in quasi-two-dimensional crystals with ferromagnetic order is now extended to collinear antiferromagnetic order. Numerical calculations of the dipolar energy are carried out for systems with tetragonally distorted fcc [001] structures, the case of NiO and MnO ultrathin film grown in non-magnetic substrates, where the magnetic phase is a consequence of superexchange and dipolar interactions. The employed approximation allows to demonstrate that dipolar coupling between atomic layers is responsible for the orientation of the magnetization when it differs from the one in a single layer. The ground state energy of a given NiO or MnO film is found to depend not only on the strain, but also on how much the interlayer separation and the 2D lattice constant are changed with respect to the ideal values corresponding to the non-distorted cubic structure. Nevertheless, it is shown that the orientation of the magnetization in the magnetic phase of any of these films is determined by the strain exclusively. A striped phase with the magnetization along the [112 ¯ ] direction appears as the ground state configuration of NiO and MnO ultrathin films. In films with equally oriented stripes along the layers this magnetic phase is twofold degenerate, while in films with multidomain layers it is eightfold degenerate. These results are not in contradiction with experimentally observed out-of-plane or in-plane magnetization of striped phases in NiO and MnO ultrathin films. - Highlights: ► Dipolar energy in collinear antiferromagnetic ultrathin films is calculated. ► Numerical results are presented for distorted fcc [001] structures. ► The lowest energy of a system depends on how the tetragonal distortion is achieved. ► A striped phase with magnetization in the [112 ¯ ] direction is the ground state. ► In multidomain NiO and MnO films it is eightfold degenerate.

  16. Salt forms of the pharmaceutical amide dihydrocarbamazepine.

    Science.gov (United States)

    Buist, Amanda R; Kennedy, Alan R

    2016-02-01

    Carbamazepine (CBZ) is well known as a model active pharmaceutical ingredient used in the study of polymorphism and the generation and comparison of cocrystal forms. The pharmaceutical amide dihydrocarbamazepine (DCBZ) is a less well known material and is largely of interest here as a structural congener of CBZ. Reaction of DCBZ with strong acids results in protonation of the amide functionality at the O atom and gives the salt forms dihydrocarbamazepine hydrochloride {systematic name: [(10,11-dihydro-5H-dibenzo[b,f]azepin-5-yl)(hydroxy)methylidene]azanium chloride, C15H15N2O(+)·Cl(-)}, dihydrocarbamazepine hydrochloride monohydrate {systematic name: [(10,11-dihydro-5H-dibenzo[b,f]azepin-5-yl)(hydroxy)methylidene]azanium chloride monohydrate, C15H15N2O(+)·Cl(-)·H2O} and dihydrocarbamazepine hydrobromide monohydrate {systematic name: [(10,11-dihydro-5H-dibenzo[b,f]azepin-5-yl)(hydroxy)methylidene]azanium bromide monohydrate, C15H15N2O(+)·Br(-)·H2O}. The anhydrous hydrochloride has a structure with two crystallographically independent ion pairs (Z' = 2), wherein both cations adopt syn conformations, whilst the two hydrated species are mutually isostructural and have cations with anti conformations. Compared to neutral dihydrocarbamazepine structures, protonation of the amide group is shown to cause changes to both the molecular (C=O bond lengthening and C-N bond shortening) and the supramolecular structures. The amide-to-amide and dimeric hydrogen-bonding motifs seen for neutral polymorphs and cocrystalline species are replaced here by one-dimensional polymeric constructs with no direct amide-to-amide bonds. The structures are also compared with, and shown to be closely related to, those of the salt forms of the structurally similar pharmaceutical carbamazepine.

  17. Chemoselective reductive nucleophilic addition to tertiary amides, secondary amides, and N-methoxyamides.

    Science.gov (United States)

    Nakajima, Minami; Oda, Yukiko; Wada, Takamasa; Minamikawa, Ryo; Shirokane, Kenji; Sato, Takaaki; Chida, Noritaka

    2014-12-22

    As the complexity of targeted molecules increases in modern organic synthesis, chemoselectivity is recognized as an important factor in the development of new methodologies. Chemoselective nucleophilic addition to amide carbonyl centers is a challenge because classical methods require harsh reaction conditions to overcome the poor electrophilicity of the amide carbonyl group. We have successfully developed a reductive nucleophilic addition of mild nucleophiles to tertiary amides, secondary amides, and N-methoxyamides that uses the Schwartz reagent [Cp2 ZrHCl]. The reaction took place in a highly chemoselective fashion in the presence of a variety of sensitive functional groups, such as methyl esters, which conventionally require protection prior to nucleophilic addition. The reaction will be applicable to the concise synthesis of complex natural alkaloids from readily available amide groups. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. A new approach for applying residual dipolar couplings as restraints in structure elucidation

    International Nuclear Information System (INIS)

    Meiler, Jens; Blomberg, Niklas; Nilges, Michael; Griesinger, Christian

    2000-01-01

    Residual dipolar couplings are useful global structural restraints. The dipolar couplings define the orientation of a vector with respect to the alignment tensor. Although the size of the alignment tensor can be derived from the distribution of the experimental dipolar couplings, its orientation with respect to the coordinate system of the molecule is unknown at the beginning of structure determination. This causes convergence problems in the simulated annealing process. We therefore propose a protocol that translates dipolar couplings into intervector projection angles, which are independent of the orientation of the alignment tensor with respect to the molecule. These restraints can be used during the whole simulated annealing protocol

  19. Propagation of Dipolarization Signatures Observed by the Van Allen Probes in the Inner Magnetosphere

    Science.gov (United States)

    Ohtani, S.; Motoba, T.; Gkioulidou, M.; Takahashi, K.; Kletzing, C.

    2017-12-01

    Dipolarization, the change of the local magnetic field from a stretched to a more dipolar configuration, is one of the most fundamental processes of magnetospheric physics. It is especially critical for the dynamics of the inner magnetosphere. The associated electric field accelerates ions and electrons and transports them closer to Earth. Such injected ions intensify the ring current, and electrons constitute the seed population of the radiation belt. Those ions and electrons may also excite various waves that play important roles in the enhancement and loss of the radiation belt electrons. Despite such critical consequences, the general characteristics of dipolarization in the inner magnetosphere still remain to be understood. The Van Allen Probes mission, which consists of two probes that orbit through the equatorial region of the inner magnetosphere, provides an ideal opportunity to examine dipolarization signatures in the core of the ring current. In the present study we investigate the spatial expansion of the dipolarization region by examining the correlation and time delay of dipolarization signatures observed by the two probes. Whereas in general it requires three-point measurements to deduce the propagation of a signal on a certain plane, we statically examined the observed time delays and found that dipolarization signatures tend to propagate radially inward as well as away from midnight. In this paper we address the propagation of dipolarization signatures quantitatively and compare with the propagation velocities reported previously based on observations made farther away from Earth. We also discuss how often and under what conditions the dipolarization region expands.

  20. Effect of amides on lithium tetraborate solubility

    Energy Technology Data Exchange (ETDEWEB)

    Tsekhanskij, R S; Skvortsov, V C; Molodkin, A K; Sadetdi-pov, Sh V [Chuvashskij Gosudarstvennyj Pedagogicheskij Inst., Cheboksary (USSR); Universitet Druzhby Narodov, Moscow (USSR))

    1983-03-01

    Using the methods of solubility, densi- and refractometry at 25 deg C, it has been established that the systems lithium tetraborate-formamide (acetamide, dimethyl-formamide)-water are of a simple eutonic type. Amides decrease the salt solubility. Lyotropic effect, as calculated for molar concentrations (-Lsub(M)) relative to the absolute value, increases from formamide to dimethyl-formamide. The sequence is determined by the fact that, when there is one or two hydrophilic methyl groups in amide molecules which are in contact with tetraborate, they decrease the hydration energy of lithium cations.

  1. Effect of amides on sodium tetraborate solubility

    International Nuclear Information System (INIS)

    Tsekhanskij, R.S.; Skvortsov, V.G.; Molodkin, A.K.; Sadetdinov, Sh.V.

    1986-01-01

    Methods of solubility and refractometry at 25 deg C were applied to investigate sodium tetraborate - formamide (dimethylformamide) - water systems. It is stated that they are of simple eutonic type as well as the earlier described sodium tetraborate-acetamide-water system. Amides reduce solubility of the salt. The effect of contact interaction between dissolved substances on salt cation hydration and thus on the value of liotropic amide effect is confirmed. This value is found to be also depend on the number of molecules of coordination water in the initial crystalline hydrate

  2. Effect of amides on lithium tetraborate solubility

    International Nuclear Information System (INIS)

    Tsekhanskij, R.S.; Skvortsov, V.C.; Molodkin, A.K.; Sadetdi- pov, Sh.V.

    1983-01-01

    Using the methods of solubility, densi- and refractometry at 25 deg C, it has been established that the systemS lithium tetraborate-formamide (acetamide, dimethyl-formamide)-water are of a simple eutonic type. Amides decrease the salt solubility. Lyotropic effect, as calculated for molar concentrations (-Lsub(M)) relative to the absolute value, increases from formamide to dimethylformamide. The sequence is determined by the fact that, when there is one or two hydrophilic methyl groups in amide molecules which are in contact with tetraborate, they decrease the hydration energy of lithium cations

  3. Effect of amides on sodium tetraborate solubility

    Energy Technology Data Exchange (ETDEWEB)

    Tsekhanskij, R S; Skvortsov, V G; Molodkin, A K; Sadetdinov, Sh V

    1986-11-01

    Methods of solubility and refractometry at 25 deg C were applied to investigate sodium tetraborate - formamide (dimethylformamide) - water systems. It is stated that they are of simple eutonic type as well as the earlier described sodium tetraborate-acetamide-water system. Amides reduce solubility of the salt. The effect of contact interaction between dissolved substances on salt cation hydration and thus on the value of liotropic amide effect is confirmed. This value is found to be also depend on the number of molecules of coordination water in the initial crystalline hydrate.

  4. Polyimides Containing Amide And Perfluoroisopropyl Links

    Science.gov (United States)

    Dezem, James F.

    1993-01-01

    New polyimides synthesized from reactions of aromatic hexafluoroisopropyl dianhydrides with asymmetric amide diamines. Soluble to extent of at least 10 percent by weight at temperature of about 25 degrees C in common amide solvents such as N-methylpyrrolidone, N,N-dimethylacetamide, and N,N-dimethylformamide. Polyimides form tough, flexible films, coatings, and moldings. Glass-transition temperatures ranged from 300 to 365 degrees C, and crystalline melting temperatures observed between 543 and 603 degrees C. Display excellent physical, chemical, and electrical properties. Useful as adhesives, laminating resins, fibers, coatings for electrical and decorative purposes, films, wire enamels, and molding compounds.

  5. Friedel-Crafts Acylation with Amides

    Science.gov (United States)

    Raja, Erum K.; DeSchepper, Daniel J.; Nilsson Lill, Sten O.; Klumpp, Douglas A.

    2012-01-01

    Friedel-Crafts acylation has been known since the 1870s and it is an important organic synthetic reaction leading to aromatic ketone products. Friedel-Crafts acylation is usually done with carboxylic acid chlorides or anhydrides while amides are generally not useful substrates in these reactions. Despite being the least reactive carboxylic acid derivative, we have found a series of amides capable of providing aromatic ketones in good yields (55–96%, 17 examples). We propose a mechanism involving diminished C-N resonance through superelectrophilic activation and subsequent cleavage to acyl cations. PMID:22690740

  6. Amide-transforming activity of Streptomyces: possible application to the formation of hydroxy amides and aminoalcohols.

    Science.gov (United States)

    Yamada, Shinya; Miyagawa, Taka-Aki; Yamada, Ren; Shiratori-Takano, Hatsumi; Sayo, Noboru; Saito, Takao; Takano, Hideaki; Beppu, Teruhiko; Ueda, Kenji

    2013-07-01

    To develop an efficient bioconversion process for amides, we screened our collection of Streptomyces strains, mostly obtained from soil, for effective transformers. Five strains, including the SY007 (NBRC 109343) and SY435 (NBRC 109344) of Streptomyces sp., exhibited marked conversion activities from the approximately 700 strains analyzed. These strains transformed diverse amide compounds such as N-acetyltetrahydroquinoline, N-benzoylpyrrolidine, and N-benzoylpiperidine into alcohols or N,O-acetals with high activity and regioselectivity. N,O-acetal was transformed into alcohol by serial tautomerization and reduction reactions. As such, Streptomyces spp. can potentially be used for the efficient preparation of hydroxy amides and aminoalcohols.

  7. Enantioselective synthesis of α-oxy amides via Umpolung amide synthesis.

    Science.gov (United States)

    Leighty, Matthew W; Shen, Bo; Johnston, Jeffrey N

    2012-09-19

    α-Oxy amides are prepared through enantioselective synthesis using a sequence beginning with a Henry addition of bromonitromethane to aldehydes and finishing with Umpolung Amide Synthesis (UmAS). Key to high enantioselection is the finding that ortho-iodo benzoic acid salts of the chiral copper(II) bis(oxazoline) catalyst deliver both diastereomers of the Henry adduct with high enantiomeric excess, homochiral at the oxygen-bearing carbon. Overall, this approach to α-oxy amides provides an innovative complement to alternatives that focus almost entirely on the enantioselective synthesis of α-oxy carboxylic acids.

  8. The effect of dipolar interaction on the magnetic isotope effect

    DEFF Research Database (Denmark)

    Mojaza, Matin; Pedersen, Jørgen Boiden; Lukzen, Nikita

    2010-01-01

    A multi-channel kinetic description is used to study the magnetic isotope effect (MIE) in zero magnetic field. The maximal isotope effect is equal to the number of channels, two for the hyperfine interaction but four for the electron spin dipole–dipole interaction of the intermediate radical pair....... Quantum mechanical calculations agree with these conclusion and show that large MIE may be obtained even in the presence of a strong exchange interaction. The observed magnesium isotope effect on the rate of enzymatic synthesis of adenosine triphosphate (ATP) is approximately 3 implying that the dipolar...... interaction is responsible for the effect. Our calculations provide support for the proposed mechanism....

  9. Magnetic holes in the dipolarized magnetotail: ion and electron anisotropies

    Science.gov (United States)

    Shustov, P.; Artemyev, A.; Zhang, X. J.; Yushkov, E.; Petrukovich, A. A.

    2017-12-01

    We conduct statistics on magnetic holes observed by THEMIS spacecraft in the near-Earth magnetotail. Groups of holes are detected after dipolarizations in the quiet, equatorial plasma sheet. Magnetic holes are characterized by significant magnetic field depressions (up to 50%) and strong electron currents ( 10-50 nA/m2), with spatial scales much smaller than the ion gyroradius. These magnetic holes are populated by hot (>10 keV), transversely anisotropic electrons supporting the pressure balance. We present statistical properties of these sub-ion scale magnetic holes and discuss possible mechanisms on the hole formation.

  10. Dipolar interaction in arrays of magnetic nanotubes

    International Nuclear Information System (INIS)

    Velázquez-Galván, Y; Martínez-Huerta, J M; Encinas, A; De La Torre Medina, J; Danlée, Y; Piraux, L

    2014-01-01

    The dipolar interaction field in arrays of nickel nanotubes has been investigated on the basis of expressions derived from the effective demagnetizing field of the assembly as well as magnetometry measurements. The model incorporates explicitly the wall thickness and aspect ratio, as well as the spatial order of the nanotubes. The model and experiment show that the interaction field in nanotubes is smaller than that in solid nanowires due to the packing fraction reduction in tubes related to their inner cavity. Finally, good agreement between the model and experiment is found for the variation of the interaction field as a function of the tube wall thickness. (paper)

  11. Spreading dynamics of 2D dipolar Langmuir monolayer phases.

    Science.gov (United States)

    Heinig, P; Wurlitzer, S; Fischer, Th M

    2004-07-01

    We study the spreading of a liquid 2D dipolar droplet in a Langmuir monolayer. Interfacial tensions (line tensions) and microscopic contact angles depend on the scale on which they are probed and obey a scaling law. Assuming rapid equilibration of the microscopic contact angle and ideal slippage of the 2D solid/liquid and solid/gas boundary, the driving force of spreading is merely expressed by the shape-dependent long-range interaction integrals. We obtain good agreement between experiment and numerical simulations using this theory.

  12. Synchronization of spin torque nano-oscillators through dipolar interactions

    International Nuclear Information System (INIS)

    Chen, Hao-Hsuan; Wu, Jong-Ching; Horng, Lance; Lee, Ching-Ming; Chang, Ching-Ray; Chang, Jui-Hang

    2014-01-01

    In an array of spin-torque nano-oscillators (STNOs) that combine a perpendicular polarized fixed layer with strong in-plane anisotropy in the free layers, magnetic dipolar interactions can effectively phase-lock the array, thus further enhancing the power of the output microwave signals. We perform a qualitative analysis of the synchronization of an array based on the Landau-Lifshitz-Gilbert equation, with a spin-transfer torque that assumes strong in-plane anisotropy. Finally, we present the numerical results for four coupled STNOs to provide further evidence for the proposed theory

  13. Synchronization of spin torque nano-oscillators through dipolar interactions

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Hao-Hsuan, E-mail: d95222014@ntu.edu.tw; Wu, Jong-Ching, E-mail: phjcwu@cc.ncue.edu.tw; Horng, Lance [Department of Physics, National Changhua University of Education, Changhua 500, Taiwan (China); Lee, Ching-Ming [Graduate School of Materials Science, National Yunlin University of Science and Technology, Douliou, 64002, Taiwan (China); Chang, Ching-Ray, E-mail: crchang@phys.ntu.edu.tw; Chang, Jui-Hang [Department of Physics and Center for Quantum Sciences and Engineering, National Taiwan University, Taipei 10617, Taiwan (China)

    2014-04-07

    In an array of spin-torque nano-oscillators (STNOs) that combine a perpendicular polarized fixed layer with strong in-plane anisotropy in the free layers, magnetic dipolar interactions can effectively phase-lock the array, thus further enhancing the power of the output microwave signals. We perform a qualitative analysis of the synchronization of an array based on the Landau-Lifshitz-Gilbert equation, with a spin-transfer torque that assumes strong in-plane anisotropy. Finally, we present the numerical results for four coupled STNOs to provide further evidence for the proposed theory.

  14. Nickel-Catalyzed Reductive Transamidation of Secondary Amides with Nitroarenes

    OpenAIRE

    Cheung, Chi Wai; Ploeger, Marten Leendert; Hu, Xile

    2017-01-01

    Transmidation is an attractive method for amide synthesis. However, transamidation of secondary amides is challenging. Here, we describe a reductive transamidation method that employs readily available nitro(hetero)arenes as the nitrogen sources, zinc or manganese as reductant, and simple nickel salt and ligand as a catalyst system. The scope of amides includes both alkyl and aryl secondary amides, with high functional group compatibility.

  15. Metabolism of amino acid amides in Pseudomonas putida ATCC 12633

    NARCIS (Netherlands)

    Hermes, H.F.M.; Croes, L.M.; Peeters, W.P.H.; Peters, P.J.H.; Dijkhuizen, L.

    1993-01-01

    The metabolism of the natural amino acid L-valine, the unnatural amino acids D-valine, and D-, L-phenylglycine (D-, L-PG), and the unnatural amino acid amides D-, L-phenylglycine amide (D, L-PG-NH2) and L-valine amide (L-Val-NH2) was studied in Pseudomonas putida ATCC 12633. The organism possessed

  16. Highly efficient aerobic oxidation of alcohols by using less-hindered nitroxyl-radical/copper catalysis: optimum catalyst combinations and their substrate scope.

    Science.gov (United States)

    Sasano, Yusuke; Kogure, Naoki; Nishiyama, Tomohiro; Nagasawa, Shota; Iwabuchi, Yoshiharu

    2015-04-01

    The oxidation of alcohols into their corresponding carbonyl compounds is one of the most fundamental transformations in organic chemistry. In our recent report, 2-azaadamantane N-oxyl (AZADO)/copper catalysis promoted the highly chemoselective aerobic oxidation of unprotected amino alcohols into amino carbonyl compounds. Herein, we investigated the extension of the promising AZADO/copper-catalyzed aerobic oxidation of alcohols to other types of alcohol. During close optimization of the reaction conditions by using various alcohols, we found that the optimum combination of nitroxyl radical, copper salt, and solution concentration was dependent on the type of substrate. Various alcohols, including highly hindered and heteroatom-rich ones, were efficiently oxidized into their corresponding carbonyl compounds under mild conditions with lower amounts of the catalysts. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Mass Spectra Analyses of Amides and Amide Dimers of Steviol, Isosteviol, and Steviolbioside

    Directory of Open Access Journals (Sweden)

    Lin-Wen Lee

    2012-01-01

    Full Text Available The mass spectra of a series of stevioside analogues including the amide and dimer compounds of steviol, isosteviol, and steviolbioside were examined. Positive ion mass spectral fragmentation of new steviol, isosteviol, and steviolbioside amides and the amide dimers are reported and discussed. The techniques included their synthesis procedures, fast-atom bombardment (FAB, and LC/MS/MS mass spectra. Intense [M+H]+ and [M+Na]+ ion peaks were observed on the FAB and ESI spectra. LC/MS/MS also yielded ES+ and ES− ion peaks that fairly agreed with the results of the FAB and ESI studies. Mass spectral analysis of compounds 4p-q, 5a-g, 6, and 7 revealed the different cleavage pathway patterns that can help in identifying the structures of steviolbioside and its amide derivatives.

  18. Amides and an alkaloid from Portulaca oleracea.

    Science.gov (United States)

    Kokubun, Tetsuo; Kite, Geoffrey C; Veitch, Nigel C; Simmonds, Monique S J

    2012-08-01

    A total of 16 phenolic compounds, including one new and five known N-cinnamoyl phenylethylamides, one new pyrrole alkaloid named portulacaldehyde, five phenylpropanoid acids and amides, and derivatives of benzaldehyde and benzoic acid, were isolated and identified from a polar fraction of an extract of Portulaca oleracea. Their structures were determined through spectroscopic analyses.

  19. 76 FR 69636 - Amides, C5

    Science.gov (United States)

    2011-11-09

    ... in guinea pigs showed that amides, C 5 - C 9 , N-[3-(dimethylamino) propyl] was not a skin sensitizer.... Potentially affected entities may include, but are not limited to: Crop production (NAICS code 111). Animal production (NAICS code 112). Food manufacturing (NAICS code 311). Pesticide manufacturing (NAICS code 32532...

  20. Direct Amination of alpha-Hydroxy Amides

    NARCIS (Netherlands)

    Chandgude, Ajay L.; Dömling, Alexander

    A TiCl4-mediated reaction for the direct amination of alpha-hydroxy amides has been developed. This simple, general, additive/base/ligand-free reaction is mediated by economical TiCl4. The reaction runs under mild conditions. This highly efficient C-N bond formation protocol is valid for diverse

  1. Steroids linked with amide bond - extended cholesterol

    Czech Academy of Sciences Publication Activity Database

    Černý, Ivan; Buděšínský, Miloš; Pouzar, Vladimír; Drašar, P.

    2009-01-01

    Roč. 74, č. 1 (2009), s. 88-94 ISSN 0039-128X R&D Projects: GA MŠk(CZ) LC06077; GA AV ČR KAN200200651 Institutional research plan: CEZ:AV0Z40550506 Keywords : synthesis * oligomers * amides Subject RIV: CC - Organic Chemistry Impact factor: 2.905, year: 2009

  2. Visualization of magnetic dipolar interaction based on scanning transmission X-ray microscopy

    International Nuclear Information System (INIS)

    Ohtori, Hiroyuki; Iwano, Kaoru; Takeichi, Yasuo; Ono, Kanta; Mitsumata, Chiharu; Yano, Masao; Kato, Akira; Miyamoto, Noritaka; Shoji, Tetsuya; Manabe, Akira

    2014-01-01

    Using scanning transmission X-ray microscopy (STXM), in this report we visualized the magnetic dipolar interactions in nanocrystalline Nd-Fe-B magnets and imaged their magnetization distributions at various applied fields. We calculated the magnetic dipolar interaction by analyzing the interaction between the magnetization at each point and those at the other points on the STXM image.

  3. Evidence for several dipolar quasi-invariants in liquid crystals

    Science.gov (United States)

    Bonin, C. J.; González, C. E.; Segnorile, H. H.; Zamar, R. C.

    2013-10-01

    The quasi-equilibrium states of an observed quantum system involve as many constants of motion as the dimension of the operator basis which spans the blocks of all the degenerate eigenvalues of the Hamiltonian that drives the system dynamics, however, the possibility of observing such quasi-invariants in solid-like spin systems in Nuclear Magnetic Resonance (NMR) is not a strictly exact prediction. The aim of this work is to provide experimental evidence of several quasi-invariants, in the proton NMR of small spin clusters, like nematic liquid crystal molecules, in which the use of thermodynamic arguments is not justified. We explore the spin states prepared with the Jeener-Broekaert pulse sequence by analyzing the time-domain signals yielded by this sequence as a function of the preparation times, in a variety of dipolar networks, solids, and liquid crystals. We observe that the signals can be explained with two dipolar quasi-invariants only within a range of short preparation times, however at longer times liquid crystal signals show an echo-like behaviour whose description requires assuming more quasi-invariants. We study the multiple quantum coherence content of such signals on a basis orthogonal to the z-basis and see that such states involve a significant number of correlated spins. Therefore, we show that the NMR signals within the whole preparation time-scale can only be reconstructed by assuming the occurrence of multiple quasi-invariants which we experimentally isolate.

  4. Observation of roton mode population in a dipolar quantum gas

    Science.gov (United States)

    Chomaz, L.; van Bijnen, R. M. W.; Petter, D.; Faraoni, G.; Baier, S.; Becher, J. H.; Mark, M. J.; Wächtler, F.; Santos, L.; Ferlaino, F.

    2018-05-01

    The concept of a roton, a special kind of elementary excitation forming a minimum of energy at finite momentum, has been essential for the understanding of the properties of superfluid 4He (ref. 1). In quantum liquids, rotons arise from the strong interparticle interactions, whose microscopic description remains debated2. In the realm of highly controllable quantum gases, a roton mode has been predicted to emerge due to magnetic dipole-dipole interactions despite their weakly interacting character3. This prospect has raised considerable interest4-12; yet roton modes in dipolar quantum gases have remained elusive to observations. Here we report experimental and theoretical studies of the momentum distribution in Bose-Einstein condensates of highly magnetic erbium atoms, revealing the existence of the long-sought roton mode. Following an interaction quench, the roton mode manifests itself with the appearance of symmetric peaks at well-defined finite momentum. The roton momentum follows the predicted geometrical scaling with the inverse of the confinement length along the magnetization axis. From the growth of the roton population, we probe the roton softening of the excitation spectrum in time and extract the corresponding imaginary roton gap. Our results provide a further step in the quest towards supersolidity in dipolar quantum gases13.

  5. Finite-size corrections in simulation of dipolar fluids

    Science.gov (United States)

    Belloni, Luc; Puibasset, Joël

    2017-12-01

    Monte Carlo simulations of dipolar fluids are performed at different numbers of particles N = 100-4000. For each size of the cubic cell, the non-spherically symmetric pair distribution function g(r,Ω) is accumulated in terms of projections gmnl(r) onto rotational invariants. The observed N dependence is in very good agreement with the theoretical predictions for the finite-size corrections of different origins: the explicit corrections due to the absence of fluctuations in the number of particles within the canonical simulation and the implicit corrections due to the coupling between the environment around a given particle and that around its images in the neighboring cells. The latter dominates in fluids of strong dipolar coupling characterized by low compressibility and high dielectric constant. The ability to clean with great precision the simulation data from these corrections combined with the use of very powerful anisotropic integral equation techniques means that exact correlation functions both in real and Fourier spaces, Kirkwood-Buff integrals, and bridge functions can be derived from box sizes as small as N ≈ 100, even with existing long-range tails. In the presence of dielectric discontinuity with the external medium surrounding the central box and its replica within the Ewald treatment of the Coulombic interactions, the 1/N dependence of the gmnl(r) is shown to disagree with the, yet well-accepted, prediction of the literature.

  6. Rhodium-catalyzed asymmetric hydroboration of γ,δ-unsaturated amide derivatives: δ-borylated amides.

    Science.gov (United States)

    Hoang, G L; Zhang, S; Takacs, J M

    2018-05-08

    γ,δ-Unsaturated amides in which the alkene moiety bears an aryl or heteroaryl substituent undergo regioselective rhodium-catalyzed δ-borylation by pinacolborane to afford chiral secondary benzylic boronic esters. The results contrast the γ-borylation of γ,δ-unsaturated amides in which the disubstituted alkene moiety bears only alkyl substituents; the reversal in regiochemistry is coupled with a reversal in the sense of π-facial selectivity.

  7. When Ethyl Isocyanoacetate Meets Isatins: A 1,3-Dipolar/Inverse 1,3-Dipolar/Olefination Reaction for Access to 3-Ylideneoxindoles.

    Science.gov (United States)

    Yuan, Wen-Kui; Cui, Tao; Liu, Wei; Wen, Li-Rong; Li, Ming

    2018-03-16

    A new CuI/1,10-phen-catalyzed reaction for the synthesis of 3-ylideneoxindoles from readily available isatins and ethyl isocyanoacetate, in which ethyl isocyanoacetate acts as a latent two-carbon donor like the Wittig reagent, is reported. A tandem procedure including 1,3-dipolar cycloaddition/inverse 1,3-dipolar ring opening/olefination allows the preparation of 3-ylideneoxindoles with broad functional group tolerance.

  8. Quantum Fluctuations in Quasi-One-Dimensional Dipolar Bose-Einstein Condensates.

    Science.gov (United States)

    Edler, D; Mishra, C; Wächtler, F; Nath, R; Sinha, S; Santos, L

    2017-08-04

    Recent experiments have revealed that beyond-mean-field corrections are much more relevant in weakly interacting dipolar condensates than in their nondipolar counterparts. We show that in quasi-one-dimensional geometries quantum corrections in dipolar and nondipolar condensates are strikingly different due to the peculiar momentum dependence of the dipolar interactions. The energy correction of the condensate presents not only a modified density dependence, but it may even change from attractive to repulsive at a critical density due to the surprising role played by the transversal directions. The anomalous quantum correction translates into a strongly modified physics for quantum-stabilized droplets and dipolar solitons. Moreover, and for similar reasons, quantum corrections of three-body correlations, and hence of three-body losses, are strongly modified by the dipolar interactions. This intriguing physics can be readily probed in current experiments with magnetic atoms.

  9. N-Methylamino Pyrimidyl Amides (MAPA): Highly Reactive, Electronically-Activated Amides in Catalytic N-C(O) Cleavage.

    Science.gov (United States)

    Meng, Guangrong; Lalancette, Roger; Szostak, Roman; Szostak, Michal

    2017-09-01

    Despite recent progress in catalytic cross-coupling technologies, the direct activation of N-alkyl-N-aryl amides has been a challenging transformation. Here, we report the first Suzuki cross-coupling of N-methylamino pyrimidyl amides (MAPA) enabled by the controlled n N → π Ar conjugation and the resulting remodeling of the partial double bond character of the amide bond. The new mode of amide activation is suitable for generating acyl-metal intermediates from unactivated primary and secondary amides.

  10. Quantum simulation and quantum information processing with molecular dipolar crystals

    International Nuclear Information System (INIS)

    Ortner, M.

    2011-01-01

    In this thesis interactions between dipolar crystals and neutral atoms or separated molecules have been investigated. They were motivated to realize new kinds of lattice models in mixtures of atoms and polar molecules where an MDC functions as an underlying periodic lattice structure for the second species. Such models bring out the peculiar features of MDC's, that include a controllable, potentially sub-optical wavelength periodicity and strong particle phonon interactions. Only stable collisional configurations have been investigated, excluding chemical reactions between the substituents, and crystal distortions beyond the scope of perturbation theory. The system was treated in the polaron picture where particles of the second species are dressed by surrounding crystal phonons. To describe the competition between coherent and incoherent dynamics of the polarons, a master equation in the Brownian motion limit was used with phonons treated as a thermal heat bath. It was shown analytically that in a wide range of realistic parameters the corrections to the coherent time evolution are small, and that the dynamics of the dressed particles can be described by an effective extended Hubbard model with controllable system parameters. The last chapter of this thesis contains a proposal for QIP with cold polar molecules that, in contrast to previous works, uses an MDC as a quantum register. It was motivated by the unique features of dipolar molecules and to exploit the peculiar physical conditions in dipolar crystals. In this proposal the molecular dipole moments were tailored by non-local fields to include a small, switchable, state-dependent dipole moment in addition to the large internal state independent moment that stabilizes the crystal. It was shown analytically that a controllable, non-trivial phonon-mediated interaction can be generated that exceeds non-trivial, direct dipole-dipole couplings. The addressability problem due to high crystal densities was overcome by

  11. Twisted Amides: From Obscurity to Broadly Useful Transition-Metal-Catalyzed Reactions by N-C Amide Bond Activation.

    Science.gov (United States)

    Liu, Chengwei; Szostak, Michal

    2017-05-29

    The concept of using amide bond distortion to modulate amidic resonance has been known for more than 75 years. Two classic twisted amides (bridged lactams) ingeniously designed and synthesized by Kirby and Stoltz to feature fully perpendicular amide bonds, and as a consequence emanate amino-ketone-like reactivity, are now routinely recognized in all organic chemistry textbooks. However, only recently the use of amide bond twist (distortion) has advanced to the general organic chemistry mainstream enabling a host of highly attractive N-C amide bond cross-coupling reactions of broad synthetic relevance. In this Minireview, we discuss recent progress in this area and present a detailed overview of the prominent role of amide bond destabilization as a driving force in the development of transition-metal-catalyzed cross-coupling reactions by N-C bond activation. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Layers of Cold Dipolar Molecules in the Harmonic Approximation

    DEFF Research Database (Denmark)

    R. Armstrong, J.; Zinner, Nikolaj Thomas; V. Fedorov, D.

    2012-01-01

    We consider the N-body problem in a layered geometry containing cold polar molecules with dipole moments that are polarized perpendicular to the layers. A harmonic approximation is used to simplify the hamiltonian and bound state properties of the two-body inter-layer dipolar potential are used...... to adjust this effective interaction. To model the intra-layer repulsion of the polar molecules, we introduce a repulsive inter-molecule potential that can be parametrically varied. Single chains containing one molecule in each layer, as well as multi-chain structures in many layers are discussed...... and their energies and radii determined. We extract the normal modes of the various systems as measures of their volatility and eventually of instability, and compare our findings to the excitations in crystals. We find modes that can be classified as either chains vibrating in phase or as layers vibrating against...

  13. Electron Jet Detected by MMS at Dipolarization Front

    Science.gov (United States)

    Liu, C. M.; Fu, H. S.; Vaivads, A.; Khotyaintsev, Y. V.; Gershman, D. J.; Hwang, K.-J.; Chen, Z. Z.; Cao, D.; Xu, Y.; Yang, J.; Peng, F. Z.; Huang, S. Y.; Burch, J. L.; Giles, B. L.; Ergun, R. E.; Russell, C. T.; Lindqvist, P.-A.; Le Contel, O.

    2018-01-01

    Using MMS high-resolution measurements, we present the first observation of fast electron jet (Ve 2,000 km/s) at a dipolarization front (DF) in the magnetotail plasma sheet. This jet, with scale comparable to the DF thickness ( 0.9 di), is primarily in the tangential plane to the DF current sheet and mainly undergoes the E × B drift motion; it contributes significantly to the current system at the DF, including a localized ring-current that can modify the DF topology. Associated with this fast jet, we observed a persistent normal electric field, strong lower hybrid drift waves, and strong energy conversion at the DF. Such strong energy conversion is primarily attributed to the electron-jet-driven current (E ṡ je ≈ 2 E ṡ ji), rather than the ion current suggested in previous studies.

  14. Synthesis of Spiroisoxazolines by 1,3-Dipolar Cycloaddition

    Directory of Open Access Journals (Sweden)

    Peter Ertl

    1997-04-01

    Full Text Available The cycloaddition of the chiral nitrile oxide 1 to 1-R-substituted 3,3-methylene-5,5-dimethyl-2-pyrrolidinones 2 (where R is H, n-butyl-, 1,1-dimethylethoxycarbonyl-, 1-methylethenyl- and acetyl- proceeds regioselectively under the formation of spiroisoxazolines, namely 7-R-substituted-6-oxo-8,8-dimethyl-1-oxa-2,7-diazaspiro[4,4]non-2-enes 5 and 6. The asymmetric induction expected by the a-chiral centre of the nitrile oxide 1 was not very effective, diastereoisomers 5 and 6 were formed in an approximate 50:50 ratio. The stereoselectivity of the 1,3-dipolar cycloaddition of the arylnitrile oxide 7 with the chiral lactam 3 and the achiral lactone 4 are investigated. The attack of the 1,3-dipole occurred from the less hindered face of the dipolarophile 3 and 4, giving the major isomer 8 and 10, respectively.

  15. Nuclear dipolar magnetism around one microkelvin in calciumhydroxide

    International Nuclear Information System (INIS)

    Marks, J.

    1985-01-01

    This thesis is devoted to a study of dipolar magnetism of the proton spins in Ca(OH) 2 . First, cooling techniques are described. The energy of different spin configurations are calculated in the Weiss-field approximation. Crystallographic characteristics of Ca(OH) 2 are described, as well as a method to produce monocrystals and a method for crystal doping using 1.5 MeV electron beams. It is shown that the polarization mechanism of the proton spins in Ca(OH) 2 doped with O 2 - centra is the 'Solid Effect'. Susceptibility measurements are presented as a function of the polarization. Results imply that both at positive and at negative temperatures state ordering sets in, characterized by a plateau in the susceptibility. (Auth/G.J.P.)

  16. Hidden magnetism in periodically modulated one dimensional dipolar fermions

    Science.gov (United States)

    Fazzini, S.; Montorsi, A.; Roncaglia, M.; Barbiero, L.

    2017-12-01

    The experimental realization of time-dependent ultracold lattice systems has paved the way towards the implementation of new Hubbard-like Hamiltonians. We show that in a one-dimensional two-components lattice dipolar Fermi gas the competition between long range repulsion and correlated hopping induced by periodically modulated on-site interaction allows for the formation of hidden magnetic phases, with degenerate protected edge modes. The magnetism, characterized solely by string-like nonlocal order parameters, manifests in the charge and/or in the spin degrees of freedom. Such behavior is enlighten by employing Luttinger liquid theory and numerical methods. The range of parameters for which hidden magnetism is present can be reached by means of the currently available experimental setups and probes.

  17. Drag Effect in Double-Layer Dipolar Fermi Gases

    International Nuclear Information System (INIS)

    Tanatar, B; Renklioglu, B; Oktel, M O

    2014-01-01

    We consider two parallel layers of two-dimensional spin-polarized dipolar Fermi gas without any tunneling between the layers. The effective interactions describing screening and correlation effects between the dipoles in a single layer (intra-layer) and across the layers (interlayer) are modeled within the Hubbard approximation. We calculate the rate of momentum transfer between the layers when the gas in one layer has a steady flow. The momentum transfer induces a steady flow in the second layer which is assumed initially at rest. This is the drag effect familiar from double-layer semiconductor and graphene structures. Our calculations show that the momentum relaxation time has temperature dependence similar to that in layers with charged particles which we think is related to the contributions from the collective modes of the system

  18. Structure refinement of flexible proteins using dipolar couplings: Application to the protein p8MTCP1

    International Nuclear Information System (INIS)

    Demene, Helene; Ducat, Thierry; Barthe, Philippe; Delsuc, Marc-Andre; Roumestand, Christian

    2002-01-01

    The present study deals with the relevance of using mobility-averaged dipolar couplings for the structure refinement of flexible proteins. The 68-residue protein p8 MTCP1 has been chosen as model for this study. Its solution state consists mainly of three α-helices. The two N-terminal helices are strapped in a well-determined α-hairpin, whereas, due to an intrinsic mobility, the position of the third helix is less well defined in the NMR structure. To further characterize the degrees of freedom of this helix, we have measured the dipolar coupling constants in the backbone of p8 MTCP1 in a bicellar medium. We show here that including D HN dip dipolar couplings in the structure calculation protocol improves the structure of the α-hairpin but not the positioning of the third helix. This is due to the motional averaging of the dipolar couplings measured in the last helix. Performing two calculations with different force constants for the dipolar restraints highlights the inconstancy of these mobility-averaged dipolar couplings. Alternatively, prior to any structure calculations, comparing the values of the dipolar couplings measured in helix III to values back-calculated from an ideal helix demonstrates that they are atypical for a helix. This can be partly attributed to mobility effects since the inclusion of the 15 N relaxation derived order parameter allows for a better fit

  19. Equilibrium phases of dipolar lattice bosons in the presence of random diagonal disorder

    Science.gov (United States)

    Zhang, C.; Safavi-Naini, A.; Capogrosso-Sansone, B.

    2018-01-01

    Ultracold gases offer an unprecedented opportunity to engineer disorder and interactions in a controlled manner. In an effort to understand the interplay between disorder, dipolar interactions, and quantum degeneracy, we study two-dimensional hard-core dipolar lattice bosons in the presence of on-site bound disorder. Our results are based on large-scale path-integral quantum Monte Carlo simulations by the worm algorithm. We study the ground-state phase diagram at a fixed half-integer filling factor for which the clean system is either a superfluid at a lower dipolar interaction strength or a checkerboard solid at a larger dipolar interaction strength. We find that, even for weak dipolar interactions, superfluidity is destroyed in favor of a Bose glass at a relatively low disorder strength. Interestingly, in the presence of disorder, superfluidity persists for values of the dipolar interaction strength for which the clean system is a checkerboard solid. At a fixed disorder strength, as the dipolar interaction is increased, superfluidity is destroyed in favor of a Bose glass. As the interaction is further increased, the system eventually develops extended checkerboard patterns in the density distribution. Due to the presence of disorder, though, grain boundaries and defects, responsible for a finite residual compressibility, are present in the density distribution. Finally, we study the robustness of the superfluid phase against thermal fluctuations.

  20. Particle-in-cell Simulation of Dipolarization Front Associated Whistlers

    Science.gov (United States)

    Lin, D.; Scales, W.; Ganguli, G.; Crabtree, C. E.

    2017-12-01

    Dipolarization fronts (DFs) are dipolarized magnetic field embedded in the Earthward propagating bursty bulk flows (BBFs), which separates the hot, tenuous high-speed flow from the cold, dense, and slowly convecting surrounding plasma [Runov et al. 2011]. Broadband fluctuations have been observed at DFs including the electromagnetic whistler waves and electrostatic lower hybrid waves in the Very Low Frequency (VLF) range [e.g., Zhou et al. 2009, Deng et al. 2010]. There waves are suggested to be able heat electrons and play a critical role in the plasma sheet dynamics [Chaston et al., 2012, Angelopoulos et al., 2013]. However, their generation mechanism and role in the energy conversion are still under debate. The gradient scale of magnetic field, plasma density at DFs in the near-Earth magnetotail is comparable to or lower than the ion gyro radius [Runov et al., 2011, Fu et al., 2012, Breuillard et al., 2016]. Such strongly inhomogeneous configuration could be unstable to the electron-ion hybrid (EIH) instability, which arises from strongly sheared transverse flow and is in the VLF range [Ganguli et al. 1988, Ganguli et al. 2014]. The equilibrium of the EIH theory implies an anisotropy of electron temperature, which are likely to drive the whistler waves observed in DFs [Deng et al., 2010, Gary et al., 2011]. In order to better understand how the whistler waves are generated in DFs and whether the EIH theory is applicable, a fully electromagnetic particle-in-cell (EMPIC) model is used to simulate the EIH instability with similar equilibrium configurations in DF observations. The EMPIC model deals with three dimensions in the velocity space and two dimensions in the configuration space, which is quite ready to include the third configuration dimension. Simulation results will be shown in this presentation.

  1. Vibrational lifetimes of protein amide modes

    International Nuclear Information System (INIS)

    Peterson, K.A.; Rella, C.A.

    1995-01-01

    Measurement of the lifetimes of vibrational modes in proteins has been achieved with a single frequency infrared pump-probe technique using the Stanford Picosecond Free-electron Laser, These are the first direct measurements of vibrational dynamics in the polyamide structure of proteins. In this study, modes associated with the protein backbone are investigated. Results for the amide I band, which consists mainly of the stretching motion of the carbonyl unit of the amide linkage, show that relaxation from the first vibrational excited level (v=1) to the vibrational ground state (v=0) occurs within 1.5 picoseconds with apparent first order kinetics. Comparison of lifetimes for myoglobin and azurin, which have differing secondary structures, show a small but significant difference. The lifetime for the amide I band of myoglobin is 300 femtoseconds shorter than for azurin. Further measurements are in progress on other backbone vibrational modes and on the temperature dependence of the lifetimes. Comparison of vibrational dynamics for proteins with differing secondary structure and for different vibrational modes within a protein will lead to a greater understanding of energy transfer and dissipation in biological systems. In addition, these results have relevance to tissue ablation studies which have been conducted with pulsed infrared lasers. Vibrational lifetimes are necessary for calculating the rate at which the energy from absorbed infrared photons is converted to equilibrium thermal energy within the irradiated volume. The very fast vibrational lifetimes measured here indicate that mechanisms which involve direct vibrational up-pumping of the amide modes with consecutive laser pulses, leading to bond breakage or weakening, are not valid

  2. Polyimides containing amide and perfluoroisopropylidene connecting groups

    Science.gov (United States)

    Dezern, James F. (Inventor)

    1993-01-01

    New, thermooxidatively stable polyimides were prepared from the reaction of aromatic dianhydrides containing isopropylidene bridging groups with aromatic diamines containing amide connecting groups between the rings. Several of these polyimides were shown to be semi-crystalline as evidenced by wide angle x ray scattering and differential scanning calorimetry. Most of the polyimides form tough, flexible films with high tensile properties. These polyimide films exhibit enhanced solubility in organic solvents.

  3. Energetic Electron Acceleration and Injection During Dipolarization Events in Mercury's Magnetotail

    Science.gov (United States)

    Dewey, Ryan M.; Slavin, James A.; Raines, Jim M.; Baker, Daniel N.; Lawrence, David J.

    2017-12-01

    Energetic particle bursts associated with dipolarization events within Mercury's magnetosphere were first observed by Mariner 10. The events appear analogous to particle injections accompanying dipolarization events at Earth. The Energetic Particle Spectrometer (3 s resolution) aboard MESSENGER determined the particle bursts are composed entirely of electrons with energies ≳ 300 keV. Here we use the Gamma-Ray Spectrometer high-time-resolution (10 ms) energetic electron measurements to examine the relationship between energetic electron injections and magnetic field dipolarization in Mercury's magnetotail. Between March 2013 and April 2015, we identify 2,976 electron burst events within Mercury's magnetotail, 538 of which are closely associated with dipolarization events. These dipolarizations are detected on the basis of their rapid ( 2 s) increase in the northward component of the tail magnetic field (ΔBz 30 nT), which typically persists for 10 s. Similar to those at Earth, we find that these dipolarizations appear to be low-entropy, depleted flux tubes convecting planetward following the collapse of the inner magnetotail. We find that electrons experience brief, yet intense, betatron and Fermi acceleration during these dipolarizations, reaching energies 130 keV and contributing to nightside precipitation. Thermal protons experience only modest betatron acceleration. While only 25% of energetic electron events in Mercury's magnetotail are directly associated with dipolarization, the remaining events are consistent with the Near-Mercury Neutral Line model of magnetotail injection and eastward drift about Mercury, finding that electrons may participate in Shabansky-like closed drifts about the planet. Magnetotail dipolarization may be the dominant source of energetic electron acceleration in Mercury's magnetosphere.

  4. Synthesis and uses of the amides extractants

    International Nuclear Information System (INIS)

    Musikas, C.

    1989-01-01

    Carboxylic acids amides (RR'NCOCR''), malonic acid amides (RR'NCOCH 2 CONRR') and substituted malonic acid amides (RR'NCOCHR'' CONRR') are extractants of the actinides ions. They show good prospects for use in the nuclear industry because of their complete incinerability. In addition, their degradation products interfer much more less in the separation processes when compared with organophosphorus extractants. The synthesis and the purification of two typical extractants: N-N-di (2-ethylhexyl) butyramide (C 4 H 9 CHC 2 H 5 CH 2 ) 2 NCOC 3 H 7 and N,N'-dimethyl N,N'-dibutyl 1.3 diamide 2(3-oxa)nonyl propane (C 4 H 9 CH 3 NCO) 2 CHC 2 H 4 OC 6 H 13 are described. The purities, checked by NMR, elemental analysis and potentiometry, were in the range 98 to 99.5%. The yields for monoamides were in the range 70 to 90% and for the diamides 20 to 40%. 3 figs, 3 tabs, 10 refs

  5. Chiral-glass transition in a diluted dipolar-interaction Heisenberg system

    International Nuclear Information System (INIS)

    Zhang Kaicheng; Liu Guibin; Zhu Yan

    2011-01-01

    Recently, numerical simulations reveal that a spin-glass transition can occur in the three-dimensional diluted dipolar system. By defining the chirality of triple spins in a diluted dipolar Heisenberg spin glass, we study the chiral ordering in the system using parallel tempering algorithm and heat bath method. The finite-size scaling analysis reveals that the system undergoes a chiral-glass transition at finite temperature. - Highlights: → We define the chirality in a diluted dipolar Heisenberg system. → The system undergoes a chiral-glass transition at finite temperature. → We extract the critical exponents of the chiral-glass transition.

  6. Many-body formation and dissociation of a dipolar chain crystal

    International Nuclear Information System (INIS)

    You, Jhih-Shih; Wang, Daw-Wei

    2014-01-01

    We propose an experimental scheme to effectively assemble chains of dipolar gases with a uniform length in a multi-layer system. The obtained dipolar chains can form a chain crystal with the system temperature easily controlled by the initial lattice potential and the external field strength during processing. When the density of chains increases, we further observe a second order quantum phase transition for the chain crystal to be dissociated toward layers of 2D crystal, where the quantum fluctuation dominates the classical energy and the compressibility diverges at the phase boundary. The experimental implication of such a dipolar chain crystal and its quantum phase transition is also discussed. (paper)

  7. Structures of Highly Twisted Amides Relevant to Amide N-C Cross-Coupling: Evidence for Ground-State Amide Destabilization.

    Science.gov (United States)

    Pace, Vittorio; Holzer, Wolfgang; Meng, Guangrong; Shi, Shicheng; Lalancette, Roger; Szostak, Roman; Szostak, Michal

    2016-10-04

    Herein, we show that acyclic amides that have recently enabled a series of elusive transition-metal-catalyzed N-C activation/cross-coupling reactions are highly twisted around the N-C(O) axis by a new destabilization mechanism of the amide bond. A unique effect of the N-glutarimide substituent, leading to uniformly high twist (ca. 90°) irrespective of the steric effect at the carbon side of the amide bond has been found. This represents the first example of a twisted amide that does not bear significant steric hindrance at the α-carbon atom. The (15) N NMR data show linear correlations between electron density at nitrogen and amide bond twist. This study strongly supports the concept of amide bond ground-state twist as a blueprint for activation of amides toward N-C bond cleavage. The new mechanism offers considerable opportunities for organic synthesis and biological processes involving non-planar amide bonds. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. An Efficient Amide-Aldehyde-Alkene Condensation: Synthesis for the N-Allyl Amides.

    Science.gov (United States)

    Quan, Zheng-Jun; Wang, Xi-Cun

    2016-02-01

    The allylamine skeleton represents a significant class of biologically active nitrogen compounds that are found in various natural products and drugs with well-recognized pharmacological properties. In this personal account, we will briefly discuss the synthesis of allylamine skeletons. We will focus on showing a general protocol for Lewis acid-catalyzed N-allylation of electron-poor N-heterocyclic amides and sulfonamide via an amide-aldehyde-alkene condensation reaction. The substrate scope with respect to N-heterocyclic amides, aldehydes, and alkenes will be discussed. This method is also capable of preparing the Naftifine motif from N-methyl-1-naphthamide or methyl (naphthalene-1-ylmethyl)carbamate, with paraformaldehyde and styrene in a one-pot manner. © 2016 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Luciferin Amides Enable in Vivo Bioluminescence Detection of Endogenous Fatty Acid Amide Hydrolase Activity.

    Science.gov (United States)

    Mofford, David M; Adams, Spencer T; Reddy, G S Kiran Kumar; Reddy, Gadarla Randheer; Miller, Stephen C

    2015-07-15

    Firefly luciferase is homologous to fatty acyl-CoA synthetases. We hypothesized that the firefly luciferase substrate d-luciferin and its analogs are fatty acid mimics that are ideally suited to probe the chemistry of enzymes that release fatty acid products. Here, we synthesized luciferin amides and found that these molecules are hydrolyzed to substrates for firefly luciferase by the enzyme fatty acid amide hydrolase (FAAH). In the presence of luciferase, these molecules enable highly sensitive and selective bioluminescent detection of FAAH activity in vitro, in live cells, and in vivo. The potency and tissue distribution of FAAH inhibitors can be imaged in live mice, and luciferin amides serve as exemplary reagents for greatly improved bioluminescence imaging in FAAH-expressing tissues such as the brain.

  10. Conversion of amides to esters by the nickel-catalysed activation of amide C-N bonds.

    Science.gov (United States)

    Hie, Liana; Fine Nathel, Noah F; Shah, Tejas K; Baker, Emma L; Hong, Xin; Yang, Yun-Fang; Liu, Peng; Houk, K N; Garg, Neil K

    2015-08-06

    Amides are common functional groups that have been studied for more than a century. They are the key building blocks of proteins and are present in a broad range of other natural and synthetic compounds. Amides are known to be poor electrophiles, which is typically attributed to the resonance stability of the amide bond. Although amides can readily be cleaved by enzymes such as proteases, it is difficult to selectively break the carbon-nitrogen bond of an amide using synthetic chemistry. Here we demonstrate that amide carbon-nitrogen bonds can be activated and cleaved using nickel catalysts. We use this methodology to convert amides to esters, which is a challenging and underdeveloped transformation. The reaction methodology proceeds under exceptionally mild reaction conditions, and avoids the use of a large excess of an alcohol nucleophile. Density functional theory calculations provide insight into the thermodynamics and catalytic cycle of the amide-to-ester transformation. Our results provide a way to harness amide functional groups as synthetic building blocks and are expected to lead to the further use of amides in the construction of carbon-heteroatom or carbon-carbon bonds using non-precious-metal catalysis.

  11. New Umami Amides: Structure-Taste Relationship Studies of Cinnamic Acid Derived Amides and the Natural Occurrence of an Intense Umami Amide in Zanthoxylum piperitum.

    Science.gov (United States)

    Frerot, Eric; Neirynck, Nathalie; Cayeux, Isabelle; Yuan, Yoyo Hui-Juan; Yuan, Yong-Ming

    2015-08-19

    A series of aromatic amides were synthesized from various acids and amines selected from naturally occurring structural frameworks. These synthetic amides were evaluated for umami taste in comparison with monosodium glutamate. The effect of the substitution pattern of both the acid and the amine parts on umami taste was investigated. The only intensely umami-tasting amides were those made from 3,4-dimethoxycinnamic acid. The amine part was more tolerant to structural changes. Amides bearing an alkyl- or alkoxy-substituted phenylethylamine residue displayed a clean umami taste as 20 ppm solutions in water. Ultraperformance liquid chromatography coupled with a high quadrupole-Orbitrap mass spectrometer (UPLC/MS) was subsequently used to show the natural occurrence of these amides. (E)-3-(3,4-Dimethoxyphenyl)-N-(4-methoxyphenethyl)acrylamide was shown to occur in the roots and stems of Zanthoxylum piperitum, a plant of the family Rutaceae growing in Korea, Japan, and China.

  12. Poly(ester-amide)s derived from PET containing uniform bisester amide segments

    OpenAIRE

    Ascanio Nuñez, Yanireth

    2013-01-01

    Poly(ethylene terephthalate) has experienced a growth in its demand as a bottle container and food packaging material. However, in order to expand its uses, its barrier properties to gases like carbon dioxide and oxygen, have to be improved. In this way, bisester amide units have been introduced as a third component in the main chain of PET, with the aim to reduce both CO2 and O2 permeability. In this project, poly(ester-amide)s based on PET (PETxMXy) have been synthesized, according to th...

  13. Synthesis of Nitriles via Palladium-Catalyzed Water Shuffling from Amides to Acetonitrile

    OpenAIRE

    Zhang, Wandi; Haskins, Christopher W.; Yang, Yang; Dai, Mingji

    2014-01-01

    Palladium-catalyzed synthesis of nitriles from amides has been described. Two similar, but complementary reaction conditions have been identified to convert various amides including α,β,γ,δ-unsaturated amides, cinnamides, aromatic amides and alkyl amides to the corresponding nitriles in good to excellent yield.

  14. Synthesis of nitriles via palladium-catalyzed water shuffling from amides to acetonitrile.

    Science.gov (United States)

    Zhang, Wandi; Haskins, Christopher W; Yang, Yang; Dai, Mingji

    2014-12-07

    Palladium-catalyzed synthesis of nitriles from amides has been described. Two similar, but complementary reaction conditions have been identified to convert various amides including α,β,γ,δ-unsaturated amides, cinnamides, aromatic amides and alkyl amides to the corresponding nitriles in good to excellent yield.

  15. Analytical applications of resins containing amide and polyamine functional groups

    International Nuclear Information System (INIS)

    Orf, G.M.

    1977-12-01

    A dibutyl amide resin is used for the separation of uranium(VI), thorium(IV), and zirconium(IV) from each other and several other metal ions. Uranium(VI) and thorium(IV) are determined in the presence of large excesses of foreign metal ions and anions. A practical application of the amide resin is studied by determining uranium in low grade uranium ores. The amide resin is also used for the selective concentration of gold(III) from sea water

  16. Analytical applications of resins containing amide and polyamine functional groups

    Energy Technology Data Exchange (ETDEWEB)

    Orf, Gene Michael [Iowa State Univ., Ames, IA (United States)

    1977-12-01

    A dibutyl amide resin is used for the separation of uranium(VI), thorium(IV), and zirconium(IV) from each other and several other metal ions. Uranium(VI) and thorium(IV) are determined in the presence of large excesses of foreign metal ions and anions. A practical application of the amide resin is studied by determining uranium in low grade uranium ores. The amide resin is also used for the selective concentration of gold(III) from sea water.

  17. Facile access to amides and hydroxamic acids directly from nitroarenes.

    Science.gov (United States)

    Jain, Shreyans K; Aravinda Kumar, K A; Bharate, Sandip B; Vishwakarma, Ram A

    2014-09-07

    A new method for synthesis of amides and hydroxamic acids from nitroarenes and aldehydes is described. The MnO2 catalyzed thermal deoxygenation of nitrobenzene resulted in formation of a reactive nitroso intermediate which on reaction with aldehydes provided amides and hydroxamic acids. The thermal neat reaction in the presence of 0.01 mmol KOH predominantly led to formation of hydroxamic acid whereas reaction in the presence of 1 mmol acetic acid produced amides as the only product.

  18. Regio- and stereochemistry of 1,3-dipolar cycloaddition of nitrile oxides to alkenes

    International Nuclear Information System (INIS)

    Litvinovskaya, Raisa P; Khripach, Vladimir A

    2001-01-01

    The published data on the chemistry of intermolecular 1,3-dipolar cycloaddition of nitrile oxides to different types of alkene derivatives are systematised. Various aspects of stereo- and regiochemistry of this reaction are considered. The bibliography includes 182 references.

  19. Structures and dynamics in a two-dimensional dipolar dust particle system

    Science.gov (United States)

    Hou, X. N.; Liu, Y. H.; Kravchenko, O. V.; Lapushkina, T. A.; Azarova, O. A.; Chen, Z. Y.; Huang, F.

    2018-05-01

    The effects of electric dipole moment, the number of dipolar particles, and system temperature on the structures and dynamics of a dipolar dust particle system are studied by molecular dynamics simulations. The results show that the larger electric dipole moment is favorable for the formation of a long-chain structure, the larger number of dipolar dust particles promotes the formation of the multi-chain structure, and the higher system temperature can cause higher rotation frequency. The trajectories, mean square displacement (MSD), and the corresponding spectrum functions of the MSDs are also calculated to illustrate the dynamics of the dipolar dust particle system, which is also closely related to the growth of dust particles. Some simulations are qualitatively in agreement with our experiments and can provide a guide for the study on dust growth, especially on the large-sized particles.

  20. Cluster-cluster aggregation of Ising dipolar particles under thermal noise

    KAUST Repository

    Suzuki, Masaru; Kun, Ferenc; Ito, Nobuyasu

    2009-01-01

    The cluster-cluster aggregation processes of Ising dipolar particles under thermal noise are investigated in the dilute condition. As the temperature increases, changes in the typical structures of clusters are observed from chainlike (D1

  1. Electrochemical reduction of nitrate in the presence of an amide

    Science.gov (United States)

    Dziewinski, Jacek J.; Marczak, Stanislaw

    2002-01-01

    The electrochemical reduction of nitrates in aqueous solutions thereof in the presence of amides to gaseous nitrogen (N.sub.2) is described. Generally, electrochemical reduction of NO.sub.3 proceeds stepwise, from NO.sub.3 to N.sub.2, and subsequently in several consecutive steps to ammonia (NH.sub.3) as a final product. Addition of at least one amide to the solution being electrolyzed suppresses ammonia generation, since suitable amides react with NO.sub.2 to generate N.sub.2. This permits nitrate reduction to gaseous nitrogen to proceed by electrolysis. Suitable amides include urea, sulfamic acid, formamide, and acetamide.

  2. SOLID-PHASE PEPTIDE SYNTHESIS OF ISOTOCIN WITH AMIDE ...

    African Journals Online (AJOL)

    SOLID-PHASE PEPTIDE SYNTHESIS OF ISOTOCIN WITH AMIDE OF ASPARAGINE PROTECTED WITH 1-TETRALINYL. TRIFLUOROMETHANESULPHONIC ACID (TFMSA) DEPROTECTION, CLEAVAGE AND AIR OXIDATION OF MERCAPTO GROUPS TO DISULPHIDE.

  3. The phase transition in the anisotropic Heisenberg model with long range dipolar interactions

    International Nuclear Information System (INIS)

    Mól, L.A.S.; Costa, B.V.

    2014-01-01

    In this work we have used extensive Monte Carlo calculations to study the planar to paramagnetic phase transition in the two-dimensional anisotropic Heisenberg model with dipolar interactions (AHd) considering the true long-range character of the dipolar interactions by means of the Ewald summation. Our results are consistent with an order–disorder phase transition with unusual critical exponents in agreement with our previous results for the Planar Rotator model with dipolar interactions. Nevertheless, our results disagree with the Renormalization Group results of Maier and Schwabl [Phys. Rev. B, 70, 134430 (2004)] [13] and the results of Rapini et al. [Phys. Rev. B, 75, 014425 (2007)] [12], where the AHd was studied using a cut-off in the evaluation of the dipolar interactions. We argue that besides the long-range character of dipolar interactions their anisotropic character may have a deeper effect in the system than previously believed. Besides, our results show that the use of a cut-off radius in the evaluation of dipolar interactions must be avoided when analyzing the critical behavior of magnetic systems, since it may lead to erroneous results. - Highlights: • The anisotropic Heisenberg model with dipolar interactions is studied. • True long-range interactions were considered by means of Ewald summation. • We found an order–disorder phase transition with unusual critical exponents. • Previous results show a different behavior when a cut-off radius is introduced. • The use of a cut-off radius must be avoided when dealing with dipolar systems

  4. Statistical mechanics of molecular fluids. The RHNC theory applied to hard dipolar spheres

    International Nuclear Information System (INIS)

    Lombardero, M.; Lado, F.; Abascal, J.L.F.; Lago, S.; Enciso, E.

    1988-01-01

    The RHNC (reference hipernetted chain) equation, together with an optimization criterion which extremalizes the Helmholtz free energy, is used to obtain structural, thermodynamic, and dielectric properties of a system made up of hard dipolar spheres. The comparison with simulation results is made in the same boundary conditions and then the properties of an infinite system are evaluated for a variaty of states at different densities and dipolar moments. (Author)

  5. Energetic electron injections and dipolarization events in Mercury's magnetotail: Substorm dynamics

    Science.gov (United States)

    Dewey, R. M.; Slavin, J. A.; Raines, J. M.; Imber, S.; Baker, D. N.; Lawrence, D. J.

    2017-12-01

    Despite its small size, Mercury's terrestrial-like magnetosphere experiences brief, yet intense, substorm intervals characterized by features similar to at Earth: loading/unloading of the tail lobes with open magnetic flux, dipolarization of the magnetic field at the inner edge of the plasma sheet, and, the focus of this presentation, energetic electron injection. We use the Gamma-Ray Spectrometer's high-time resolution (10 ms) energetic electron measurements to determine the relationship between substorm activity and energetic electron injections coincident with dipolarization fronts in the magnetotail. These dipolarizations were detected on the basis of their rapid ( 2 s) increase in the northward component of the tail magnetic field (ΔBz 30 nT), which typically persists for 10 s. We estimate the typical flow channel to be 0.15 RM, planetary convection speed of 750 km/s, cross-tail potential drop of 7 kV, and flux transport of 0.08 MWb for each dipolarization event, suggesting multiple simultaneous and sequential dipolarizations are required to unload the >1 MWb of magnetic flux typically returned to the dayside magnetosphere during a substorm interval. Indeed, while we observe most dipolarization-injections to be isolated or in small chains of events (i.e., 1-3 events), intervals of sawtooth-like injections with >20 sequential events are also present. The typical separation between dipolarization-injection events is 10 s. Magnetotail dipolarization, in addition to being a powerful source of electron acceleration, also plays a significant role in the substorm process at Mercury.

  6. AC susceptibility as a tool to probe the dipolar interaction in magnetic nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Landi, Gabriel T., E-mail: gtlandi@gmail.com [Universidade Federal do ABC, 09210-580 Santo André (Brazil); Arantes, Fabiana R. [Universidade Federal do ABC, 09210-580 Santo André (Brazil); Cornejo, Daniel R. [Instituto de Física da Universidade de São Paulo, São Paulo 05508-090 (Brazil); Bakuzis, Andris F. [Instituto de Física, Universidade Federal de Goiás, 74690-900 Goiânia-GO (Brazil); Andreu, Irene; Natividad, Eva [Instituto de Ciencia de Materiales de Aragón (ICMA), CSIC-Universidad de Zaragoza, Zaragoza 50018 (Spain)

    2017-01-01

    The dipolar interaction is known to substantially affect the properties of magnetic nanoparticles. This is particularly important when the particles are kept in a fluid suspension or packed within nano-carriers. In addition to its usual long-range nature, in these cases the dipolar interaction may also induce the formation of clusters of particles, thereby strongly modifying their magnetic anisotropies. In this paper we show how AC susceptibility may be used to obtain information regarding the influence of the dipolar interaction in a sample. We develop a model which includes both aspects of the dipolar interaction and may be fitted directly to the susceptibility data. The usual long-range nature of the interaction is implemented using a mean-field approximation, whereas the particle-particle aggregation is modeled using a distribution of anisotropy constants. The model is then applied to two samples studied at different concentrations. One consists of spherical magnetite nanoparticles dispersed in oil and the other of cubic magnetite nanoparticles embedded on polymeric nanospheres. We also introduce a simple technique to address the presence of the dipolar interaction in a given sample, based on the height of the AC susceptibility peaks for different driving frequencies. - Highlights: We discuss the importance of the dipolar interaction in magnetic nanoparticle samples. It is shown that AC susceptibility may be used to estimate the extent of this interaction. We develop a model that accounts for particle aggregation. The theoretical model is then fitted to distinct magnetite samples.

  7. Controlling residual dipolar couplings in high-resolution NMR of proteins by strain induced alignment in a gel

    International Nuclear Information System (INIS)

    Ishii, Yoshitaka; Markus, Michelle A.; Tycko, Robert

    2001-01-01

    Water-soluble biological macromolecules can be weakly aligned by dissolution in a strained, hydrated gel such as cross-linked polyacrylamide, an effect termed 'strain-induced alignment in a gel' (SAG). SAG induces nonzero nuclear magnetic dipole-dipole couplings that can be measured in high-resolution NMR spectra and used as structural constraints. The dependence of experimental 15 N- 1 H dipolar couplings extracted from two-dimensional heteronuclear single quantum coherence (HSQC) spectra on several properties of compressed polyacrylamide, including the extent of compression, the polyacrylamide concentration, and the cross-link density, is reported for the B1 immunoglobulin binding domain of streptococcal protein G (protein G/B1, 57 residues). It is shown that the magnitude of macromolecular alignment can be widely varied by adjusting these properties, although the orientation and asymmetry of the alignment tensor are not affected significantly. The dependence of the 15 N relaxation times T 1 and T 2 of protein G/B1 on polyacrylamide concentration are also reported. In addition, the results of 15 N relaxation and HSQC experiments on the RNA binding domain of prokaryotic protein S4 from Bacillus stearothermophilus (S4 Δ41, residues 43-200) in a compressed polyacrylamide gel are presented. These results demonstrate the applicability of SAG to proteins of higher molecular weight and greater complexity. A modified in-phase/anti-phase (IPAP) HSQC technique is described that suppresses natural-abundance 15 N background signals from amide groups in polyacrylamide, resulting in cleaner HSQC spectra in SAG experiments. The mechanism of protein alignment in strained polyacrylamide gels is contrasted with that in liquid crystalline media

  8. Reaction mechanism of the acidic hydrolysis of highly twisted amides: Rate acceleration caused by the twist of the amide bond.

    Science.gov (United States)

    Mujika, Jon I; Formoso, Elena; Mercero, Jose M; Lopez, Xabier

    2006-08-03

    We present an ab initio study of the acid hydrolysis of a highly twisted amide and a planar amide analogue. The aim of these studies is to investigate the effect that the twist of the amide bond has on the reaction barriers and mechanism of acid hydrolysis. Concerted and stepwise mechanisms were investigated using density functional theory and polarizable continuum model calculations. Remarkable differences were observed between the mechanism of twisted and planar amide, due mainly to the preference for N-protonation of the former and O-protonation of the latter. In addition, we were also able to determine that the hydrolytic mechanism of the twisted amide will be pH dependent. Thus, there is a preference for a stepwise mechanism with formation of an intermediate in the acid hydrolysis, whereas the neutral hydrolysis undergoes a concerted-type mechanism. There is a nice agreement between the characterized intermediate and available X-ray data and a good agreement with the kinetically estimated rate acceleration of hydrolysis with respect to analogous undistorted amide compounds. This work, along with previous ab initio calculations, describes a complex and rich chemistry for the hydrolysis of highly twisted amides as a function of pH. The theoretical data provided will allow for a better understanding of the available kinetic data of the rate acceleration of amides upon twisting and the relation of the observed rate acceleration with intrinsic differential reactivity upon loss of amide bond resonance.

  9. Conversion of Amides to Esters by the Nickel-Catalyzed Activation of Amide C–N Bonds

    Science.gov (United States)

    Hie, Liana; Fine Nathel, Noah F.; Shah, Tejas K.; Baker, Emma L.; Hong, Xin; Yang, Yun-Fang; Liu, Peng; Houk, K. N.; Garg, Neil K.

    2015-01-01

    Amides are common functional groups that have been well studied for more than a century.1 They serve as the key building blocks of proteins and are present in an broad range of other natural and synthetic compounds. Amides are known to be poor electrophiles, which is typically attributed to resonance stability of the amide bond.1,2 Whereas Nature can easily cleave amides through the action of enzymes, such as proteases,3 the ability to selectively break the C–N bond of an amide using synthetic chemistry is quite difficult. In this manuscript, we demonstrate that amide C–N bonds can be activated and cleaved using nickel catalysts. We have used this methodology to convert amides to esters, which is a challenging and underdeveloped transformation. The reaction methodology proceeds under exceptionally mild reaction conditions, and avoids the use of a large excess of an alcohol nucleophile. Density functional theory (DFT) calculations provide insight into the thermodynamics and catalytic cycle of this unusual transformation. Our results provide a new strategy to harness amide functional groups as synthons and are expected fuel the further use of amides for the construction of carbon–heteroatom or carbon–carbon bonds using non-precious metal catalysis. PMID:26200342

  10. New Developments in Spin Labels for Pulsed Dipolar EPR

    Directory of Open Access Journals (Sweden)

    Alistair J. Fielding

    2014-10-01

    Full Text Available Spin labelling is a chemical technique that enables the integration of a molecule containing an unpaired electron into another framework for study. Given the need to understand the structure, dynamics, and conformational changes of biomacromolecules, spin labelling provides a relatively non-intrusive technique and has certain advantages over X-ray crystallography; which requires high quality crystals. The technique relies on the design of binding probes that target a functional group, for example, the thiol group of a cysteine residue within a protein. The unpaired electron is typically supplied through a nitroxide radical and sterically shielded to preserve stability. Pulsed electron paramagnetic resonance (EPR techniques allow small magnetic couplings to be measured (e.g., <50 MHz providing information on single label probes or the dipolar coupling between multiple labels. In particular, distances between spin labels pairs can be derived which has led to many protein/enzymes and nucleotides being studied. Here, we summarise recent examples of spin labels used for pulse EPR that serve to illustrate the contribution of chemistry to advancing discoveries in this field.

  11. Testing physical models for dipolar asymmetry with CMB polarization

    Science.gov (United States)

    Contreras, D.; Zibin, J. P.; Scott, D.; Banday, A. J.; Górski, K. M.

    2017-12-01

    The cosmic microwave background (CMB) temperature anisotropies exhibit a large-scale dipolar power asymmetry. To determine whether this is due to a real, physical modulation or is simply a large statistical fluctuation requires the measurement of new modes. Here we forecast how well CMB polarization data from Planck and future experiments will be able to confirm or constrain physical models for modulation. Fitting several such models to the Planck temperature data allows us to provide predictions for polarization asymmetry. While for some models and parameters Planck polarization will decrease error bars on the modulation amplitude by only a small percentage, we show, importantly, that cosmic-variance-limited (and in some cases even Planck) polarization data can decrease the errors by considerably better than the expectation of √{2 } based on simple ℓ-space arguments. We project that if the primordial fluctuations are truly modulated (with parameters as indicated by Planck temperature data) then Planck will be able to make a 2 σ detection of the modulation model with 20%-75% probability, increasing to 45%-99% when cosmic-variance-limited polarization is considered. We stress that these results are quite model dependent. Cosmic variance in temperature is important: combining statistically isotropic polarization with temperature data will spuriously increase the significance of the temperature signal with 30% probability for Planck.

  12. Phase transitions in random uniaxial systems with dipolar interactions

    International Nuclear Information System (INIS)

    Schuster, H.G.

    1977-01-01

    The critical behaviour of random uniaxial ferromagnetic (ferroelectric) systems with both short range and long range dipolar interactions is investigated, using the field theoretic renormalization method of Brezin et al. for the free energy above and below transition point Tsub(c). The randomness is due to externally introduced fluctuations in the short range interactions (quenched case) or (and) magneto-elastic coupling to the lattice (annealed case). Strong deviations in the critical behaviour with respect to the pure systems are found. In the quenched case, e.g., the specific heat C and the coefficient f 2 (of M 3 in the equation of state, where M is the magnetization) change from C proportional to abs ln abs t abs abssup(1/3), f 2 proportional to abs ln abs t abs abs sup(1/3), f 2 proportional to abs ln abs t abs abs -1 in the pure system to C = A+- + C+-exp[-4√ 3 106 abs ln abs t abs abs], f 2 proportional to abs ln abs t abs abs sup(-1/2) (where t = (T-Tsub(c)) / Tsub(c) is the reduced temperature and A+-, C+- are constants) in the random situation. (orig.) [de

  13. Focal mechanism of seismic events with a dipolar component

    Directory of Open Access Journals (Sweden)

    R. Console

    1995-06-01

    Full Text Available In this paper we model the geometry of a seismic source as a dislocation occurring on an elemental flat fault in an arbitrary direction with respect to the fault plane. This implies the use of a fourth parameter in addition to the three usual ones describing a simple double couple mechanism. We applied the radiation pattern obtained from the theory to a computer code written for the inversion of the observation data (amplitudes and polarities of the first onsets recorded by a network of stations. It allows the determination of the fault mechanism gener- alized in the above mentioned way. The computer code was verified on synthetic data and then applied to real data recorded by the seismic network operated by the Ente Nazionale per l'Energia Elettrica (ENEL, monitoring the geothermal field of Larderello. The experimental data show that for some events the source mechanism exhibits a significant dipolar component. However, due to the high standard deviation of the amplitude data, F-test applied to the results of the analysis shows that only for two events the confidence level for the general- ized model exceeds 90%.

  14. Classical and quantum phases of low-dimensional dipolar systems

    Energy Technology Data Exchange (ETDEWEB)

    Cartarius, Florian

    2016-09-22

    In this thesis we present a detailed study of the phase diagram of ultracold bosonic atoms confined along a tight atomic wave guide, along which they experience an optical lattice potential. In this quasi-one dimensional model we analyse the interplay between interactions and quantum fluctuations in (i) determining the non-equilibrium steady state after a quench and (ii) giving rise to novel equilibrium phases, when the interactions combine the s-wave contact interaction and the anisotropic long range dipole-dipole interactions. In detail, in the first part of the thesis we study the depinning of a gas of impenetrable bosons following the sudden switch of of the optical lattice. By means of a Bose-Fermi mapping we infer the exact quantum dynamical evolution and show that in the thermodynamic limit the system is in a non-equilibrium steady state without quasi-long range order. In the second part of the thesis, we study the effect of quantum fluctuations on the linear-zigzag instability in the ground state of ultracold dipolar bosons, as a function of the strength of the transverse confinement. We first analyse the linear-zigzag instability in the classical regime, and then use our results to develop a multi-mode Bose-Hubbard model for the system. We then develop several numerical methods, to determine the ground state.

  15. Photoinduced gelation by stilbene oxalyl amide compounds.

    Science.gov (United States)

    Miljanić, Snezana; Frkanec, Leo; Meić, Zlatko; Zinić, Mladen

    2005-03-29

    Oxalyl amide derivatives bearing 4-dodecyloxy-stilbene as a cis-trans photoisomerizing unit were synthesized. The trans derivative acted as a versatile gelator of various organic solvents, whereas the corresponding cis derivative showed a poor gelation ability or none at all. In diluted solution (c = 2.0 x10(-5) mol dm(-3), ethanol), the cis isomer was photochemically converted into the trans isomer within 4 min. Depending on the radiation wavelength, the trans isomer was stable or liable to photodecomposition. When exposed to irradiation, a concentrated solution of the cis isomer (c = 2.0 x 10(-2) mol dm(-3), ethanol) turned into a gel. The FT-Raman, FT-IR, and 1H NMR spectra demonstrated that the gelation process occurred because of a rapid cis --> trans photoisomerization followed by a self-assembly of the trans molecules. Apart from the formation of hydrogen bonding between the oxalyl amide parts of the molecules, confirmed by FT-IR spectroscopy, it was assumed that the pi-pi stacking between the trans-stilbene units of the molecule and a lipophilic interaction between long alkyl chains were the interactions responsible for gelation.

  16. Amide-N-oxide heterosynthon and amide dimer homosynthon in cocrystals of carboxamide drugs and pyridine N-oxides.

    Science.gov (United States)

    Babu, N Jagadeesh; Reddy, L Sreenivas; Nangia, Ashwini

    2007-01-01

    The carboxamide-pyridine N-oxide heterosynthon is sustained by syn(amide)N-H...O-(oxide) hydrogen bond and auxiliary (N-oxide)C-H...O(amide) interaction (Reddy, L. S.; Babu, N. J.; Nangia, A. Chem. Commun. 2006, 1369). We evaluate the scope and utility of this heterosynthon in amide-containing molecules and drugs (active pharmaceutical ingredients, APIs) with pyridine N-oxide cocrystal former molecules (CCFs). Out of 10 cocrystals in this study and 7 complexes from previous work, amide-N-oxide heterosynthon is present in 12 structures and amide dimer homosynthon occurs in 5 structures. The amide dimer is favored over amide-N-oxide synthon in cocrystals when there is competition from another H-bonding functional group, e.g., 4-hydroxybenzamide, or because of steric factors, as in carbamazepine API. The molecular organization in carbamazepine.quinoxaline N,N'-dioxide 1:1 cocrystal structure is directed by amide homodimer and anti(amide)N-H...O-(oxide) hydrogen bond. Its X-ray crystal structure matches with the third lowest energy frame calculated in Polymorph Predictor (Cerius(2), COMPASS force field). Apart from generating new and diverse supramolecular structures, hydration is controlled in one substance. 4-Picoline N-oxide deliquesces within a day, but its cocrystal with barbital does not absorb moisture at 50% RH and 30 degrees C up to four weeks. Amide-N-oxide heterosynthon has potential utility in both amide and N-oxide type drug molecules with complementary CCFs. Its occurrence probability in the Cambridge Structural Database is 87% among 27 structures without competing acceptors and 78% in 41 structures containing OH, NH, H(2)O functional groups.

  17. Fatty acid amides from freshwater green alga Rhizoclonium hieroglyphicum.

    Science.gov (United States)

    Dembitsky, V M; Shkrob, I; Rozentsvet, O A

    2000-08-01

    Freshwater green algae Rhizoclonium hieroglyphicum growing in the Ural Mountains were examined for their fatty acid amides using capillary gas chromatography-mass spectrometry (GC-MS). Eight fatty acid amides were identified by GC-MS. (Z)-9-octadecenamide was found to be the major component (2.26%).

  18. Oxidative activation of dihydropyridine amides to reactive acyl donors

    DEFF Research Database (Denmark)

    Funder, Erik Daa; Trads, Julie Brender; Gothelf, Kurt Vesterager

    2015-01-01

    Amides of 1,4-dihydropyridine (DHP) are activated by oxidation for acyl transfer to amines, alcohols and thiols. In the reduced form the DHP amide is stable towards reaction with amines at room temperature. However, upon oxidation with DDQ the acyl donor is activated via a proposed pyridinium...

  19. Cytotoxic Amides from Fruits of Kawakawa, Macropiper excelsum.

    Science.gov (United States)

    Lei, Jeremy; Burgess, Elaine J; Richardson, Alistair T B; Hawkins, Bill C; Baird, Sarah K; Smallfield, Bruce M; van Klink, John W; Perry, Nigel B

    2015-08-01

    Cytotoxic amides have been isolated from the fruits of the endemic New Zealand medicinal plant kawakawa, Macropiper excelsum (Piperaceae). The main amide was piperchabamide A and this is the first report of this rare compound outside the genus Piper. Eleven other amides were purified including two new compounds with the unusual 3,4-dihydro-1(2H)-pyridinyl group. The new compounds were fully characterized by 2D NMR spectroscopy, which showed a slow exchange between two rotamers about the amide bond, and they were chemically synthesized. In view of the antitumor activity of the related piperlongumine, all of these amides plus four synthetic analogs were tested for cytotoxicity. The most active was the piperine homolog piperdardine, with an IC50 of 14 µM against HT 29 colon cancer cells. Georg Thieme Verlag KG Stuttgart · New York.

  20. Biosynthesis and function of simple amides in Xenorhabdus doucetiae.

    Science.gov (United States)

    Bode, Edna; He, Yue; Vo, Tien Duy; Schultz, Roland; Kaiser, Marcel; Bode, Helge B

    2017-11-01

    Xenorhabdus doucetiae, the bacterial symbiont of the entomopathogenic nematode Steinernema diaprepesi produces several different fatty acid amides. Their biosynthesis has been studied using a combination of analysis of gene deletions and promoter exchanges in X. doucetiae and heterologous expression of candidate genes in E. coli. While a decarboxylase is required for the formation of all observed phenylethylamides and tryptamides, the acyltransferase XrdE encoded in the xenorhabdin biosynthesis gene cluster is responsible for the formation of short chain acyl amides. Additionally, new, long-chain and cytotoxic acyl amides were identified in X. doucetiae infected insects and when X. doucetiae was grown in Galleria Instant Broth (GIB). When the bioactivity of selected amides was tested, a quorum sensing modulating activity was observed for the short chain acyl amides against the two different quorum sensing systems from Chromobacterium and Janthinobacterium. © 2017 Society for Applied Microbiology and John Wiley & Sons Ltd.

  1. Response of energetic particles to local magnetic dipolarization inside geosynchronous orbit

    Science.gov (United States)

    Motoba, T.; Ohtani, S.; Gkioulidou, M.; Takahashi, K.

    2017-12-01

    Magnetic field dipolarization and energetic particle injections are the most distinct phenomena observed in the inner magnetosphere during the substorm expansion phase. Compared to a wealth of knowledge about the phenomenology of magnetic dipolarizations and particle injections at/outside geosynchronous orbit (GEO), our understanding of them inside GEO remains incomplete because of a very limited number of previous studies. In the present study, we statistically examine the response of 1-1000 keV energetic particles to local magnetic dipolarization by performing a superposed epoch analysis of energetic particle fluxes with the zero epoch defined as the dipolarization onset times. Based on data from the Van Allen Probes tail seasons in 2012-2016, we identified a total of 97 magnetic dipolarization events which occurred closer to the magnetic equator (i.e., BH, which is antiparallel to the Earth's dipole axis, is the dominant component of the local magnetic field at least for 5 min before the onset). For major ion species (hydrogen, helium, and oxygen ions), the relative flux intensity to the pre-onset level increases at > 50 keV and decreases at inverse energy dispersion. For dipolarizations with strong impulsive westward electric fields, the relative electron flux intensity increases up to 5-10 times, in particular most significant at several tens of keV. This result suggests that the impulsive electric field acts as an efficient factor in the rapid energization of the tens-of-keV electrons. We also discuss how the response of energetic particles to dipolarization depends on MLT, radial distance, and pitch angle.

  2. Amide proton temperature coefficients as hydrogen bond indicators in proteins

    International Nuclear Information System (INIS)

    Cierpicki, Tomasz; Otlewski, Jacek

    2001-01-01

    Correlations between amide proton temperature coefficients (Δσ HN /ΔT) and hydrogen bonds were investigated for a data set of 793 amides derived from 14 proteins. For amide protons showing temperature gradients more positive than -4.6 ppb/K there is a hydrogen bond predictivity value exceeding 85%. It increases to over 93% for amides within the range between -4 and -1 ppb/K. Detailed analysis shows an inverse proportionality between amide proton temperature coefficients and hydrogen bond lengths. Furthermore, for hydrogen bonds of similar bond lengths, values of temperature gradients in α-helices are on average 1 ppb/K more negative than in β-sheets. In consequence, a number of amide protons in α-helices involved in hydrogen bonds shorter than 2 A show Δσ HN /ΔT 10 helices and 98% in β-turns have temperature coefficients more positive than -4.6ppb/K. Ring current effect also significantly influences temperature coefficients of amide protons. In seven out of eight cases non-hydrogen bonded amides strongly deshielded by neighboring aromatic rings show temperature coefficients more positive than -2 ppb/K. In general, amide proton temperature gradients do not change with pH unless they correspond to conformational changes. Three examples of pH dependent equilibrium showing hydrogen bond formation at higher pH were found. In conclusion, amide proton temperature coefficients offer an attractive and simple way to confirm existence of hydrogen bonds in NMR determined structures

  3. Amide to Alkyne Interconversion via a Nickel/Copper-Catalyzed Deamidative Cross-Coupling of Aryl and Alkenyl Amides

    KAUST Repository

    Srimontree, Watchara

    2017-06-05

    A nickel-catalyzed deamidative cross-coupling reaction of amides with terminal alkynes as coupling partners was disclosed. This newly developed methodology allows the direct interconversion of amides to alkynes and enables a facile route for C(sp2)-C(sp) bond formation in a straightforward and mild fashion.

  4. Amide to Alkyne Interconversion via a Nickel/Copper-Catalyzed Deamidative Cross-Coupling of Aryl and Alkenyl Amides.

    Science.gov (United States)

    Srimontree, Watchara; Chatupheeraphat, Adisak; Liao, Hsuan-Hung; Rueping, Magnus

    2017-06-16

    A nickel-catalyzed deamidative cross-coupling reaction of amides with terminal alkynes as coupling partners was disclosed. This newly developed methodology allows the direct interconversion of amides to alkynes and enables a facile route for C(sp2)-C(sp) bond formation in a straightforward and mild fashion.

  5. Amide to Alkyne Interconversion via a Nickel/Copper-Catalyzed Deamidative Cross-Coupling of Aryl and Alkenyl Amides

    KAUST Repository

    Srimontree, Watchara; Chatupheeraphat, Adisak; Liao, Hsuan-Hung; Rueping, Magnus

    2017-01-01

    A nickel-catalyzed deamidative cross-coupling reaction of amides with terminal alkynes as coupling partners was disclosed. This newly developed methodology allows the direct interconversion of amides to alkynes and enables a facile route for C(sp2)-C(sp) bond formation in a straightforward and mild fashion.

  6. Understanding the anisotropic ion distributions within magnetotail dipolarizing flux bundles

    Science.gov (United States)

    Zhou, X.; Runov, A.; Angelopoulos, V.; Birn, J.

    2017-12-01

    Dipolarizing flux bundles (DFBs), earthward-propagating structures with enhanced northward magnetic field (Bz) component, are usually believed to carry a different plasma population from that in the ambient magnetotail plasma sheet. The ion distribution functions within the DFB, however, are recently found to be largely controlled by the ion adiabaticity parameter κ in the ambient plasma sheet outside the DFBs. According to these observations, the ambient κ values of 2-3 usually correspond to a strong perpendicular anisotropy of suprathermal ions within the DFBs, whereas for lower κ values the ions inside the DFBs become more isotropic. Here we utilize a simple, test-particle model to explore the nature of the anisotropy and its dependence on the ambient κ values. We find that the ion anisotropy originates from successive ion reflections and reentries to the DFBs, during which the ions can be consecutively accelerated in the perpendicular direction by the DFB-carried electric field. This acceleration process may be interrupted, however, when the magnetic field lines are highly curved in the ambient plasma sheet. In this case, the ion trajectories are most stochastic outside the DFB region, which makes the reflected ions less likely to return to the DFBs for another cycle of acceleration; as a consequence, the perpendicular ion anisotropy does not appear. Given that the DFB ions are a free energy source for instabilities when they are injected towards Earth, our simple model (that reproduces most observational features on the anisotropic DFB ion distributions) may shed new lights on the coupling process between the magnetotail and the inner magneosphere.

  7. Physics of Substorm Growth Phase, Onset, and Dipolarization

    Energy Technology Data Exchange (ETDEWEB)

    C.Z. Cheng

    2003-10-22

    A new scenario of substorm growth phase, onset, and depolarization during expansion phase and the corresponding physical processes are presented. During the growth phase, as a result of enhanced plasma convection, the plasma pressure and its gradient are continued to be enhanced over the quiet-time values in the plasma sheet. Toward the late growth phase, a strong cross-tail current sheet is formed in the near-Earth plasma sheet region, where a local magnetic well is formed, the plasma beta can reach a local maximum with value larger than 50 and the cross-tail current density can be enhanced to over 10nA/m{sup 2} as obtained from 3D quasi-static magnetospheric equilibrium solutions for the growth phase. The most unstable kinetic ballooning instabilities (KBI) are expected to be located in the tailward side of the strong cross-tail current sheet region. The field lines in the most unstable KBI region map to the transition region between the region-1 and region-2 currents in the ionosphere, which is consistent with the observed initial brightening location of the breakup arc in the intense proton precipitation region. The KBI explains the AMPTE/CCE observations that a low-frequency instability with a wave period of 50-75 seconds is excited about 2-3 minutes prior to substorm onset and grows exponentially to a large amplitude at the onset of current disruption (or current reduction). At the current disruption onset higher frequency instabilities are excited so that the plasma and electromagnetic field fluctuations form a strong turbulent state. Plasma transport takes place due to the strong turbulence to relax the ambient plasma pressure profile so that the plasma pressure and current density are reduced and the ambient magnetic field intensity increases by more than a factor of 2 in the high-beta(sub)eq region and the field line geometry recovers from tail-like to dipole-like dipolarization.

  8. Physics of Substorm Growth Phase, Onset, and Dipolarization

    International Nuclear Information System (INIS)

    Cheng, C.Z.

    2003-01-01

    A new scenario of substorm growth phase, onset, and depolarization during expansion phase and the corresponding physical processes are presented. During the growth phase, as a result of enhanced plasma convection, the plasma pressure and its gradient are continued to be enhanced over the quiet-time values in the plasma sheet. Toward the late growth phase, a strong cross-tail current sheet is formed in the near-Earth plasma sheet region, where a local magnetic well is formed, the plasma beta can reach a local maximum with value larger than 50 and the cross-tail current density can be enhanced to over 10nA/m 2 as obtained from 3D quasi-static magnetospheric equilibrium solutions for the growth phase. The most unstable kinetic ballooning instabilities (KBI) are expected to be located in the tailward side of the strong cross-tail current sheet region. The field lines in the most unstable KBI region map to the transition region between the region-1 and region-2 currents in the ionosphere, which is consistent with the observed initial brightening location of the breakup arc in the intense proton precipitation region. The KBI explains the AMPTE/CCE observations that a low-frequency instability with a wave period of 50-75 seconds is excited about 2-3 minutes prior to substorm onset and grows exponentially to a large amplitude at the onset of current disruption (or current reduction). At the current disruption onset higher frequency instabilities are excited so that the plasma and electromagnetic field fluctuations form a strong turbulent state. Plasma transport takes place due to the strong turbulence to relax the ambient plasma pressure profile so that the plasma pressure and current density are reduced and the ambient magnetic field intensity increases by more than a factor of 2 in the high-beta(sub)eq region and the field line geometry recovers from tail-like to dipole-like dipolarization

  9. Hepatoprotective amide constituents from the fruit of Piper chaba: Structural requirements, mode of action, and new amides.

    Science.gov (United States)

    Matsuda, Hisashi; Ninomiya, Kiyofumi; Morikawa, Toshio; Yasuda, Daisuke; Yamaguchi, Itadaki; Yoshikawa, Masayuki

    2009-10-15

    The 80% aqueous acetone extract from the fruit of Piper chaba (Piperaceae) was found to have hepatoprotective effects on D-galactosamine (D-GalN)/lipopolysaccharide-induced liver injury in mice. From the ethyl acetate-soluble fraction, three new amides, piperchabamides E, G, and H, 33 amides, and four aromatic constituents were isolated. Among the isolates, several amide constituents inhibited D-GalN/tumor necrosis factor-alpha (TNF-alpha)-induced death of hepatocytes, and the following structural requirements were suggested: (i) the amide moiety is essential for potent activity; and (ii) the 1,9-decadiene structure between the benzene ring and the amide moiety tended to enhance the activity. Moreover, a principal constituent, piperine, exhibited strong in vivo hepatoprotective effects at doses of 5 and 10 mg/kg, po and its mode of action was suggested to depend on the reduced sensitivity of hepatocytes to TNF-alpha.

  10. Structural Characterization of N-Alkylated Twisted Amides: Consequences for Amide Bond Resonance and N-C Cleavage.

    Science.gov (United States)

    Hu, Feng; Lalancette, Roger; Szostak, Michal

    2016-04-11

    Herein, we describe the first structural characterization of N-alkylated twisted amides prepared directly by N-alkylation of the corresponding non-planar lactams. This study provides the first experimental evidence that N-alkylation results in a dramatic increase of non-planarity around the amide N-C(O) bond. Moreover, we report a rare example of a molecular wire supported by the same amide C=O-Ag bonds. Reactivity studies demonstrate rapid nucleophilic addition to the N-C(O) moiety of N-alkylated amides, indicating the lack of n(N) to π*(C=O) conjugation. Most crucially, we demonstrate that N-alkylation activates the otherwise unreactive amide bond towards σ N-C cleavage by switchable coordination. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Cytotoxic cassaine diterpenoid-diterpenoid amide dimers and diterpenoid amides from the leaves of Erythrophleum fordii.

    Science.gov (United States)

    Du, Dan; Qu, Jing; Wang, Jia-Ming; Yu, Shi-Shan; Chen, Xiao-Guang; Xu, Song; Ma, Shuang-Gang; Li, Yong; Ding, Guang-Zhi; Fang, Lei

    2010-10-01

    Detailed phytochemical investigation from the leaves of Erythrophleum fordii resulted in the isolation of 13 compounds, including three cassaine diterpenoid-diterpenoid amide dimers (1, 3 and 5), and seven cassaine diterpenoid amides (6 and 8-13), together with three previously reported ones, erythrophlesins D (2), C (4) and 3beta-hydroxynorerythrosuamide (7). Compounds 1, 3 and 5 are further additions to the small group of cassaine diterpenoid dimers represented by erythrophlesins A-D. Their structures were determined by analysis of extensive one- and two-dimensional NMR experiments and ESIMS methods. Cytotoxic activities of the isolated compounds were tested against HCT-8, Bel-7402, BGC-823, A549 and A2780 human cancer cell lines in the MTT test. Results showed that compounds 1 and 3-5 exhibited significantly selective cytotoxic activities (IC(50)<10 microM) against these cells, respectively. Copyright © 2010 Elsevier Ltd. All rights reserved.

  12. Benzoylureas as removable cis amide inducers: synthesis of cyclic amides via ring closing metathesis (RCM).

    Science.gov (United States)

    Brady, Ryan M; Khakham, Yelena; Lessene, Guillaume; Baell, Jonathan B

    2011-02-07

    Rapid and high yielding synthesis of medium ring lactams was made possible through the use of a benzoylurea auxiliary that serves to stabilize a cisoid amide conformation, facilitating cyclization. The auxiliary is released after activation under the mild conditions required to deprotect a primary amine, such as acidolysis of a Boc group in the examples given here. This methodology is a promising tool for the synthesis of medium ring lactams, macrocyclic natural products and peptides.

  13. The structure of the interface in the solvent mediated interaction of dipolar surfaces

    International Nuclear Information System (INIS)

    Dzhavakhidze, P.G.; Levadny, V.G.

    1987-08-01

    Interaction of two dipolar surfaces separated by a polar medium is considered within the framework of nonlocal electrostatics. The dipolar surface layers are modelled as regular lattices with fixed orientation of dipoles which are immersed into the solvent; solvent response is characterized by nonlocal dielectric function. The model is elaborated in order to reveal the role of the dipolar layer discreteness in the electric field produced by one surface and the interaction between two surfaces (which gives rise to the so called ''hydration'' or ''structural'' force acting between mineral surfaces and phospholipid bilayers). The discreteness effects are present only for commensurate lattices. Their special mutual arrangement then may lead to considerable reduction of structural forces, viz. the usual repulsion regime may change at short distances to attraction. Conditions are considered when repulsion is entirely replaced by attraction, i.e. the ''hydration barrier'' disappears. In appended note we discuss the role of solvation of surface dipolar groups. We propose an explanation of why two modes of decay (one with oscillative fine structure) may be present in the dependence of the force upon distance if the surface dipolar groups are immersed deep enough in the solvent and how the long-range oscillative mode disappears when the surface is but weakly solvated. (author). 35 refs, 5 figs

  14. Naturally occurring antifungal aromatic esters and amides

    International Nuclear Information System (INIS)

    Ali, M.S.; Shahnaz; Tabassum, S.; Ogunwande, I.A.; Pervez, M.K.

    2010-01-01

    During the search of antifungal natural products from terrestrial plants, a new long chained aromatic ester named grandiflorate along with spatazoate from Portulaca grandiflora and N-[2-methoxy-2-(4-methoxyphenyl) ethyl]-trans-cinnamide and aegeline from Solanum erianthum of Nigeria were isolated and tested against six fungal species. The known constituents have not been reported so far from mentioned investigated plants. Structures of the isolated compounds were elucidated with the aid of spectroscopic techniques including two dimensional NMR experiments. Among the compounds, the esters found more potent than amides against Candida albicans and Aspergillus flavus. The new compound grandiflorate gave response against all tested fungal species while aegeline was found to give lowest inhibition during this study. (author)

  15. Naturally occurring antifungal aromatic esters and amides

    Energy Technology Data Exchange (ETDEWEB)

    Ali, M S; Shahnaz,; Tabassum, S; Ogunwande, I A; Pervez, M K [University of Karachi (Pakistan). HEJ Research Inst. of Chemistry, International Centre for Chemical and Biological Sciences

    2010-08-15

    During the search of antifungal natural products from terrestrial plants, a new long chained aromatic ester named grandiflorate along with spatazoate from Portulaca grandiflora and N-[2-methoxy-2-(4-methoxyphenyl) ethyl]-trans-cinnamide and aegeline from Solanum erianthum of Nigeria were isolated and tested against six fungal species. The known constituents have not been reported so far from mentioned investigated plants. Structures of the isolated compounds were elucidated with the aid of spectroscopic techniques including two dimensional NMR experiments. Among the compounds, the esters found more potent than amides against Candida albicans and Aspergillus flavus. The new compound grandiflorate gave response against all tested fungal species while aegeline was found to give lowest inhibition during this study. (author)

  16. Protein resonance assignment at MAS frequencies approaching 100 kHz: a quantitative comparison of J-coupling and dipolar-coupling-based transfer methods

    Energy Technology Data Exchange (ETDEWEB)

    Penzel, Susanne; Smith, Albert A.; Agarwal, Vipin; Hunkeler, Andreas [ETH Zürich, Physical Chemistry (Switzerland); Org, Mai-Liis; Samoson, Ago, E-mail: ago.samoson@ttu.ee [Tallinn University of Technology, NMR Instituut, Tartu Teadus, Tehnomeedikum (Estonia); Böckmann, Anja, E-mail: a.bockmann@ibcp.fr [UMR 5086 CNRS/Université de Lyon 1, Institut de Biologie et Chimie des Protéines (France); Ernst, Matthias, E-mail: maer@ethz.ch; Meier, Beat H., E-mail: beme@ethz.ch [ETH Zürich, Physical Chemistry (Switzerland)

    2015-10-15

    We discuss the optimum experimental conditions to obtain assignment spectra for solid proteins at magic-angle spinning (MAS) frequencies around 100 kHz. We present a systematic examination of the MAS dependence of the amide proton T{sub 2}′ times and a site-specific comparison of T{sub 2}′ at 93 kHz versus 60 kHz MAS frequency. A quantitative analysis of transfer efficiencies of building blocks, as they are used for typical 3D experiments, was performed. To do this, we compared dipolar-coupling and J-coupling based transfer steps. The building blocks were then combined into 3D experiments for sequential resonance assignment, where we evaluated signal-to-noise ratio and information content of the different 3D spectra in order to identify the best assignment strategy. Based on this comparison, six experiments were selected to optimally assign the model protein ubiquitin, solely using spectra acquired at 93 kHz MAS. Within 3 days of instrument time, the required spectra were recorded from which the backbone resonances have been assigned to over 96 %.

  17. New organic semiconductors with imide/amide-containing molecular systems.

    Science.gov (United States)

    Liu, Zitong; Zhang, Guanxin; Cai, Zhengxu; Chen, Xin; Luo, Hewei; Li, Yonghai; Wang, Jianguo; Zhang, Deqing

    2014-10-29

    Due to their high electron affinities, chemical and thermal stabilities, π-conjugated molecules with imide/amide frameworks have received considerable attentions as promising candidates for high-performance optoelectronic materials, particularly for organic semiconductors with high carrier mobilities. The purpose of this Research News is to give an overview of recent advances in development of high performance imide/amide based organic semiconductors for field-effect transistors. It covers naphthalene diimide-, perylene diimide- and amide-based conjugated molecules and polymers for organic semiconductors. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Biosynthesis, degradation, and pharmacological importance of the fatty acid amides

    Science.gov (United States)

    Farrell, Emma K.; Merkler, David J.

    2008-01-01

    The identification of two biologically active fatty acid amides, N-arachidonoylethanolamine (anandamide) and oleamide, has generated a great deal of excitement and stimulated considerable research. However, anandamide and oleamide are merely the best-known and best-understood members of a much larger family of biologically-occurring fatty acid amides. In this review, we will outline which fatty acid amides have been isolated from mammalian sources, detail what is known about how these molecules are made and degraded in vivo, and highlight their potential for the development of novel therapeutics. PMID:18598910

  19. Picosecond thermometer in the amide I band of myoglobin

    DEFF Research Database (Denmark)

    Austin, R.H.; Xie, A.; Meer, L. van der

    2005-01-01

    The amide I and II bands in myoglobin show a heterogeneous temperature dependence, with bands at 6.17 and 6.43 mu m which are more intense at low temperatures. The amide I band temperature dependence is on the long wavelength edge of the band, while the short wavelength side has almost...... can be used to determine the time it takes vibrational energy to flow into the hydration shell. We determine that vibrational energy flow to the hydration shell from the amide I takes approximately 20 ps to occur....

  20. Tunnel-induced Dipolar Resonances in a Double-well Potential.

    Science.gov (United States)

    Schulz, Bruno; Saenz, Alejandro

    2016-11-18

    A system of two dipolar particles that are confined in a double-well potential and interact via a realistic isotropic interaction potential is investigated as a protoype for ultracold atoms with a magnetic dipole moment or ultracold dipolar heteronuclear diatomic molecules in double-well traps or in optical lattices. The resulting energy spectrum is discussed as a function of the dipole-dipole interaction strength. The variation of the strength of the dipole-dipole interaction is found to lead to various resonance phenomena. Among those are the previously discussed inelastic confinement-induced resonances as well as the dipole-induced resonances. It is found that the double-well potential gives rise to a new type of resonances, tunnel-induced dipolar ones. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Dipolar Antiferromagnetism and Quantum Criticality in LiErF4

    International Nuclear Information System (INIS)

    Kraemer, Conradin; Nikseresht, Neda; Piatek, Julian; Tsyrulin, Nikolay; Piazza, Bastien; Kiefer, Klaus; Klemke, Bastian; Rosenbaum, Thomas; Aeppli, Gabriel; Gannarelli, Che; Prokes, Karel; Straessle, Thierry; Keller, Lukas; Zaharko, Oksana; Kraemer, Karl; Ronnow, Henrik

    2012-01-01

    Magnetism has been predicted to occur in systems in which dipolar interactions dominate exchange. We present neutron scattering, specific heat, and magnetic susceptibility data for LiErF 4 , establishing it as a model dipolar-coupled antiferromagnet with planar spin-anisotropy and a quantum phase transition in applied field H c# parallel# = 4.0 ± 0.1 kilo-oersteds. We discovered non-mean-field critical scaling for the classical phase transition at the antiferromagnetic transition temperature that is consistent with the two-dimensional XY/h 4 universality class; in accord with this, the quantum phase transition at H c exhibits three-dimensional classical behavior. The effective dimensional reduction may be a consequence of the intrinsic frustrated nature of the dipolar interaction, which strengthens the role of fluctuations.

  2. A reduced-amide inhibitor of Pin1 binds in a conformation resembling a twisted-amide transition state.

    Science.gov (United States)

    Xu, Guoyan G; Zhang, Yan; Mercedes-Camacho, Ana Y; Etzkorn, Felicia A

    2011-11-08

    The mechanism of the cell cycle regulatory peptidyl prolyl isomerase (PPIase), Pin1, was investigated using reduced-amide inhibitors designed to mimic the twisted-amide transition state. Inhibitors, R-pSer-Ψ[CH(2)N]-Pro-2-(indol-3-yl)ethylamine, 1 [R = fluorenylmethoxycarbonyl (Fmoc)] and 2 (R = Ac), of Pin1 were synthesized and bioassayed. Inhibitor 1 had an IC(50) value of 6.3 μM, which is 4.5-fold better for Pin1 than our comparable ground-state analogue, a cis-amide alkene isostere-containing inhibitor. The change of Fmoc to Ac in 2 improved aqueous solubility for structural determination and resulted in an IC(50) value of 12 μM. The X-ray structure of the complex of 2 bound to Pin1 was determined to 1.76 Å resolution. The structure revealed that the reduced amide adopted a conformation similar to the proposed twisted-amide transition state of Pin1, with a trans-pyrrolidine conformation of the prolyl ring. A similar conformation of substrate would be destabilized relative to the planar amide conformation. Three additional reduced amides, with Thr replacing Ser and l- or d-pipecolate (Pip) replacing Pro, were slightly weaker inhibitors of Pin1.

  3. Reduced-Amide Inhibitor of Pin1 Binds in a Conformation Resembling a Twisted-Amide Transition State†

    Science.gov (United States)

    Xu, Guoyan G.; Zhang, Yan; Mercedes-Camacho, Ana Y.; Etzkorn, Felicia A.

    2011-01-01

    The mechanism of the cell cycle regulatory peptidyl prolyl isomerase (PPIase), Pin1, was investigated using reduced-amide inhibitors designed to mimic the twisted-amide transition state. Inhibitors, R–pSer–Ψ[CH2N]–Pro–2-(indol-3-yl)-ethylamine, 1 (R = fluorenylmethoxycarbonyl, Fmoc), and 2 (R = Ac), of Pin1 were synthesized and bioassayed. Inhibitor 1 had an IC50 value of 6.3 μM, which is 4.5-fold better inhibition for Pin1 than our comparable ground state analogue, a cis-amide alkene isostere containing inhibitor. The change of Fmoc to Ac in 2 improved aqueous solubility for structural determination, and resulted in an IC50 value of 12 μM. The X-ray structure of the complex of 2 bound to Pin1 was determined to 1.76 Å resolution. The structure revealed that the reduced amide adopted a conformation similar to the proposed twisted-amide transition state of Pin1, with a trans-pyrrolidine conformation of the prolyl ring. A similar conformation of substrate would be destabilized relative to the planar amide conformation. Three additional reduced amides, with Thr replacing Ser, and l- or d-pipecolate (Pip) replacing Pro, were slightly weaker inhibitors of Pin1. PMID:21980916

  4. Pitch angle distributions of electrons at dipolarization sites during geomagnetic activity: THEMIS observations

    Science.gov (United States)

    Wang, Kaiti; Lin, Ching-Huei; Wang, Lu-Yin; Hada, Tohru; Nishimura, Yukitoshi; Turner, Drew L.; Angelopoulos, Vassilis

    2014-12-01

    Changes in pitch angle distributions of electrons with energies from a few eV to 1 MeV at dipolarization sites in Earth's magnetotail are investigated statistically to determine the extent to which adiabatic acceleration may contribute to these changes. Forty-two dipolarization events from 2008 and 2009 observed by Time History of Events and Macroscale Interactions during Substorms probes covering the inner plasma sheet from 8 RE to 12 RE during geomagnetic activity identified by the AL index are analyzed. The number of observed events with cigar-type distributions (peaks at 0° and 180°) decreases sharply below 1 keV after dipolarization because in many of these events, electron distributions became more isotropized. From above 1 keV to a few tens of keV, however, the observed number of cigar-type events increases after dipolarization and the number of isotropic events decreases. These changes can be related to the ineffectiveness of Fermi acceleration below 1 keV (at those energies, dipolarization time becomes comparable to electron bounce time). Model-calculated pitch angle distributions after dipolarization with the effect of betatron and Fermi acceleration tested indicate that these adiabatic acceleration mechanisms can explain the observed patterns of event number changes over a large range of energies for cigar events and isotropic events. Other factors still need to be considered to assess the observed increase in cigar events around 2 keV. Indeed, preferential directional increase/loss of electron fluxes, which may contribute to the formation of cigar events, was observed. Nonadiabatic processes to accelerate electrons in a parallel direction may also be important for future study.

  5. The structure of ions and zwitterionic lipids regulates the charge of dipolar membranes.

    Science.gov (United States)

    Szekely, Or; Steiner, Ariel; Szekely, Pablo; Amit, Einav; Asor, Roi; Tamburu, Carmen; Raviv, Uri

    2011-06-21

    In pure water, zwitterionic lipids form lamellar phases with an equilibrium water gap on the order of 2 to 3 nm as a result of the dominating van der Waals attraction between dipolar bilayers. Monovalent ions can swell those neutral lamellae by a small amount. Divalent ions can adsorb onto dipolar membranes and charge them. Using solution X-ray scattering, we studied how the structure of ions and zwitterionic lipids regulates the charge of dipolar membranes. We found that unlike monovalent ions that weakly interact with all of the examined dipolar membranes, divalent and trivalent ions adsorb onto membranes containing lipids with saturated tails, with an association constant on the order of ∼10 M(-1). One double bond in the lipid tail is sufficient to prevent divalent ion adsorption. We suggest that this behavior is due to the relatively loose packing of lipids with unsaturated tails that increases the area per lipid headgroup, enabling their free rotation. Divalent ion adsorption links two lipids and limits their free rotation. The ion-dipole interaction gained by the adsorption of the ions onto unsaturated membranes is insufficient to compensate for the loss of headgroup free-rotational entropy. The ion-dipole interaction is stronger for cations with a higher valence. Nevertheless, polyamines behave as monovalent ions near dipolar interfaces in the sense that they interact weakly with the membrane surface, whereas in the bulk their behavior is similar to that of multivalent cations. Advanced data analysis and comparison with theory provide insight into the structure and interactions between ion-induced regulated charged interfaces. This study models biologically relevant interactions between cell membranes and various ions and the manner in which the lipid structure governs those interactions. The ability to monitor these interactions creates a tool for probing systems that are more complex and forms the basis for controlling the interactions between dipolar

  6. Stepwise π-extension of meso-alkylidenyl porphyrins through sequential 1,3-dipolar cycloaddition and redox reactions.

    Science.gov (United States)

    Park, Dowoo; Jeong, Seung Doo; Ishida, Masatoshi; Lee, Chang-Hee

    2014-08-25

    Several regioselectively π-extended, pyrrole fused porphyrinoids have been synthesized by the 1,3-dipolar cycloaddition of meso-alkylidene-(benzi)porphyrins. Pd(II) complexes gave oxidation resistant, bis-pyrrole fused adducts. The repeated 1,3-dipolar cycloaddition followed by oxidation-reduction of pentaphyrin analogs afforded π-extended porphyrin analogs.

  7. Diazo Compounds as Highly Tunable Reactants in 1,3-Dipolar Cycloaddition Reactions with Cycloalkynes†

    Science.gov (United States)

    McGrath, Nicholas A.

    2012-01-01

    Diazo compounds, which can be accessed directly from azides by deimidogenation, are shown to be extremely versatile dipoles in 1,3-dipolar cycloaddition reactions with a cyclooctyne. The reactivity of a diazo compound can be much greater or much less than its azide analog, and is enhanced markedly in polar-protic solvents. These reactivities are predictable from frontier molecular orbital energies. The most reactive diazo compound exhibited the highest known second-order rate constant to date for a dipolar cycloaddition with a cycloalkyne. These data provide a new modality for effecting chemoselective reactions in a biological context. PMID:23227302

  8. 1,3-Dipolar Cycloadditions of Diazo Compounds in the Presence of Azides.

    Science.gov (United States)

    Aronoff, Matthew R; Gold, Brian; Raines, Ronald T

    2016-04-01

    The diazo group has untapped utility in chemical biology. The tolerance of stabilized diazo groups to cellular metabolism is comparable to that of azido groups. However, chemoselectivity has been elusive, as both groups undergo 1,3-dipolar cycloadditions with strained alkynes. Removing strain and tuning dipolarophile electronics yields diazo group selective 1,3-dipolar cycloadditions that can be performed in the presence of an azido group. For example, diazoacetamide but not its azido congener react with dehydroalanine residues, as in the natural product nisin.

  9. Simulation of transverse beam splitting using time-dependent dipolar or quadrupolar kicks

    CERN Document Server

    Capoani, Federico

    2017-01-01

    Two simple systems with high relevance for accelerator physics have been studied in detail in the context of this Summer Student Project. These systems describe the motion under the influence of detuning with amplitude due to non-linear magnets and an external, time-dependent force of dipolar or quadrupolar nature.Two simple systems with high relevance for accelerator physics have been studied in detail in the context of this Summer Student Project. These systems describe the motion under the influence of detuning with amplitude due to non-linear magnets and an external, time-dependent force of dipolar or quadrupolar nature.

  10. A liquid crystalline medium for measuring residual dipolar couplings over a wide range of temperatures

    Energy Technology Data Exchange (ETDEWEB)

    Wang Hong; Eberstadt, Matthias; Olejniczak, Edward T.; Meadows, Robert P.; Fesik, Stephen W. [Abbott Laboratories (United States)

    1998-10-15

    A mixture of dilauroyl phosphatidylcholine (DLPC) and 3-(cholamidopropyl)dimethylammonio-2-hydroxyl-1-propane sulfonate (CHAPSO) in water forms disc shaped bicelles that become ordered at high magnetic fields over a wide range of temperatures. As illustrated for the FK506 binding protein (FKBP), large residual dipolar couplings can be measured for proteins dissolved in low concentrations (5% w/v) of a DLPC/CHAPSO medium at a molar ratio of 4.2:1. This system is especially useful for measuring residual dipolar couplings for molecules that are only stable at low temperatures.

  11. An initial boundary value problem for modeling a piezoelectric dipolar body

    Science.gov (United States)

    Marin, Marin; Öchsner, Andreas

    2018-03-01

    This study deals with the first initial boundary value problem in elasticity of piezoelectric dipolar bodies. We consider the most general case of an anisotropic and inhomogeneous elastic body having a dipolar structure. For two different types of restrictions imposed on the problem data, we prove two results regarding the uniqueness of solution, by using a different but accessible method. Then, the mixed problem is transformed in a temporally evolutionary equation on a Hilbert space, conveniently constructed based on the problem data. With the help of a known result from the theory of semigroups of operators, the existence and uniqueness of the weak solution for this equation are proved.

  12. Dipolar Quinoidal Acene Analogues as Stable Isoelectronic Structures of Pentacene and Nonacene

    KAUST Repository

    Shi, Xueliang

    2015-10-08

    Quinoidal thia-acene analogues, as the respective isoelectronic structures of pentacene and nonacene, were synthesized and an unusual 1,2-sulfur migration was observed during the Friedel-Crafts alkylation reaction. The analogues display a closed-shell quinoidal structure in the ground state with a distinctive dipolar character. In contrast to their acene isoelectronic structures, both compounds are stable because of the existence of more aromatic sextet rings, a dipolar character, and kinetic blocking. They exhibit unique packing in single crystals resulting from balanced dipole-dipole and [C-H⋯π]/[C-H⋯S] interactions.

  13. Ground-state candidate for the classical dipolar kagome Ising antiferromagnet

    Science.gov (United States)

    Chioar, I. A.; Rougemaille, N.; Canals, B.

    2016-06-01

    We have investigated the low-temperature thermodynamic properties of the classical dipolar kagome Ising antiferromagnet using Monte Carlo simulations, in the quest for the ground-state manifold. In spite of the limitations of a single-spin-flip approach, we managed to identify certain ordering patterns in the low-temperature regime and we propose a candidate for this unknown state. This configuration presents some intriguing features and is fully compatible with the extrapolations of the at-equilibrium thermodynamic behavior sampled so far, making it a very likely choice for the dipolar long-range ordered state of the classical kagome Ising antiferromagnet.

  14. New and Efficient Synthesis of Amides from Acid Chlorides Using Diisobutyl(amino)aluminum

    Energy Technology Data Exchange (ETDEWEB)

    Park, Jae Kyo; Shin, Won Kyu; An, Duk Keun [Kangwon National Univ., Chuncheon (Korea, Republic of)

    2013-05-15

    In conclusion, we have developed a facile, alternative method for the formation of secondary and tertiary amides including morpholine amides from acid chlorides by using diisobutyl(amino)aluminum under mild reaction conditions. The advantages of the present method include the high product yields, simple experimental procedure, short reaction time (10 min), and the fact that an excess amount of amine is not required. This result suggests that our new method can provide an alternative method for the synthesis of useful amides from acid chlorides. Amides are valuable functional groups in biological, agrochemical, and pharmaceutical molecules. Several amides such as Weinreb amides, morpholine amides, and pyrrolidine amides are useful intermediates for the synthesis of aldehydes or ketones. Among them, morpholine amides are a cheap and good substitute for Weinreb amides.

  15. New and Efficient Synthesis of Amides from Acid Chlorides Using Diisobutyl(amino)aluminum

    International Nuclear Information System (INIS)

    Park, Jae Kyo; Shin, Won Kyu; An, Duk Keun

    2013-01-01

    In conclusion, we have developed a facile, alternative method for the formation of secondary and tertiary amides including morpholine amides from acid chlorides by using diisobutyl(amino)aluminum under mild reaction conditions. The advantages of the present method include the high product yields, simple experimental procedure, short reaction time (10 min), and the fact that an excess amount of amine is not required. This result suggests that our new method can provide an alternative method for the synthesis of useful amides from acid chlorides. Amides are valuable functional groups in biological, agrochemical, and pharmaceutical molecules. Several amides such as Weinreb amides, morpholine amides, and pyrrolidine amides are useful intermediates for the synthesis of aldehydes or ketones. Among them, morpholine amides are a cheap and good substitute for Weinreb amides

  16. AMIDE: A Free Software Tool for Multimodality Medical Image Analysis

    Directory of Open Access Journals (Sweden)

    Andreas Markus Loening

    2003-07-01

    Full Text Available Amide's a Medical Image Data Examiner (AMIDE has been developed as a user-friendly, open-source software tool for displaying and analyzing multimodality volumetric medical images. Central to the package's abilities to simultaneously display multiple data sets (e.g., PET, CT, MRI and regions of interest is the on-demand data reslicing implemented within the program. Data sets can be freely shifted, rotated, viewed, and analyzed with the program automatically handling interpolation as needed from the original data. Validation has been performed by comparing the output of AMIDE with that of several existing software packages. AMIDE runs on UNIX, Macintosh OS X, and Microsoft Windows platforms, and it is freely available with source code under the terms of the GNU General Public License.

  17. Synthesis of amide isosteres of schweinfurthin-based stilbenes.

    Science.gov (United States)

    Stockdale, David P; Beutler, John A; Wiemer, David F

    2017-10-15

    The schweinfurthins are plant-derived stilbenes with an intriguing profile of anti-cancer activity. To obtain analogues of the schweinfurthins that might preserve the biological activity but have greater water solubility, a formal replacement of the central olefin with an amide has been explored. Two pairs of amides have been prepared, each containing the same hexahydroxanthene "left half" joined through an amide linkage to two different "right halves." In each series, the amide has been inserted in both possible orientations, placing the carbonyl group on the tricyclic ABC ring system and the amine on the D-ring, or placing the amine on the hexahydroxanthene and the carbonyl group on the D-ring. The four new schweinfurthin analogues have been tested in the NCI 60 cell line screen, and in both cases the more active isomer carried the carbonyl group on the C-ring. Copyright © 2017 Elsevier Ltd. All rights reserved.

  18. ‘Umpolung’ Reactivity in Semiaqueous Amide and Peptide Synthesis

    Science.gov (United States)

    Shen, Bo; Makley, Dawn M.; Johnston, Jeffrey N.

    2010-01-01

    The amide functional group is one of Nature’s key functional and structural elements, most notably within peptides. Amides are also key intermediates in the preparation of a diverse range of therapeutic small molecules. Its construction using available methods focuses principally upon dehydrative approaches, although oxidative and radical-based methods are representative alternatives. During the carbon-nitrogen bond forming step in most every example, the carbon and nitrogen bear electrophilic and nucleophilic character, respectively. Here we show that activation of amines and nitroalkanes with an electrophilic iodine source in wet THF can lead directly to amide products. Preliminary observations support a mechanistic construct in which reactant polarity is reversed (umpolung) during C-N bond formation relative to traditional approaches. The use of nitroalkanes as acyl anion equivalents provides a conceptually innovative approach to amide and peptide synthesis, and one that might ultimately provide for efficient peptide synthesis that is fully reliant on enantioselective methods. PMID:20577205

  19. Synthesis and characterization of new optically active poly(amide ...

    African Journals Online (AJOL)

    Synthesis and characterization of new optically active poly(amide-imide)s based on N -trimellitimido- ... Bulletin of the Chemical Society of Ethiopia ... (DMAc), dimethyl sulfoxide (DMSO) and N-methyl-2-pyrrolidone (NMP) at room temperature.

  20. MICROBIAL DEGRADATION OF SEVEN AMIDES BY SUSPENDED BACTERIAL POPULATIONS

    Science.gov (United States)

    Microbial transformation rate constants were determined for seven amides in natural pond water. A second-order mathematical rate expression served as the model for describing the microbial transformation. Also investigated was the relationship between the infrared spectra and the...

  1. Silver-catalyzed synthesis of amides from amines and aldehydes

    Science.gov (United States)

    Madix, Robert J; Zhou, Ling; Xu, Bingjun; Friend, Cynthia M; Freyschlag, Cassandra G

    2014-11-18

    The invention provides a method for producing amides via the reaction of aldehydes and amines with oxygen adsorbed on a metallic silver or silver alloy catalyst. An exemplary reaction is shown in Scheme 1: (I), (II), (III). ##STR00001##

  2. Stability of Medium-Bridged Twisted Amides in Aqueous Solutions

    Science.gov (United States)

    Szostak, Michal; Yao, Lei; Aubé, Jeffrey

    2012-01-01

    “Twisted” amides containing non-standard dihedral angles are typically hypersensitive to hydrolysis, a feature that has stringently limited their utility in water. We have synthesized a series of bridged lactams that contain a twisted amide linkage but which exhibit enhanced stability in aqueous environments. Many of these compounds were extracted unchanged from aqueous mixtures ranging from the strongly basic to the strongly acidic. NMR experiments showed that tricyclic lactams undergo reversible hydrolysis at extreme pH ranges, but that a number of compounds in this structure class are indefinitely stable under physiologically relevant pH conditions; one bicyclic example was additionally water-soluble. We examined the effect of structure on the reversibility of amide bond hydrolysis, which we attributed to the transannular nature of the amino acid analogs. These data suggest that medium-bridged lactams of these types should provide useful platforms for studying the behavior of twisted amides in aqueous systems. PMID:19178141

  3. Novel amide-based inhibitors of inosine 5'-monophosphate dehydrogenase.

    Science.gov (United States)

    Watterson, Scott H; Liu, Chunjian; Dhar, T G Murali; Gu, Henry H; Pitts, William J; Barrish, Joel C; Fleener, Catherine A; Rouleau, Katherine; Sherbina, N Z; Hollenbaugh, Diane L; Iwanowicz, Edwin J

    2002-10-21

    A series of novel amide-based small molecule inhibitors of inosine monophosphate dehydrogenase (IMPDH) was explored. The synthesis and the structure-activity relationships (SARs) derived from in vitro studies are described.

  4. Phase space investigation of the lithium amide halides

    Energy Technology Data Exchange (ETDEWEB)

    Davies, Rosalind A. [Hydrogen Storage Chemistry Group, School of Chemistry, University of Birmingham, Edgbaston, Birmingham B15 2TT (United Kingdom); Hydrogen and Fuel Cell Group, School of Chemical Engineering, University of Birmingham, Edgbaston B15 2TT (United Kingdom); Hewett, David R.; Korkiakoski, Emma [Hydrogen Storage Chemistry Group, School of Chemistry, University of Birmingham, Edgbaston, Birmingham B15 2TT (United Kingdom); Thompson, Stephen P. [Diamond Light Source, Harwell Science and Innovation Campus, Didcot, Oxfordshire OX11 0QX (United Kingdom); Anderson, Paul A., E-mail: p.a.anderson@bham.ac.uk [Hydrogen Storage Chemistry Group, School of Chemistry, University of Birmingham, Edgbaston, Birmingham B15 2TT (United Kingdom)

    2015-10-05

    Highlights: • The lower limits of halide incorporation in lithium amide have been investigated. • The only amide iodide stoichiometry observed was Li{sub 3}(NH{sub 2}){sub 2}I. • Solid solutions were observed in both the amide chloride and amide bromide systems. • A 46% reduction in chloride content resulted in a new phase: Li{sub 7}(NH{sub 2}){sub 6}Cl. • New low-chloride phase maintained improved H{sub 2} desorption properties of Li{sub 4}(NH{sub 2}){sub 3}Cl. - Abstract: An investigation has been carried out into the lower limits of halide incorporation in lithium amide (LiNH{sub 2}). It was found that the lithium amide iodide Li{sub 3}(NH{sub 2}){sub 2}I was unable to accommodate any variation in stoichiometry. In contrast, some variation in stoichiometry was accommodated in Li{sub 7}(NH{sub 2}){sub 6}Br, as shown by a decrease in unit cell volume when the bromide content was reduced. The amide chloride Li{sub 4}(NH{sub 2}){sub 3}Cl was found to adopt either a rhombohedral or a cubic structure depending on the reaction conditions. Reduction in chloride content generally resulted in a mixture of phases, but a new rhombohedral phase with the stoichiometry Li{sub 7}(NH{sub 2}){sub 6}Cl was observed. In comparison to LiNH{sub 2}, this new low-chloride phase exhibited similar improved hydrogen desorption properties as Li{sub 4}(NH{sub 2}){sub 3}Cl but with a much reduced weight penalty through addition of chloride. Attempts to dope lithium amide with fluoride ions have so far proved unsuccessful.

  5. Actinides complexes in solvent extraction. The amide type of extractants

    International Nuclear Information System (INIS)

    Musikas, C.; Condamines, N.; Charbonnel, M.C.; Hubert, H.

    1989-01-01

    The N,N-dialkylamides and the N,N'-tetraalkyl. 2-alkyl 1,3-diamide propane are two promising classes of extractants which could replace advantageously the organophosphorus molecules for the separations of the actinide. The main advantages of the amides lie in their complete incinerability and the small interference of their radiolytic and hydrolytic degradation products for the processes. The actinide extraction chemistry with various amides is reviewed in this paper

  6. Highly Stereoselective Intermolecular Haloetherification and Haloesterification of Allyl Amides

    Science.gov (United States)

    Soltanzadeh, Bardia; Jaganathan, Arvind; Staples, Richard J.

    2016-01-01

    An organocatalytic and highly regio-, diastereo-, and enantioselective intermolecular haloetherification and haloesterification reaction of allyl amides is reported. A variety of alkene substituents and substitution patterns are compatible with this chemistry. Notably, electronically unbiased alkene substrates exhibit exquisite regio- and diastereoselectivity for the title transformation. We also demonstrate that the same catalytic system can be used in both chlorination and bromination reactions of allyl amides with a variety of nucleophiles with little or no modification. PMID:26110812

  7. A new phenylethyl alkyl amide from the Ambrostoma quadriimpressum Motschulsky

    Directory of Open Access Journals (Sweden)

    Guolei Zhao

    2011-09-01

    Full Text Available A new phenylethyl alkyl amide, (10R-10-hydroxy-N-phenethyloctadecanamide (1, was isolated from the beetle Ambrostoma quadriimpressum Motschulsky. The structure of the amide was determined by NMR and MS. The absolute configuration of compound 1 was confirmed by an asymmetric total synthesis, which was started from L-glutamic acid. The construction of the aliphatic chain was accomplished by the selective protection of the hydroxy groups and two-time implementation of the Wittig olefination reaction.

  8. Predicting protein amidation sites by orchestrating amino acid sequence features

    Science.gov (United States)

    Zhao, Shuqiu; Yu, Hua; Gong, Xiujun

    2017-08-01

    Amidation is the fourth major category of post-translational modifications, which plays an important role in physiological and pathological processes. Identifying amidation sites can help us understanding the amidation and recognizing the original reason of many kinds of diseases. But the traditional experimental methods for predicting amidation sites are often time-consuming and expensive. In this study, we propose a computational method for predicting amidation sites by orchestrating amino acid sequence features. Three kinds of feature extraction methods are used to build a feature vector enabling to capture not only the physicochemical properties but also position related information of the amino acids. An extremely randomized trees algorithm is applied to choose the optimal features to remove redundancy and dependence among components of the feature vector by a supervised fashion. Finally the support vector machine classifier is used to label the amidation sites. When tested on an independent data set, it shows that the proposed method performs better than all the previous ones with the prediction accuracy of 0.962 at the Matthew's correlation coefficient of 0.89 and area under curve of 0.964.

  9. Hydrogen Bonding Interaction between Atmospheric Gaseous Amides and Methanol

    Directory of Open Access Journals (Sweden)

    Hailiang Zhao

    2016-12-01

    Full Text Available Amides are important atmospheric organic–nitrogen compounds. Hydrogen bonded complexes of methanol (MeOH with amides (formamide, N-methylformamide, N,N-dimethylformamide, acetamide, N-methylacetamide and N,N-dimethylacetamide have been investigated. The carbonyl oxygen of the amides behaves as a hydrogen bond acceptor and the NH group of the amides acts as a hydrogen bond donor. The dominant hydrogen bonding interaction occurs between the carbonyl oxygen and the OH group of methanol as well as the interaction between the NH group of amides and the oxygen of methanol. However, the hydrogen bonds between the CH group and the carbonyl oxygen or the oxygen of methanol are also important for the overall stability of the complexes. Comparable red shifts of the C=O, NH- and OH-stretching transitions were found in these MeOH–amide complexes with considerable intensity enhancement. Topological analysis shows that the electron density at the bond critical points of the complexes fall in the range of hydrogen bonding criteria, and the Laplacian of charge density of the O–H∙∙∙O hydrogen bond slightly exceeds the upper value of the Laplacian criteria. The energy decomposition analysis further suggests that the hydrogen bonding interaction energies can be mainly attributed to the electrostatic, exchange and dispersion components.

  10. Synthesis and biological activity of pyridazine amides, hydrazones and hydrazides.

    Science.gov (United States)

    Buysse, Ann M; Yap, Maurice Ch; Hunter, Ricky; Babcock, Jonathan; Huang, Xinpei

    2017-04-01

    Optimization studies on compounds initially designed to be herbicides led to the discovery of a series of [6-(3-pyridyl)pyridazin-3-yl]amides exhibiting aphicidal properties. Systematic modifications of the amide moiety as well as the pyridine and pyridazine rings were carried out to determine if these changes could improve insecticidal potency. Structure-activity relationship (SAR) studies showed that changes to the pyridine and pyridazine rings generally resulted in a significant loss of insecticidal potency against green peach aphids [Myzus persicae (Sulzer)] and cotton aphids [(Aphis gossypii (Glover)]. However, replacement of the amide moiety with hydrazines, hydrazones, or hydrazides appeared to be tolerated, with small aliphatic substituents being especially potent. A series of aphicidal [6-(3-pyridyl)pyridazin-3-yl]amides were discovered as a result of random screening of compounds that were intially investigated as herbicides. Follow-up studies of the structure-activity relationship of these [6-(3-pyridyl)pyridazin-3-yl]amides showed that biosteric replacement of the amide moiety was widely tolerated suggesting that further opportunities for exploitation may exist for this new area of insecticidal chemistry. Insecticidal efficacy from the original hit, compound 1, to the efficacy of compound 14 produced greater than 10-fold potency improvement against Aphis gossypii and greater than 14-fold potency improvement against Myzus persicae. © 2016 Society of Chemical Industry. © 2016 Society of Chemical Industry.

  11. Hydrogen Bonding Interaction between Atmospheric Gaseous Amides and Methanol.

    Science.gov (United States)

    Zhao, Hailiang; Tang, Shanshan; Xu, Xiang; Du, Lin

    2016-12-30

    Amides are important atmospheric organic-nitrogen compounds. Hydrogen bonded complexes of methanol (MeOH) with amides (formamide, N -methylformamide, N , N -dimethylformamide, acetamide, N -methylacetamide and N , N -dimethylacetamide) have been investigated. The carbonyl oxygen of the amides behaves as a hydrogen bond acceptor and the NH group of the amides acts as a hydrogen bond donor. The dominant hydrogen bonding interaction occurs between the carbonyl oxygen and the OH group of methanol as well as the interaction between the NH group of amides and the oxygen of methanol. However, the hydrogen bonds between the CH group and the carbonyl oxygen or the oxygen of methanol are also important for the overall stability of the complexes. Comparable red shifts of the C=O, NH- and OH-stretching transitions were found in these MeOH-amide complexes with considerable intensity enhancement. Topological analysis shows that the electron density at the bond critical points of the complexes fall in the range of hydrogen bonding criteria, and the Laplacian of charge density of the O-H∙∙∙O hydrogen bond slightly exceeds the upper value of the Laplacian criteria. The energy decomposition analysis further suggests that the hydrogen bonding interaction energies can be mainly attributed to the electrostatic, exchange and dispersion components.

  12. Amide temperature coefficients in the protein G B1 domain

    International Nuclear Information System (INIS)

    Tomlinson, Jennifer H.; Williamson, Mike P.

    2012-01-01

    Temperature coefficients have been measured for backbone amide 1 H and 15 N nuclei in the B1 domain of protein G (GB1), using temperatures in the range 283–313 K, and pH values from 2.0 to 9.0. Many nuclei display pH-dependent coefficients, which were fitted to one or two pK a values. 1 H coefficients showed the expected behaviour, in that hydrogen-bonded amides have less negative values, but for those amides involved in strong hydrogen bonds in regular secondary structure there is a negative correlation between strength of hydrogen bond and size of temperature coefficient. The best correlation to temperature coefficient is with secondary shift, indicative of a very approximately uniform thermal expansion. The largest pH-dependent changes in coefficient are for amides in loops adjacent to sidechain hydrogen bonds rather than the amides involved directly in hydrogen bonds, indicating that the biggest determinant of the temperature coefficient is temperature-dependent loss of structure, not hydrogen bonding. Amide 15 N coefficients have no clear relationship with structure.

  13. Nonplanar tertiary amides in rigid chiral tricyclic dilactams. Peptide group distortions and vibrational optical activity.

    Science.gov (United States)

    Pazderková, Markéta; Profant, Václav; Hodačová, Jana; Sebestík, Jaroslav; Pazderka, Tomáš; Novotná, Pavlína; Urbanová, Marie; Safařík, Martin; Buděšínský, Miloš; Tichý, Miloš; Bednárová, Lucie; Baumruk, Vladimír; Maloň, Petr

    2013-08-22

    We investigate amide nonplanarity in vibrational optical activity (VOA) spectra of tricyclic spirodilactams 5,8-diazatricyclo[6,3,0,0(1,5)]undecan-4,9-dione (I) and its 6,6',7,7'-tetradeuterio derivative (II). These rigid molecules constrain amide groups to nonplanar geometries with twisted pyramidal arrangements of bonds to amide nitrogen atoms. We have collected a full range vibrational circular dichroism (VCD) and Raman optical activity (ROA) spectra including signals of C-H and C-D stretching vibrations. We report normal-mode analysis and a comparison of calculated to experimental VCD and ROA. The data provide band-to-band assignment and offer a possibility to evaluate roles of constrained nonplanar tertiary amide groups and rigid chiral skeletons. Nonplanarity shows as single-signed VCD and ROA amide I signals, prevailing the couplets expected to arise from the amide-amide interaction. Amide-amide coupling dominates amide II (mainly C'-N stretching, modified in tertiary amides by the absence of a N-H bond) transitions (strong couplet in VCD, no significant ROA) probably due to the close proximity of amide nitrogen atoms. At lower wavenumbers, ROA spectra exhibit another likely manifestation of amide nonplanarity, showing signals of amide V (δ(oop)(N-C) at ~570 cm(-1)) and amide VI (δ(oop)(C'═O) at ~700 cm(-1) and ~650 cm(-1)) vibrations.

  14. Synthesis of Secondary Aromatic Amides via Pd-Catalyzed Aminocarbonylation of Aryl Halides Using Carbamoylsilane as an Amide Source.

    Science.gov (United States)

    Tong, Wenting; Cao, Pei; Liu, Yanhong; Chen, Jianxin

    2017-11-03

    Using N-methoxymethyl-N-organylcarbamoyl(trimethyl)silanes as secondary amides source, the direct transformation of aryl halides into the corresponding secondary aromatic amides via palladium-catalyzed aminocarbonylation is described. The reactions tolerated a broad range of functional groups on the aryl ring except big steric hindrance of substituent. The types and the relative position of substituents on the aryl ring impact the coupling efficiency.

  15. Selective Formation of Secondary Amides via the Copper-Catalyzed Cross-Coupling of Alkylboronic Acids with Primary Amides

    Science.gov (United States)

    Rossi, Steven A.; Shimkin, Kirk W.; Xu, Qun; Mori-Quiroz, Luis M.; Watson, Donald A.

    2014-01-01

    For the first time, a general catalytic procedure for the cross coupling of primary amides and alkylboronic acids is demonstrated. The key to the success of this reaction was the identification of a mild base (NaOSiMe3) and oxidant (di-tert-butyl peroxide) to promote the copper-catalyzed reaction in high yield. This transformation provides a facile, high-yielding method for the mono-alkylation of amides. PMID:23611591

  16. Wave Vector Dependent Susceptibility at T>Tc in a Dipolar Ising Ferromagnet

    DEFF Research Database (Denmark)

    Als-Nielsen, Jens Aage; Holmes, L. M:; Guggenheim, H. J.

    1974-01-01

    The wave-vector-dependent susceptibility of LiTbF4 has been investigated by means of neutron scattering. The observations show a singularity of the susceptibility near wave vector Q=0 which is characteristic of the dipolar Coulomb interaction and good agreement with theory is obtained...

  17. A kinetic study of 1,3-dipolar cycloadditions in micellar media

    NARCIS (Netherlands)

    Rispens, T; Engberts, JBFN

    2003-01-01

    The kinetics of the 1,3-dipolar cycloadditions (DC) of benzonitrile oxide with a series of N-substituted maleimides in micellar media have been investigated. Surfactants studied include anionic sodium dodecyl sulfate, cationic cetyltrimethylammonium bromide, and a series of nonionic alkyl

  18. Electron dynamics during substorm dipolarization in Mercury's magnetosphere

    Directory of Open Access Journals (Sweden)

    D. C. Delcourt

    2005-11-01

    Full Text Available We examine the nonlinear dynamics of electrons during the expansion phase of substorms at Mercury using test particle simulations. A simple model of magnetic field line dipolarization is designed by rescaling a magnetic field model of the Earth's magnetosphere. The results of the simulations demonstrate that electrons may be subjected to significant energization on the time scale (several seconds of the magnetic field reconfiguration. In a similar manner to ions in the near-Earth's magnetosphere, it is shown that low-energy (up to several tens of eV electrons may not conserve the second adiabatic invariant during dipolarization, which leads to clusters of bouncing particles in the innermost magnetotail. On the other hand, it is found that, because of the stretching of the magnetic field lines, high-energy electrons (several keVs and above do not behave adiabatically and possibly experience meandering (Speiser-type motion around the midplane. We show that dipolarization of the magnetic field lines may be responsible for significant, though transient, (a few seconds precipitation of energetic (several keVs electrons onto the planet's surface. Prominent injections of energetic trapped electrons toward the planet are also obtained as a result of dipolarization. These injections, however, do not exhibit short-lived temporal modulations, as observed by Mariner-10, which thus appear to follow from a different mechanism than a simple convection surge.

  19. On the Gross–Pitaevskii equation for trapped dipolar quantum gases

    KAUST Repository

    Carles, Ré mi; Markowich, Peter A; Sparber, Christof

    2008-01-01

    We study the time-dependent Gross-Pitaevskii equation describing Bose-Einstein condensation of trapped dipolar quantum gases. Existence and uniqueness as well as the possible blow-up of solutions are studied. Moreover, we discuss the problem of dimension reduction for this nonlinear and nonlocal Schrödinger equation. © 2008 IOP Publishing Ltd and London Mathematical Society.

  20. Exploring strain-promoted 1,3-dipolar cycloadditions of end functionalized polymers

    NARCIS (Netherlands)

    Ledin, Petr A; Kolishetti, Nagesh; Hudlikar, Manish S; Boons, Geert-Jan

    2014-01-01

    Strain-promoted 1,3-dipolar cycloaddition of cyclooctynes with 1,3-dipoles such as azides, nitrones, and nitrile oxides, are of interest for the functionalization of polymers. In this study, we have explored the use of a 4-dibenzocyclooctynol (DIBO)-containing chain transfer agent in reversible

  1. Residual dipolar couplings : a new technique for structure determination of proteins in solution

    NARCIS (Netherlands)

    van Lune, Frouktje Sapke

    2004-01-01

    The aim of the work described in this thesis was to investigate how residual dipolar couplings can be used to resolve or refine the three-dimensional structure of one of the proteins of the phosphoenol-pyruvate phosphotransferase system (PTS), the main transport system for carbohydrates in

  2. Inclusion Compound Based Approach to Arrays of Artificial Dipolar Molecular Rotors. A Surface Inclusion

    Czech Academy of Sciences Publication Activity Database

    Kobr, L.; Zhao, K.; Shen, K.; Comotti, A.; Bracco, S.; Shoemaker, R. K.; Sozzani, P.; Clark, N.A.; Price, J. C.; Rogers, C. T.; Michl, Josef

    2012-01-01

    Roč. 134, č. 24 (2012), s. 10122-10131 ISSN 0002-7863 EU Projects: European Commission(XE) 227756 - DIPOLAR ROTOR ARRAY Institutional research plan: CEZ:AV0Z40550506 Keywords : controlled rotary motion * solid-state dynamics * aromatic nanochannels * NMR-spectroscopy * single-molecule Subject RIV: CC - Organic Chemistry Impact factor: 10.677, year: 2012

  3. Inclusion Compound Based Approach to Arrays of Artificial Dipolar Molecular Rotors: Bulk Inclusions

    Czech Academy of Sciences Publication Activity Database

    Kobr, L.; Zhao, K.; Shen, Y.; Polívková, Kateřina; Shoemaker, R. K.; Clark, N.A.; Price, J. C.; Rogers, C. T.; Michl, Josef

    2013-01-01

    Roč. 78, č. 5 (2013), s. 1768-1777 ISSN 0022-3263 EU Projects: European Commission(XE) 227756 - DIPOLAR ROTOR ARRAY Institutional support: RVO:61388963 Keywords : solid-state dynamics * phosphonitrilic compounds * aromatic nanochannels * triethylamine Subject RIV: CC - Organic Chemistry Impact factor: 4.638, year: 2013

  4. Tris-o-phenylenedioxycyclotriphosphazene (TPP) Inclusion Compounds Containing a Dipolar Molecular Rotor

    Czech Academy of Sciences Publication Activity Database

    Kobr, L.; Zhao, K.; Shen, Y.; Shoemaker, R. K.; Rogers, C. T.; Michl, Josef

    2014-01-01

    Roč. 14, č. 2 (2014), s. 559-568 ISSN 1528-7483 EU Projects: European Commission(XE) 227756 - DIPOLAR ROTOR ARRAY Institutional support: RVO:61388963 Keywords : aromatic nanochannels * single-molecule * dynamics Subject RIV: CC - Organic Chemistry Impact factor: 4.891, year: 2014

  5. Numerical simulation of trapped dipolar quantum gases: Collapse studies and vortex dynamics

    KAUST Repository

    Sparber, Christof; Markowich, Peter; Huang, Zhongyi

    2010-01-01

    We numerically study the three dimensional Gross-Pitaevskii equation for dipolar quantum gases using a time-splitting algorithm. We are mainly concerned with numerical investigations of the possible blow-up of solutions, i.e. collapse of the condensate, and the dynamics of vortices. © American Institute of Mathematical Sciences.

  6. Nonlinear localized modes in dipolar Bose–Einstein condensates in two-dimensional optical lattices

    International Nuclear Information System (INIS)

    Rojas-Rojas, Santiago; Naether, Uta; Delgado, Aldo; Vicencio, Rodrigo A.

    2016-01-01

    Highlights: • We study discrete two-dimensional breathers in dipolar Bose–Einstein Condensates. • Important differences in the properties of three fundamental modes are found. • Norm threshold for existence of 2D breathers varies with dipolar interaction. • The Effective Potential Method is implemented for stability analysis. • Uncommon mobility of 2D discrete solitons is observed. - Abstract: We analyze the existence and properties of discrete localized excitations in a Bose–Einstein condensate loaded into a periodic two-dimensional optical lattice, when a dipolar interaction between atoms is present. The dependence of the Number of Atoms (Norm) on the energy of solutions is studied, along with their stability. Two important features of the system are shown, namely, the absence of the Norm threshold required for localized solutions to exist in finite 2D systems, and the existence of regions in the parameter space where two fundamental solutions are simultaneously unstable. This feature enables mobility of localized solutions, which is an uncommon feature in 2D discrete nonlinear systems. With attractive dipolar interaction, a non-trivial behavior of the Norm dependence is obtained, which is well described by an analytical model.

  7. Nonlinear localized modes in dipolar Bose–Einstein condensates in two-dimensional optical lattices

    Energy Technology Data Exchange (ETDEWEB)

    Rojas-Rojas, Santiago, E-mail: srojas@cefop.cl [Center for Optics and Photonics and MSI-Nucleus on Advanced Optics, Universidad de Concepción, Casilla 160-C, Concepción (Chile); Departamento de Física, Universidad de Concepción, Casilla 160-C, Concepción (Chile); Naether, Uta [Instituto de Ciencia de Materiales de Aragón and Departamento de Física de la Materia Condensada, CSIC-Universidad de Zaragoza, 50009 Zaragoza (Spain); Delgado, Aldo [Center for Optics and Photonics and MSI-Nucleus on Advanced Optics, Universidad de Concepción, Casilla 160-C, Concepción (Chile); Departamento de Física, Universidad de Concepción, Casilla 160-C, Concepción (Chile); Vicencio, Rodrigo A. [Center for Optics and Photonics and MSI-Nucleus on Advanced Optics, Universidad de Concepción, Casilla 160-C, Concepción (Chile); Departamento de Física, Facultad de Ciencias, Universidad de Chile, Santiago (Chile)

    2016-09-16

    Highlights: • We study discrete two-dimensional breathers in dipolar Bose–Einstein Condensates. • Important differences in the properties of three fundamental modes are found. • Norm threshold for existence of 2D breathers varies with dipolar interaction. • The Effective Potential Method is implemented for stability analysis. • Uncommon mobility of 2D discrete solitons is observed. - Abstract: We analyze the existence and properties of discrete localized excitations in a Bose–Einstein condensate loaded into a periodic two-dimensional optical lattice, when a dipolar interaction between atoms is present. The dependence of the Number of Atoms (Norm) on the energy of solutions is studied, along with their stability. Two important features of the system are shown, namely, the absence of the Norm threshold required for localized solutions to exist in finite 2D systems, and the existence of regions in the parameter space where two fundamental solutions are simultaneously unstable. This feature enables mobility of localized solutions, which is an uncommon feature in 2D discrete nonlinear systems. With attractive dipolar interaction, a non-trivial behavior of the Norm dependence is obtained, which is well described by an analytical model.

  8. The structure of the interface in the solvent-mediated interaction of dipolar surfaces

    International Nuclear Information System (INIS)

    Dzhavakhidze, P.G.; Kornyshev, A.A.; Levadny, V.G.

    1988-01-01

    Interaction of two dipolar surfaces separated by a polar medium is considered within the framework of nonlocal electrostatics. The dipolar-surface layers are modelled as regular lattices with fixed orientation of dipoles which are immersed into the solvent; solvent response is characterized by nonlocal dielectric function. The model is elaborated in order to reveal the role of the dypolar-layer discreteness in the electric field produced by one surface and the interaction between two surfaces (which gives rise to the so-called ''hydration'' or ''structural'' force acting between mineral surfaces and phospholipid bilayers). The discreteness effects are present only for commensurate lattices. Their special mutual arrangement then may lead to considerable reduction of structural forces, viz. the usual repulsion regime may change at short distances to attraction. Conditions are considered when repulsion is entirely replaced by attraction, i.e. the ''hydration barrier'' disappears. In appended note it is discussed the role of solvation of surface dipolar groups. It is proposed an explanation of why two modes of decay (one with oscillative fine structure) may be present in the dependence of the force upon distance, if the surface dipolar groups are immersed deep enough in the solvent, and how the long-range oscillative mode disappears when the surface is but weakly solvated

  9. On the Gross–Pitaevskii equation for trapped dipolar quantum gases

    KAUST Repository

    Carles, Rémi

    2008-09-29

    We study the time-dependent Gross-Pitaevskii equation describing Bose-Einstein condensation of trapped dipolar quantum gases. Existence and uniqueness as well as the possible blow-up of solutions are studied. Moreover, we discuss the problem of dimension reduction for this nonlinear and nonlocal Schrödinger equation. © 2008 IOP Publishing Ltd and London Mathematical Society.

  10. Anisotropic relaxation dynamics in a dipolar Fermi gas driven out of equilibrium

    DEFF Research Database (Denmark)

    Aikawa, K.; Frisch, A.; Mark, M.

    2014-01-01

    We report on the observation of a large anisotropy in the rethermalization dynamics of an ultracold dipolar Fermi gas driven out of equilibrium. Our system consists of an ultracold sample of strongly magnetic $^{167}$Er fermions, spin-polarized in the lowest Zeeman sublevel. In this system, elastic...

  11. Simulating three dimensional self-assembly of shape modified particles using magnetic dipolar forces

    NARCIS (Netherlands)

    Alink, Laurens; Marsman, G.H. (Mathijs); Woldering, L.A.; Abelmann, Leon

    2011-01-01

    The feasibility of 3D self-assembly of milli-magnetic particles that interact via magnetic dipolar forces is investigated. Typically magnetic particles, such as isotropic spheres, self-organize in stable 2D configurations. By modifying the shape of the particles, 3D self-assembly may be enabled. The

  12. Micellar dipolar rearrangement is sensitive to hydrophobic chain length: Implication for structural switchover of piroxicam.

    Science.gov (United States)

    Sethy, Dasaratha; Chakraborty, Hirak

    2016-10-01

    The interfacial properties of the membrane are exceptionally vital in drug-membrane interaction. They not only select out a particular prototropic form of the drug molecule for incorporation, but are also potent enough to induce structural switchover of these drugs in several cases. In this work, we quantitatively monitored the change in dipolar rearrangement of the micellar interface (as a simplified membrane mimic) by measuring the dielectric constant and dipole potential with the micellization of SDS at pH 3.6. The dielectric constant and dipole potential were measured utilizing the fluorescence of polarity sensitive probe, pyrene and potential-sensitive probe, di-8-ANEPPS, respectively. Our study demonstrates that the change in dipolar rearrangement directly influences the switchover equilibrium between the anionic and neutral from of piroxicam. We have further extended our work to evaluate the effect of hydrophobic chain length of the surfactants on the dipolar rearrangement and its effect on the structural switchover of piroxicam. It is interesting that the extent of switchover of piroxicam is directly correlated with the dipolar rearrangement induced bythe varying hydrophobic chain length of the surfactants. To the best of our knowledge, our results constitute the first report to show the dependence of dipole potential on the hydrophobic chain length of the surfactant and demonstrate that the dipolar rearrangement directly tunes the extent of structural switchover of piroxicam, which was so far only intuitive. We consider that this new finding would have promising implication in drug distribution and drug efficacy. Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.

  13. The Plasma Sheet as Natural Symmetry Plane for Dipolarization Fronts in the Earth's Magnetotail

    Science.gov (United States)

    Frühauff, D.; Glassmeier, K.-H.

    2017-11-01

    In this work, observations of multispacecraft mission Time History of Events and Macroscale Interactions during Substorms are used for statistical investigation of dipolarization fronts in the near-Earth plasma sheet of the magnetotail. Using very stringent criteria, 460 events are detected in almost 10 years of mission data. Minimum variance analysis is used to determine the normal directions of the phase fronts, providing evidence for the existence of a natural symmetry of these phenomena, given by the neutral sheet of the magnetotail. This finding enables the definition of a local coordinate system based on the Tsyganenko model, reflecting the intrinsic orientation of the neutral sheet and, therefore, the dipolarization fronts. In this way, the comparison of events with very different background conditions is improved. Through this study, the statistical results of Liu, Angelopoulos, Runov, et al. (2013) are both confirmed and extended. In a case study, the knowledge of this plane of symmetry helps to explain the concave curvature of dipolarization fronts in the XZ plane through phase propagation speeds of magnetoacoustic waves. A second case study is presented to determine the central current system of a passing dipolarization front through a constellation of three spacecraft. With this information, a statistical analysis of spacecraft observations above and below the neutral sheet is used to provide further evidence for the neutral sheet as the symmetry plane and the central current system. Furthermore, it is shown that the signatures of dipolarization fronts are under certain conditions closely related to that of flux ropes, indicating a possible relationship between these two transient phenomena.

  14. Phenolic Amides Are Potent Inhibitors of De Novo Nucleotide Biosynthesis.

    Science.gov (United States)

    Pisithkul, Tippapha; Jacobson, Tyler B; O'Brien, Thomas J; Stevenson, David M; Amador-Noguez, Daniel

    2015-09-01

    An outstanding challenge toward efficient production of biofuels and value-added chemicals from plant biomass is the impact that lignocellulose-derived inhibitors have on microbial fermentations. Elucidating the mechanisms that underlie their toxicity is critical for developing strategies to overcome them. Here, using Escherichia coli as a model system, we investigated the metabolic effects and toxicity mechanisms of feruloyl amide and coumaroyl amide, the predominant phenolic compounds in ammonia-pretreated biomass hydrolysates. Using metabolomics, isotope tracers, and biochemical assays, we showed that these two phenolic amides act as potent and fast-acting inhibitors of purine and pyrimidine biosynthetic pathways. Feruloyl or coumaroyl amide exposure leads to (i) a rapid buildup of 5-phosphoribosyl-1-pyrophosphate (PRPP), a key precursor in nucleotide biosynthesis, (ii) a rapid decrease in the levels of pyrimidine biosynthetic intermediates, and (iii) a long-term generalized decrease in nucleotide and deoxynucleotide levels. Tracer experiments using (13)C-labeled sugars and [(15)N]ammonia demonstrated that carbon and nitrogen fluxes into nucleotides and deoxynucleotides are inhibited by these phenolic amides. We found that these effects are mediated via direct inhibition of glutamine amidotransferases that participate in nucleotide biosynthetic pathways. In particular, feruloyl amide is a competitive inhibitor of glutamine PRPP amidotransferase (PurF), which catalyzes the first committed step in de novo purine biosynthesis. Finally, external nucleoside supplementation prevents phenolic amide-mediated growth inhibition by allowing nucleotide biosynthesis via salvage pathways. The results presented here will help in the development of strategies to overcome toxicity of phenolic compounds and facilitate engineering of more efficient microbial producers of biofuels and chemicals. Copyright © 2015, Pisithkul et al.

  15. Phenolic Amides Are Potent Inhibitors of De Novo Nucleotide Biosynthesis

    Science.gov (United States)

    Pisithkul, Tippapha; Jacobson, Tyler B.; O'Brien, Thomas J.; Stevenson, David M.

    2015-01-01

    An outstanding challenge toward efficient production of biofuels and value-added chemicals from plant biomass is the impact that lignocellulose-derived inhibitors have on microbial fermentations. Elucidating the mechanisms that underlie their toxicity is critical for developing strategies to overcome them. Here, using Escherichia coli as a model system, we investigated the metabolic effects and toxicity mechanisms of feruloyl amide and coumaroyl amide, the predominant phenolic compounds in ammonia-pretreated biomass hydrolysates. Using metabolomics, isotope tracers, and biochemical assays, we showed that these two phenolic amides act as potent and fast-acting inhibitors of purine and pyrimidine biosynthetic pathways. Feruloyl or coumaroyl amide exposure leads to (i) a rapid buildup of 5-phosphoribosyl-1-pyrophosphate (PRPP), a key precursor in nucleotide biosynthesis, (ii) a rapid decrease in the levels of pyrimidine biosynthetic intermediates, and (iii) a long-term generalized decrease in nucleotide and deoxynucleotide levels. Tracer experiments using 13C-labeled sugars and [15N]ammonia demonstrated that carbon and nitrogen fluxes into nucleotides and deoxynucleotides are inhibited by these phenolic amides. We found that these effects are mediated via direct inhibition of glutamine amidotransferases that participate in nucleotide biosynthetic pathways. In particular, feruloyl amide is a competitive inhibitor of glutamine PRPP amidotransferase (PurF), which catalyzes the first committed step in de novo purine biosynthesis. Finally, external nucleoside supplementation prevents phenolic amide-mediated growth inhibition by allowing nucleotide biosynthesis via salvage pathways. The results presented here will help in the development of strategies to overcome toxicity of phenolic compounds and facilitate engineering of more efficient microbial producers of biofuels and chemicals. PMID:26070680

  16. Contrasting dynamics of electrons and protons in the near-Earth plasma sheet during dipolarization

    Science.gov (United States)

    Malykhin, Andrey Y.; Grigorenko, Elena E.; Kronberg, Elena A.; Koleva, Rositza; Ganushkina, Natalia Y.; Kozak, Ludmila; Daly, Patrick W.

    2018-05-01

    The fortunate location of Cluster and the THEMIS P3 probe in the near-Earth plasma sheet (PS) (at X ˜ -7-9 RE) allowed for the multipoint analysis of properties and spectra of electron and proton injections. The injections were observed during dipolarization and substorm current wedge formation associated with braking of multiple bursty bulk flows (BBFs). In the course of dipolarization, a gradual growth of the BZ magnetic field lasted ˜ 13 min and it was comprised of several BZ pulses or dipolarization fronts (DFs) with duration ≤ 1 min. Multipoint observations have shown that the beginning of the increase in suprathermal ( > 50 keV) electron fluxes - the injection boundary - was observed in the PS simultaneously with the dipolarization onset and it propagated dawnward along with the onset-related DF. The subsequent dynamics of the energetic electron flux was similar to the dynamics of the magnetic field during the dipolarization. Namely, a gradual linear growth of the electron flux occurred simultaneously with the gradual growth of the BZ field, and it was comprised of multiple short ( ˜ few minutes) electron injections associated with the BZ pulses. This behavior can be explained by the combined action of local betatron acceleration at the BZ pulses and subsequent gradient drifts of electrons in the flux pile up region through the numerous braking and diverting DFs. The nonadiabatic features occasionally observed in the electron spectra during the injections can be due to the electron interactions with high-frequency electromagnetic or electrostatic fluctuations transiently observed in the course of dipolarization. On the contrary, proton injections were detected only in the vicinity of the strongest BZ pulses. The front thickness of these pulses was less than a gyroradius of thermal protons that ensured the nonadiabatic acceleration of protons. Indeed, during the injections in the energy spectra of protons the pronounced bulge was clearly observed in a

  17. On the unconventional amide I band in acetanilide

    Science.gov (United States)

    Tenenbaum, Alexander; Campa, Alessandro; Giansanti, Andrea

    1987-04-01

    We developed a new model to study the molecular dynamics of the acetanilide (ACN) crystal by computer simulation. Low-frequency oscillations of the molecules as a whole were considered with high-frequency vibrations of the amidic degrees of freedom involved in hydrogen bonding. The low-temperature power spectrum has two peaks, shifted by 15 cm -1, in the region of the amide I band: one of them corresponds to the so-called anomalous amide I band in the IR and Raman spectra of ACN. We found that this peak is due to the coupling of the low-frequency motion in the chain of molecules with the motion of the hydrogen-bonded protons, at variance with current suggestions.

  18. TROSY of side-chain amides in large proteins

    Science.gov (United States)

    Liu, Aizhuo; Yao, Lishan; Li, Yue; Yan, Honggao

    2012-01-01

    By using the mixed solvent of 50% H2O/50% D2O and employing deuterium decoupling, TROSY experiments exclusively detect NMR signals from semideuterated isotopomers of carboxamide groups with high sensitivities for proteins with molecular weights up to 80 kDa. This isotopomer-selective strategy extends TROSY experiments from exclusively detecting backbone to both backbone and side-chain amides, particularly in large proteins. Because of differences in both TROSY effect and dynamics between 15N–HE{DZ} and 15N–HZ{DE} isotopomers of the same carboxamide, the 15N transverse magnetization of the latter relaxes significantly faster than that of the former, which provides a direct and reliable stereospecific distinction between the two configurations. The TROSY effects on the 15N–HE{DZ} isotopomers of side-chain amides are as significant as on backbone amides. PMID:17347000

  19. The radiation chemistry of organic amides: Pt. 1

    International Nuclear Information System (INIS)

    Langan, J.R.; Liu, K.J.; Salmon, G.A.; Edwards, P.P.; Ellaboudy, A.; Holton, D.M.

    1989-01-01

    Pulse radiolysis of four cyclic amides including N-methylpyrrolidinone (NMP), and the non-cyclic amide tetramethylurea (TMU) yielded absorption spectra in the near infrared that are attributed to solvated electrons. Addition of a variety of alkali-metal salts caused no detectable change in the absorption spectrum of e s - and no new absorptions attributable to alkali-metal anions were detected. The effect of dose on the decay of e s - in NMP was studied in detail. The yields of e s - in these amides were estimated by using trans-stilbene as an electron scavenger. Absorption spectra, which are not removed by saturation with N 2 O and CO 2 , are observed in the wavelength range 300-500 nm. (author)

  20. VCD Robustness of the Amide-I and Amide-II Vibrational Modes of Small Peptide Models.

    Science.gov (United States)

    Góbi, Sándor; Magyarfalvi, Gábor; Tarczay, György

    2015-09-01

    The rotational strengths and the robustness values of amide-I and amide-II vibrational modes of For(AA)n NHMe (where AA is Val, Asn, Asp, or Cys, n = 1-5 for Val and Asn; n = 1 for Asp and Cys) model peptides with α-helix and β-sheet backbone conformations were computed by density functional methods. The robustness results verify empirical rules drawn from experiments and from computed rotational strengths linking amide-I and amide-II patterns in the vibrational circular dichroism (VCD) spectra of peptides with their backbone structures. For peptides with at least three residues (n ≥ 3) these characteristic patterns from coupled amide vibrational modes have robust signatures. For shorter peptide models many vibrational modes are nonrobust, and the robust modes can be dependent on the residues or on their side chain conformations in addition to backbone conformations. These robust VCD bands, however, provide information for the detailed structural analysis of these smaller systems. © 2015 Wiley Periodicals, Inc.

  1. Exposure of Mn and FeSODs, but not Cu/ZnSOD, to NO leads to nitrosonium and nitroxyl ions generation which cause enzyme modification and inactivation: an in vitro study.

    Science.gov (United States)

    Niketíc, V; Stojanović, S; Nikolić, A; Spasić, M; Michelson, A M

    1999-11-01

    The effect of NO treatment in vitro on structural and functional alterations of Cu/Zn, Mn, and Fe type of SODs was studied. Significant difference in response to NO of Cu/ZnSOD compared to the Mn and Fe types was demonstrated. Cu/ZnSOD was shown to be stable with respect to NO: even on prolonged exposure, NO produced negligible effect on its structure and activity. In contrast, both Mn and Fe types were found to be NO-sensitive: exposure to NO led to their fast and extensive inactivation, which was accompanied by extensive structural alterations, including (in some of the samples tested) the cleavage of enzyme polypeptide chains, presumably at His residues of the enzyme metal binding sites. The generation of nitrosonium (NO+) and nitroxyl (NO-) ions in NO treated Mn and FeSODs, which produce enzyme modifications and inactivation, was demonstrated. The physiological and biomedical significance of described findings is briefly discussed.

  2. Biosynthesis of amidated joining peptide from pro-adrenocorticotropin-endorphin

    Energy Technology Data Exchange (ETDEWEB)

    Cullen, E.I.; Mains, R.E. (Johns Hopkins Univ. School of Medicine, Baltimore, MD (USA))

    1987-09-01

    Joining peptide is the major alpha-amidated product of pro-ACTH/endorphin (PAE) in AtT-20 corticotropic tumor cells. To study intracellular joining peptide synthesis, affinity purified antibodies directed against gamma-MSH, joining peptide, and ACTH were used to immunoprecipitate extracts from biosynthetically labeled AtT-20 cells. Immunoprecipitates were analyzed by sodium dodecyl sulfate-polyacrylamide gel electrophoresis and by tryptic peptide mapping on HPLC. In steady labeling experiments, radioactivity in amidated joining peptide (JP) increased roughly linearly with time, in the manner of a final product, whereas radioactivity associated with PAE (1-94)NH2 reached a constant value after 2-4 h, indicating that PAE(1-94)NH2 is an intermediate in the biosynthesis of JP. Radioactivity appeared in ACTH(1-39) well before JP, consistent with a cleavage order in which ACTH is cleaved from PAE(1-95) before JP sequences are cleaved from PAE(1-74). This conclusion was supported by tryptic peptide analyses of immunoprecipitates, which indicated that less than 5% of JP-related material is cleaved from PAE(1-74) before being cleaved from ACTH-related sequences. After a pulse label, radioactivity in PAE(1-94)NH2 reached a peak value after 1 h of chase and declined with a half-life of less than 1 h. Amidated JP increased to a constant level after 2 h of chase. Enough radiolabeled PAE(1-94)NH2 was detected to account for about half of the radioactivity found in amidated JP, indicating that about half of JP-related material is first cleaved from PAE(1-95) before being amidated. This result was corroborated using HPLC purification to determine both amidated and glycine-extended forms of JP.

  3. Biosynthesis of amidated joining peptide from pro-adrenocorticotropin-endorphin

    International Nuclear Information System (INIS)

    Cullen, E.I.; Mains, R.E.

    1987-01-01

    Joining peptide is the major alpha-amidated product of pro-ACTH/endorphin (PAE) in AtT-20 corticotropic tumor cells. To study intracellular joining peptide synthesis, affinity purified antibodies directed against gamma-MSH, joining peptide, and ACTH were used to immunoprecipitate extracts from biosynthetically labeled AtT-20 cells. Immunoprecipitates were analyzed by sodium dodecyl sulfate-polyacrylamide gel electrophoresis and by tryptic peptide mapping on HPLC. In steady labeling experiments, radioactivity in amidated joining peptide (JP) increased roughly linearly with time, in the manner of a final product, whereas radioactivity associated with PAE (1-94)NH2 reached a constant value after 2-4 h, indicating that PAE(1-94)NH2 is an intermediate in the biosynthesis of JP. Radioactivity appeared in ACTH(1-39) well before JP, consistent with a cleavage order in which ACTH is cleaved from PAE(1-95) before JP sequences are cleaved from PAE(1-74). This conclusion was supported by tryptic peptide analyses of immunoprecipitates, which indicated that less than 5% of JP-related material is cleaved from PAE(1-74) before being cleaved from ACTH-related sequences. After a pulse label, radioactivity in PAE(1-94)NH2 reached a peak value after 1 h of chase and declined with a half-life of less than 1 h. Amidated JP increased to a constant level after 2 h of chase. Enough radiolabeled PAE(1-94)NH2 was detected to account for about half of the radioactivity found in amidated JP, indicating that about half of JP-related material is first cleaved from PAE(1-95) before being amidated. This result was corroborated using HPLC purification to determine both amidated and glycine-extended forms of JP

  4. Isentropic compressibilities of (amide + water) mixtures: A comparative study

    International Nuclear Information System (INIS)

    Papamatthaiakis, Dimitris; Aroni, Fryni; Havredaki, Vasiliki

    2008-01-01

    The density and ultrasonic velocity of aqueous solutions of formamide (FA), N-methylformamide (NMF), N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMA), pyrrolidin-2-one (PYR), N-methyl-2-pyrrolidinone (NMP), and their pure phases have been measured at 298.15 K and atmospheric pressure. Densities and ultrasonic velocities in pure amides have been also measured at the temperature range 288.15 K to 308.15 K for the computation of their thermal expansivities. Isentropic compressibility, intermolecular free length, relative association, apparent molar compressibility, as well as the excess quantities, ultrasonic velocity, isentropic compressibility, intermolecular free length, have been evaluated and fitted to the Redlich-Kister type equation. The deviation from ideal mixing law in ultrasonic velocity is positive while the deviations in isentropic compressibility and intermolecular free length are negative for all (amide + water) mixtures. This behavior reveals the nature and the magnitude of intermolecular interactions between the amide-water molecules. The sequence of superimposed curves of various ultrasonic parameters vs. the amide mole fraction is related to the strength of interactions between the unlike molecules and the role of -CH 3 substitution in amides. The comparison of ultrasonic to volumetric properties reveals differences on the position of the extrema and their relation with the degree of substitution while the interpretation of these differences is discussed. Two different approaches on the computation of excess functions, applied in this work, brought out a difference in the magnitude of deviations and a partial reversion to the sequence of amides curves suggesting a different estimation in terms of deviations from ideal mixing law and therefore of the relative molecular interactions

  5. 1,3-Dipolar cycloaddition reactions of nitrile oxides in the synthesis of natural compounds and their analogues

    International Nuclear Information System (INIS)

    Kotyatkina, Anna I; Zhabinsky, Vladimir N; Khripach, Vladimir A

    2001-01-01

    The published data on the use of 1,3-dipolar cycloaddition reactions of nitrile oxides in the synthesis of natural compounds and their analogues are systematised and reviewed. The bibliography includes 145 references.

  6. The temperature dependent amide I band of crystalline acetanilide

    International Nuclear Information System (INIS)

    Cruzeiro, Leonor; Freedman, Holly

    2013-01-01

    The temperature dependent anomalous peak in the amide I band of crystalline acetanilide is thought to be due to self-trapped states. On the contrary, according to the present model, the anomalous peak comes from the fraction of ACN molecules strongly hydrogen-bonded to a neighboring ACN molecule, and its intensity decreases because, on average, this fraction decreases as temperature increases. This model provides, for the first time, an integrated and theoretically consistent view of the temperature dependence of the full amide I band and a qualitative explanation of some of the features of nonlinear pump–probe experiments.

  7. Synthesis and antituberculosis activity of new fatty acid amides.

    Science.gov (United States)

    D'Oca, Caroline Da Ros Montes; Coelho, Tatiane; Marinho, Tamara Germani; Hack, Carolina Rosa Lopes; Duarte, Rodrigo da Costa; da Silva, Pedro Almeida; D'Oca, Marcelo Gonçalves Montes

    2010-09-01

    This work reports the synthesis of new fatty acid amides from C16:0, 18:0, 18:1, 18:1 (OH), and 18:2 fatty acids families with cyclic and acyclic amines and demonstrate for the first time the activity of these compounds as antituberculosis agents against Mycobacterium tuberculosis H(37)Rv, M. tuberculosis rifampicin resistance (ATCC 35338), and M. tuberculosis isoniazid resistance (ATCC 35822). The fatty acid amides derivate from ricinoleic acid were the most potent one among a series of tested compounds, with a MIC 6.25 microg/mL for resistance strains. Copyright 2010 Elsevier Ltd. All rights reserved.

  8. The temperature dependent amide I band of crystalline acetanilide

    Energy Technology Data Exchange (ETDEWEB)

    Cruzeiro, Leonor [CCMAR, Universidade do Algarve, Campus de Gambelas, 8005-139 Faro (Portugal); Physics Department, FCT, Universidade do Algarve, Campus de Gambelas, 8005-139 Faro (Portugal); Freedman, Holly [CCMAR, Universidade do Algarve, Campus de Gambelas, 8005-139 Faro (Portugal)

    2013-10-01

    The temperature dependent anomalous peak in the amide I band of crystalline acetanilide is thought to be due to self-trapped states. On the contrary, according to the present model, the anomalous peak comes from the fraction of ACN molecules strongly hydrogen-bonded to a neighboring ACN molecule, and its intensity decreases because, on average, this fraction decreases as temperature increases. This model provides, for the first time, an integrated and theoretically consistent view of the temperature dependence of the full amide I band and a qualitative explanation of some of the features of nonlinear pump–probe experiments.

  9. The temperature dependent amide I band of crystalline acetanilide

    Science.gov (United States)

    Cruzeiro, Leonor; Freedman, Holly

    2013-10-01

    The temperature dependent anomalous peak in the amide I band of crystalline acetanilide is thought to be due to self-trapped states. On the contrary, according to the present model, the anomalous peak comes from the fraction of ACN molecules strongly hydrogen-bonded to a neighboring ACN molecule, and its intensity decreases because, on average, this fraction decreases as temperature increases. This model provides, for the first time, an integrated and theoretically consistent view of the temperature dependence of the full amide I band and a qualitative explanation of some of the features of nonlinear pump-probe experiments.

  10. Direct Reaction of Amides with Nitric Oxide To Form Diazeniumdiolates

    Science.gov (United States)

    2015-01-01

    We report the apparently unprecedented direct reaction of nitric oxide (NO) with amides to generate ions of structure R(C=O)NH–N(O)=NO–, with examples including R = Me (1a) or 3-pyridyl (1b). The sodium salts of both released NO in pH 7.4 buffer, with 37 °C half-lives of 1–3 min. As NO-releasing drug candidates, diazeniumdiolated amides would have the advantage of generating only 1 equiv of base on hydrolyzing exhaustively to NO, in contrast to their amine counterparts, which generate 2 equiv of base. PMID:25210948

  11. Multicomponent synthesis of spiropyrrolidine analogues derived from vinylindole/indazole by a 1,3-dipolar cycloaddition reaction

    Directory of Open Access Journals (Sweden)

    Manjunatha Narayanarao

    2016-12-01

    Full Text Available A new series of spiropyrrolidine compounds containing indole/indazole moieties as side chains have been accomplished via a one-pot multicomponent synthesis. The method uses the 1,3-dipolar cycloaddition reaction between N-alkylvinylindole/indazole and azomethine ylides, prepared in situ from cyclic/acyclic amino acids. The 1,3-dipolar cycloaddition proceeds efficiently under thermal conditions to afford the regio- and stereospecific cyclic adducts.

  12. Non-dipolar gauge links for transverse-momentum-dependent pion wave functions

    International Nuclear Information System (INIS)

    Wang, Y.M.

    2016-01-01

    I discuss the factorization-compatible definitions of transverse-momentum-dependent (TMD) pion wave functions which are fundamental theory inputs entering QCD factorization formulae for many hard exclusive processes. I will first demonstrate that the soft subtraction factor introduced to remove both rapidity and pinch singularities can be greatly reduced by making the maximal use of the freedom to construct the Wilson-line paths when defining the TMD wave functions. I will then turn to show that the newly proposed TMD definition with non-dipolar Wilson lines is equivalent to the one with dipolar gauge links and with a complicated soft function, to all orders of the perturbative expansion in the strong coupling, as far as the infrared behavior is concerned. (author)

  13. Determination of protein global folds using backbone residual dipolar coupling and long-range NOE restraints

    International Nuclear Information System (INIS)

    Giesen, Alexander W.; Homans, Steve W.; Brown, Jonathan Miles

    2003-01-01

    We report the determination of the global fold of human ubiquitin using protein backbone NMR residual dipolar coupling and long-range nuclear Overhauser effect (NOE) data as conformational restraints. Specifically, by use of a maximum of three backbone residual dipolar couplings per residue (N i -H N i , N i -C' i-1 , H N i - C' i-1 ) in two tensor frames and only backbone H N -H N NOEs, a global fold of ubiquitin can be derived with a backbone root-mean-square deviation of 1.4 A with respect to the crystal structure. This degree of accuracy is more than adequate for use in databases of structural motifs, and suggests a general approach for the determination of protein global folds using conformational restraints derived only from backbone atoms

  14. Two dimensional dipolar coupling in monolayers of silver and gold nanoparticles on a dielectric substrate.

    Science.gov (United States)

    Liu, Yu; Begin-Colin, Sylvie; Pichon, Benoît P; Leuvrey, Cedric; Ihiawakrim, Dris; Rastei, Mircea; Schmerber, Guy; Vomir, Mircea; Bigot, Jean Yves

    2014-10-21

    The dimensionality of assembled nanoparticles plays an important role in their optical and magnetic properties, via dipolar effects and the interaction with their environment. In this work we develop a methodology for distinguishing between two (2D) and three (3D) dimensional collective interactions on the surface plasmon resonance of assembled metal nanoparticles. Towards that goal, we elaborate different sets of Au and Ag nanoparticles as suspensions, random 3D arrangements and well organized 2D arrays. Then we model their scattering cross-section using effective field methods in dimension n, including interparticle as well as particle-substrate dipolar interactions. For this modelling, two effective field medium approaches are employed, taking into account the filling factors of the assemblies. Our results are important for realizing photonic amplifier devices.

  15. Arrays of dipolar molecular rotors in Tris(o-phenylenedioxy) cyclotriphosphazene.

    Science.gov (United States)

    Zhao, Ke; Dron, Paul I; Kaleta, Jiří; Rogers, Charles T; Michl, Josef

    2014-01-01

    Regular two-dimensional or three-dimensional arrays of mutually interacting dipolar molecular rotors represent a worthy synthetic objective. Their dielectric properties, including possible collective behavior, will be a sensitive function of the location of the rotors, the orientation of their axes, and the size of their dipoles. Host-guest chemistry is one possible approach to gaining fine control over these factors. We describe the progress that has been achieved in recent years using tris (o-phenylenedioxy)cyclotriphosphazene as a host and a series of rod-shaped dipolar molecular rotors as guests. Structures of both surface and bulk inclusion compounds have been established primarily by solid-state nuclear magnetic resonance (NMR) and powder X-ray diffraction (XRD) techniques. Low-temperature dielectric spectroscopy revealed rotational barriers as low as 1.5 kcal/mol, but no definitive evidence for collective behavior has been obtained so far.

  16. Strongly scale-dependent CMB dipolar asymmetry from super-curvature fluctuations

    Energy Technology Data Exchange (ETDEWEB)

    Byrnes, Christian [Department of Physics and Astronomy, University of Sussex, Brighton BN1 9QH (United Kingdom); Domènech, Guillem; Sasaki, Misao [Center for Gravitational Physics, Yukawa Institute for Theoretical Physics, Kyoto University, Kyoto 606-8502 (Japan); Takahashi, Tomo, E-mail: C.Byrnes@sussex.ac.uk, E-mail: guillem.domenech@yukawa.kyoto-u.ac.jp, E-mail: misao@yukawa.kyoto-u.ac.jp, E-mail: tomot@cc.saga-u.ac.jp [Department of Physics, Saga University, Saga 840-8502 (Japan)

    2016-12-01

    We reconsider the observed CMB dipolar asymmetry in the context of open inflation, where a supercurvature mode might survive the bubble nucleation. If such a supercurvature mode modulates the amplitude of the curvature power spectrum, it would easily produce an asymmetry in the power spectrum. We show that current observational data can be accommodated in a three-field model, with simple quadratic potentials and a non-trivial field-space metric. Despite the presence of three fields, we believe this model is so far the simplest that can match current observations. We are able to match the observed strong scale dependence of the dipolar asymmetry, without a fine tuning of initial conditions, breaking slow roll or adding a feature to the evolution of any field.

  17. Low-loss metamaterial electromagnetically induced transparency based on electric toroidal dipolar response

    Energy Technology Data Exchange (ETDEWEB)

    Li, Hai-ming; Liu, Shao-bin, E-mail: lsb@nuaa.edu.cn; Liu, Si-yuan; Ding, Guo-wen; Yang, Hua; Yu, Zhi-yang; Zhang, Hai-feng [Key Laboratory of Radar Imaging and Microwave Photonics, Nanjing University of Aeronautics and Astronautics, Nanjing, 210016 (China); Wang, Shen-yun [Research Center of Applied Electromagnetic, Nanjing University of Information Science and Technology, Nanjing, 210044 (China)

    2015-02-23

    In this paper, a low-loss and high transmission analogy of electromagnetically induced transparency based on electric toroidal dipolar response is numerically and experimentally demonstrated. It is obtained by the excitation of the low-loss electric toroidal dipolar response, which confines the magnetic field inside a dielectric substrate with toroidal geometry. The metamaterial electromagnetically induced transparency (EIT) structure is composed of the cut wire and asymmetric split-ring resonators. The transmission level is as high as 0.88, and the radiation loss is greatly suppressed, which can be proved by the surface currents distributions, the magnetic field distributions, and the imaginary parts of the effective permeability and permittivity. It offers an effective way to produce low-loss and high transmission metamaterial EIT.

  18. Quantum-well exciton dipolar interaction: Polarization-dependence and Z-LT splitting

    International Nuclear Information System (INIS)

    Nguyen Ba An.

    1996-12-01

    We calculate the exciton dipolar interaction in a semiconductor quantum well. The explicit polarization-dependence, i.e, the dependence on both the exciton dipole moment μ-vector and its inplane wavevector k-vector is derived. The obtained results for the three modes (L, T and Z modes) of the long-range part of the dipolar interaction satisfy the polarization sum rule for any parameters. In the long wavelength limit there is a Z-LT splitting which decreases as the well width increases reflecting a crossover from strict 2D to quasi-2D. A rough crossover from quasi-2D to 3D is also described. (author). 18 refs, 4 figs

  19. Direct Observation of Field and Temperature Induced Domain Replication in Dipolar Coupled Perpendicular Anisotropy Films

    Energy Technology Data Exchange (ETDEWEB)

    Hauet, T.; Gunther, C.M.; Pfau, B.; Eisebitt, S.; Fischer, P.; Rick, R. L.; Thiele, J.-U.; Hellwig, O.; Schabes, M.E.

    2007-07-01

    Dipolar interactions in a soft/Pd/hard [CoNi/Pd]{sub 30}/Pd/[Co/Pd]{sub 20} multilayer system, where a thick Pd layer between two ferromagnetic units prevents direct exchange coupling, are directly revealed by combining magnetometry and state-of-the-art layer resolving soft x-ray imaging techniques with sub-100-nm spatial resolution. The domains forming in the soft layer during external magnetic field reversal are found to match the domains previously trapped in the hard layer. The low Curie temperature of the soft layer allows varying its intrinsic parameters via temperature and thus studying the competition with dipolar fields due to the domains in the hard layer. Micromagnetic simulations elucidate the role of [CoNi/Pd] magnetization, exchange, and anisotropy in the duplication process. Finally, thermally driven domain replication in remanence during temperature cycling is demonstrated.

  20. Critical behaviour of nanocrystalline gadolinium: evidence for random uniaxial dipolar universality class

    International Nuclear Information System (INIS)

    Ferdinand, A; Probst, A-C; Birringer, R; Michels, A; Kaul, S N

    2014-01-01

    We report on how nanocrystal size affects the critical behaviour of the rare-earth metal Gd near the ferromagnetic-to-paramagnetic phase transition. The asymptotic critical behaviour of the coarse-grained polycrystalline sample (with an average crystallite size of L≅100 μm) is that of a (pure) uniaxial dipolar ferromagnet, as is the case with single crystal Gd, albeit the width of the asymptotic critical region (ACR) is reduced. As the grain size approaches ∼30 nm, the ACR is so narrow that it could not be accessed in the present experiments. Inaccessibly narrow ACR for L ∼ 30 nm and continuous increase in the width of the ACR as L decreases from 16 to 9.5 nm basically reflect a crossover to the random uniaxial dipolar fixed point caused by the quenched random exchange disorder prevalent at the internal interfaces (grain boundaries). (paper)

  1. Partial alignment and measurement of residual dipolar couplings of proteins under high hydrostatic pressure

    Energy Technology Data Exchange (ETDEWEB)

    Fu, Yinan; Wand, A. Joshua, E-mail: wand@mail.med.upenn.edu [University of Pennsylvania, Department of Biochemistry and Biophysics, Johnson Research Foundation (United States)

    2013-08-15

    High-pressure NMR spectroscopy has emerged as a complementary approach for investigating various structural and thermodynamic properties of macromolecules. Noticeably absent from the array of experimental restraints that have been employed to characterize protein structures at high hydrostatic pressure is the residual dipolar coupling, which requires the partial alignment of the macromolecule of interest. Here we examine five alignment media that are commonly used at ambient pressure for this purpose. We find that the spontaneous alignment of Pf1 phage, d(GpG) and a C12E5/n-hexnanol mixture in a magnetic field is preserved under high hydrostatic pressure. However, DMPC/DHPC bicelles and collagen gel are found to be unsuitable. Evidence is presented to demonstrate that pressure-induced structural changes can be identified using the residual dipolar coupling.

  2. Amides Do Not Always Work: Observation of Guest Binding in an Amide-Functionalized Porous Metal-Organic Framework.

    Science.gov (United States)

    Benson, Oguarabau; da Silva, Ivan; Argent, Stephen P; Cabot, Rafel; Savage, Mathew; Godfrey, Harry G W; Yan, Yong; Parker, Stewart F; Manuel, Pascal; Lennox, Matthew J; Mitra, Tamoghna; Easun, Timothy L; Lewis, William; Blake, Alexander J; Besley, Elena; Yang, Sihai; Schröder, Martin

    2016-11-16

    An amide-functionalized metal organic framework (MOF) material, MFM-136, shows a high CO 2 uptake of 12.6 mmol g -1 at 20 bar and 298 K. MFM-136 is the first example of an acylamide pyrimidyl isophthalate MOF without open metal sites and, thus, provides a unique platform to study guest binding, particularly the role of free amides. Neutron diffraction reveals that, surprisingly, there is no direct binding between the adsorbed CO 2 /CH 4 molecules and the pendant amide group in the pore. This observation has been confirmed unambiguously by inelastic neutron spectroscopy. This suggests that introduction of functional groups solely may not necessarily induce specific guest-host binding in porous materials, but it is a combination of pore size, geometry, and functional group that leads to enhanced gas adsorption properties.

  3. A facile regioselective synthesis of novel spiroacenaphthene pyrroloisoquinolines through 1,3-dipolar cycloaddition reactions

    International Nuclear Information System (INIS)

    Sarrafi, Yaghoub; Asghari, Asieh; Sadatshahabi, Marzieh; Hamzehloueian, Mahshid; Alimohammadi, Kamal

    2013-01-01

    An efficient one-pot three-component procedure for the synthesis of novel spiroacenaphthene pyrroloisoquinolines with high regioselectivity is described. These compounds were prepared from 1,3-dipolar cycloaddition of an azomethine ylide generated from acenaphthenequinone and 1,2,3,4-tetrahydroisoquinoline via [1,5]-H shift, with chalcone and nitrostyrene derivatives as dipolarophiles. The structure and stereochemistry of the cycloadducts have been established by single crystal X-ray structure and spectroscopic techniques. (author)

  4. Scaling parallels in the non-Debye dielectric relaxation of ionic glasses and dipolar supercooled liquids

    International Nuclear Information System (INIS)

    Sidebottom, D.L.; Green, P.F.; Brow, R.K.

    1997-01-01

    We compare the dielectric response of ionic glasses and dipolar liquids near the glass transition. Our work is divided into two parts. In the first section we examine ionic glasses and the two prominent approaches to analyzing the dielectric response. The conductivity of ion-conducting glasses displays a power law dispersion σ(ω)∝ω n , where n∼0.67, but frequently the dielectric response is analyzed using the electrical modulus M * (ω)=1/var-epsilon * (ω), where var-epsilon * (ω)=var-epsilon(ω)-iσ(ω)/ω is the complex permittivity. We reexamine two specific examples where the shape of M * (ω) changes in response to changes in (a) temperature and (b) ion concentration, to suggest fundamental changes in ion dynamics are occurring. We show, however, that these changes in the shape of M * (ω) occur in the absence of changes in the scaling properties of σ(ω), for which n remains constant. In the second part, we examine the dielectric relaxation found in dipolar liquids, for which var-epsilon * (ω) likewise exhibits changes in shape on approach to the glass transition. Guided by similarities of M * (ω) in ionic glasses and var-epsilon * (ω) in dipolar liquids, we demonstrate that a recent scaling approach proposed by Dixon and co-workers for var-epsilon * (ω) of dipolar relaxation also appears valid for M * (ω) in the ionic case. While this suggests that the Dixon scaling approach is more universal than previously recognized, we demonstrate how the dielectric response can be scaled in a linear manner using an alternative data representation. copyright 1997 The American Physical Society

  5. Enantioselective 1,3-dipolar cycloadditions of diazoacetates with electron-deficient olefins.

    Science.gov (United States)

    Sibi, Mukund P; Stanley, Levi M; Soeta, Takahiro

    2007-04-12

    [reaction: see text] A general strategy for highly enantioselective 1,3-dipolar cycloaddition of diazoesters to beta-substituted, alpha-substituted, and alpha,beta-disubstituted alpha,beta-unsaturated pyrazolidinone imides is described. Cycloadditions utilizing less reactive alpha,beta-disubstituted dipolarophiles require elevated reaction temperatures, but still provide the corresponding pyrazolines with excellent enantioselectivities. Finally, an efficient synthesis of (-)-manzacidin A employing this cycloaddition methodology as a key step is illustrated.

  6. NMR studies on 1,3-dipolar cycloaddition of nitrile oxides to norbornenes

    International Nuclear Information System (INIS)

    Gucma, Mirosław; Gołębiewski, W. Marek; Krawczyk, Maria

    2013-01-01

    The 1,3-dipolar cycloaddition reaction of nitrile oxides to norbornenes substituted with an acrylate-derived moiety was examined. Only adducts to norbornene system were formed with a good exo selectivity and complete site-selectivity. Structures of the products were elucidated by an extensive application of electrospray ionization-mass spectrometry (ESI-MS) and 2D 1 H and 13 C nuclear magnetic resonance (NMR). (author)

  7. On nonlinear dynamics of a dipolar exciton BEC in two-layer graphene

    International Nuclear Information System (INIS)

    Berman, O.L.; Kezerashvili, R.Ya.; Kolmakov, G.V.

    2012-01-01

    The nonlinear dynamics of a Bose–Einstein condensate (BEC) of dipolar excitons in two-layer graphene is studied. It is demonstrated that a steady turbulent state is formed in this system. A comparison between the dynamics of the exciton BEC in two-layer graphene and those in GaAs/AlGaAs coupled quantum wells shows that turbulence is a general effect in a BEC.

  8. The role of magnetic field fluctuations in nonadiabatic acceleration of ions during dipolarization

    Science.gov (United States)

    Ono, Y.; Nosé, M.; Christon, S. P.; Lui, A. T. Y.

    2009-05-01

    We statistically examine changes in the composition of two different ion species, proton and oxygen ions, in the near-Earth plasma sheet (X = -16 R E ˜ -6 R E ) during substorm-associated dipolarization. We use 10 years of energetic (9-212 keV/e) ion data obtained by the suprathermal ion composition spectrometer (STICS) sensor of the energetic particles and ion composition (EPIC) instrument on board the Geotail spacecraft. The results are as follows: (1) Although the percentage increase in the energy density of O+ ions before and after a dipolarization exceeds that of H+ ions in the low-energy range (9-36 keV/e), this property is not evident in the high-energy range (56-212 keV/e); (2) the energy spectrum of H+ and that of O+ become harder after dipolarization in almost all events; and (3) in some events the energy spectrum of O+ becomes harder than that of H+ as reported by previous studies, and, importantly, in other events, the spectrum of H+ becomes harder than that of O+. In order to investigate what mechanism causes these observational results, we focus on magnetic field fluctuations during dipolarization. It is found that the increase of the spectrum slope is positively correlated with the power of waves whose frequencies are close to the gyrofrequency of H+ or O+, respectively (the correlation coefficient is 0.48 for H+ and 0.68 for O+). In conclusion, ions are nonadiabatically accelerated by the electric field induced by the magnetic field fluctuations whose frequencies are close to their gyrofrequencies.

  9. Long-range dipolar order and dispersion forces in polar liquids

    Science.gov (United States)

    Besford, Quinn Alexander; Christofferson, Andrew Joseph; Liu, Maoyuan; Yarovsky, Irene

    2017-11-01

    Complex solvation phenomena, such as specific ion effects, occur in polar liquids. Interpretation of these effects in terms of structure and dispersion forces will lead to a greater understanding of solvation. Herein, using molecular dynamics, we probe the structure of polar liquids through specific dipolar pair correlation functions that contribute to the potential of mean force that is "felt" between thermally rotating dipole moments. It is shown that unique dipolar order exists at separations at least up to 20 Å for all liquids studied. When the structural order is compared with a dipolar dispersion force that arises from local co-operative enhancement of dipole moments, a strong agreement is found. Lifshitz theory of dispersion forces was compared with the structural order, where the theory is validated for all liquids that do not have significant local dipole correlations. For liquids that do have significant local dipole correlations, specifically liquid water, Lifshitz theory underestimates the dispersion force by a factor of 5-10, demonstrating that the force that leads to the increased structure in liquid water is missed by Lifshitz theory of van der Waals forces. We apply similar correlation functions to an ionic aqueous system, where long-range order between water's dipole moment and a single chloride ion is found to exist at 20 Å of separation, revealing a long-range perturbation of water's structure by an ion. Furthermore, we found that waters within the 1st, 2nd, and 3rd solvation shells of a chloride ion exhibit significantly enhanced dipolar interactions, particularly with waters at larger distances of separation. Our results provide a link between structures, dispersion forces, and specific ion effects, which may lead to a more robust understanding of solvation.

  10. NMR studies on 1,3-dipolar cycloaddition of nitrile oxides to norbornenes

    Energy Technology Data Exchange (ETDEWEB)

    Gucma, Miroslaw; Golebiewski, W. Marek; Krawczyk, Maria, E-mail: golebiewski@ipo.waw.pl [Institute of Industrial Organic Chemistry, Warsaw (Poland)

    2013-05-15

    The 1,3-dipolar cycloaddition reaction of nitrile oxides to norbornenes substituted with an acrylate-derived moiety was examined. Only adducts to norbornene system were formed with a good exo selectivity and complete site-selectivity. Structures of the products were elucidated by an extensive application of electrospray ionization-mass spectrometry (ESI-MS) and 2D {sup 1}H and {sup 13}C nuclear magnetic resonance (NMR). (author)

  11. Observation of plasmonic dipolar anti-bonding mode in silver nanoring structures

    International Nuclear Information System (INIS)

    Ye Jian; Van Dorpe, Pol; Lagae, Liesbet; Borghs, Gustaaf; Maes, Guido

    2009-01-01

    We report on a clear experimental observation of the plasmonic dipolar anti-bonding resonance in silver nanorings. The data can be explained effectively by the plasmon hybridization model, which is confirmed by the numerical calculations of the electromagnetic field and surface charge distribution profiles. The experimental demonstration of the plasmon hybridization model indicates its usefulness as a valuable tool to understand, design and predict optical properties of metallic nanostructures.

  12. Observation of plasmonic dipolar anti-bonding mode in silver nanoring structures

    Energy Technology Data Exchange (ETDEWEB)

    Ye Jian; Van Dorpe, Pol; Lagae, Liesbet; Borghs, Gustaaf [Interuniversity Microelectronics Center (IMEC), Kapeldreef 75, B-3001 Leuven (Belgium); Maes, Guido, E-mail: Jian.Ye@imec.b [Chemistry Department, Katholieke Universiteit Leuven, Celestijnenlaan 200 F, B-3001 Leuven (Belgium)

    2009-11-18

    We report on a clear experimental observation of the plasmonic dipolar anti-bonding resonance in silver nanorings. The data can be explained effectively by the plasmon hybridization model, which is confirmed by the numerical calculations of the electromagnetic field and surface charge distribution profiles. The experimental demonstration of the plasmon hybridization model indicates its usefulness as a valuable tool to understand, design and predict optical properties of metallic nanostructures.

  13. Observation of plasmonic dipolar anti-bonding mode in silver nanoring structures

    Science.gov (United States)

    Ye, Jian; Van Dorpe, Pol; Lagae, Liesbet; Maes, Guido; Borghs, Gustaaf

    2009-11-01

    We report on a clear experimental observation of the plasmonic dipolar anti-bonding resonance in silver nanorings. The data can be explained effectively by the plasmon hybridization model, which is confirmed by the numerical calculations of the electromagnetic field and surface charge distribution profiles. The experimental demonstration of the plasmon hybridization model indicates its usefulness as a valuable tool to understand, design and predict optical properties of metallic nanostructures.

  14. A facile regioselective synthesis of novel spiroacenaphthene pyrroloisoquinolines through 1,3-dipolar cycloaddition reactions

    Energy Technology Data Exchange (ETDEWEB)

    Sarrafi, Yaghoub; Asghari, Asieh; Sadatshahabi, Marzieh, E-mail: ysarrafi@umz.ac.ir [Department of Organic Chemistry, Faculty of Chemistry, University of Mazandaran (Iran, Islamic Republic of); Hamzehloueian, Mahshid [Department of Chemistry, Jouybar Branch, Islamic Azad University, Jouybar (Iran, Islamic Republic of); Alimohammadi, Kamal [Department of Chemistry, Dr. Shariati Branch, University of Farhangian, Sari (Iran, Islamic Republic of)

    2013-12-01

    An efficient one-pot three-component procedure for the synthesis of novel spiroacenaphthene pyrroloisoquinolines with high regioselectivity is described. These compounds were prepared from 1,3-dipolar cycloaddition of an azomethine ylide generated from acenaphthenequinone and 1,2,3,4-tetrahydroisoquinoline via [1,5]-H shift, with chalcone and nitrostyrene derivatives as dipolarophiles. The structure and stereochemistry of the cycloadducts have been established by single crystal X-ray structure and spectroscopic techniques. (author)

  15. Absence of Long-Range Order in a Triangular Spin System with Dipolar Interactions

    Science.gov (United States)

    Keleş, Ahmet; Zhao, Erhai

    2018-05-01

    The antiferromagnetic Heisenberg model on the triangular lattice is perhaps the best known example of frustrated magnets, but it orders at low temperatures. Recent density matrix renormalization group (DMRG) calculations find that the next nearest neighbor interaction J2 enhances the frustration, and it leads to a spin liquid for J2/J1∈(0.08 ,0.15 ). In addition, a DMRG study of a dipolar Heisenberg model with longer range interactions gives evidence for a spin liquid at a small dipole tilting angle θ ∈[0 ,1 0 ° ). In both cases, the putative spin liquid region appears to be small. Here, we show that for the triangular lattice dipolar Heisenberg model, a robust quantum paramagnetic phase exists in a surprisingly wide region, θ ∈[0 ,5 4 ° ) , for dipoles tilted along the lattice diagonal direction. We obtain the phase diagram of the model by functional renormalization group (RG), which treats all magnetic instabilities on equal footing. The quantum paramagnetic phase is characterized by a smooth continuous flow of vertex functions and spin susceptibility down to the lowest RG scale, in contrast to the apparent breakdown of RG flow in phases with stripe or spiral order. Our finding points to a promising direction to search for quantum spin liquids in ultracold dipolar molecules.

  16. Topological defect formation in rotating binary dipolar Bose–Einstein condensate

    International Nuclear Information System (INIS)

    Zhang, Xiao-Fei; Han, Wei; Jiang, Hai-Feng; Liu, Wu-Ming; Saito, Hiroki; Zhang, Shou-Gang

    2016-01-01

    We investigate the topological defects and spin structures of a rotating binary Bose–Einstein condensate, which consists of both dipolar and scalar bosonic atoms confined in spin-dependent optical lattices, for an arbitrary orientation of the dipoles with respect to their plane of motion. Our results show that the tunable dipolar interaction, especially the orientation of the dipoles, can be used to control the direction of stripe phase and its related half-vortex sheets. In addition, it can also be used to obtain a regular arrangement of various topological spin textures, such as meron, circular and cross disgyration spin structures. We point out that such topological defects and regular arrangement of spin structures arise primarily from the long-range and anisotropic nature of dipolar interaction and its competition with the spin-dependent optical lattices and rotation. - Highlights: • Effects of both strength and orientation of the dipoles are discussed. • Various topological defects can be formed in different parameter regions. • Present one possible way to obtain regular arrangements of spin textures.

  17. Quasi-parallel whistler mode waves observed by THEMIS during near-earth dipolarizations

    Science.gov (United States)

    Le Contel, O.; Roux, A.; Jacquey, C.; Robert, P.; Berthomier, M.; Chust, T.; Grison, B.; Angelopoulos, V.; Sibeck, D.; Chaston, C. C.; Cully, C. M.; Ergun, B.; Glassmeier, K.-H.; Auster, U.; McFadden, J.; Carlson, C.; Larson, D.; Bonnell, J. W.; Mende, S.; Russell, C. T.; Donovan, E.; Mann, I.; Singer, H.

    2009-06-01

    We report on quasi-parallel whistler emissions detected by the near-earth satellites of the THEMIS mission before, during, and after local dipolarization. These emissions are associated with an electron temperature anisotropy α=T⊥e/T||e>1 consistent with the linear theory of whistler mode anisotropy instability. When the whistler mode emissions are observed the measured electron anisotropy varies inversely with β||e (the ratio of the electron parallel pressure to the magnetic pressure) as predicted by Gary and Wang (1996). Narrow band whistler emissions correspond to the small α existing before dipolarization whereas the broad band emissions correspond to large α observed during and after dipolarization. The energy in the whistler mode is leaving the current sheet and is propagating along the background magnetic field, towards the Earth. A simple time-independent description based on the Liouville's theorem indicates that the electron temperature anisotropy decreases with the distance along the magnetic field from the equator. Once this variation of α is taken into account, the linear theory predicts an equatorial origin for the whistler mode. The linear theory is also consistent with the observed bandwidth of wave emissions. Yet, the anisotropy required to be fully consistent with the observations is somewhat larger than the measured one. Although the discrepancy remains within the instrumental error bars, this could be due to time-dependent effects which have been neglected. The possible role of the whistler waves in the substorm process is discussed.

  18. Quasi-parallel whistler mode waves observed by THEMIS during near-earth dipolarizations

    Directory of Open Access Journals (Sweden)

    O. Le Contel

    2009-06-01

    Full Text Available We report on quasi-parallel whistler emissions detected by the near-earth satellites of the THEMIS mission before, during, and after local dipolarization. These emissions are associated with an electron temperature anisotropy α=T⊥e/T||e>1 consistent with the linear theory of whistler mode anisotropy instability. When the whistler mode emissions are observed the measured electron anisotropy varies inversely with β||e (the ratio of the electron parallel pressure to the magnetic pressure as predicted by Gary and Wang (1996. Narrow band whistler emissions correspond to the small α existing before dipolarization whereas the broad band emissions correspond to large α observed during and after dipolarization. The energy in the whistler mode is leaving the current sheet and is propagating along the background magnetic field, towards the Earth. A simple time-independent description based on the Liouville's theorem indicates that the electron temperature anisotropy decreases with the distance along the magnetic field from the equator. Once this variation of α is taken into account, the linear theory predicts an equatorial origin for the whistler mode. The linear theory is also consistent with the observed bandwidth of wave emissions. Yet, the anisotropy required to be fully consistent with the observations is somewhat larger than the measured one. Although the discrepancy remains within the instrumental error bars, this could be due to time-dependent effects which have been neglected. The possible role of the whistler waves in the substorm process is discussed.

  19. Luttinger hydrodynamics of confined one-dimensional Bose gases with dipolar interactions

    International Nuclear Information System (INIS)

    Citro, R; Palo, S De; Orignac, E; Pedri, P; Chiofalo, M-L

    2008-01-01

    Ultracold bosonic and fermionic quantum gases confined to quasi-one-dimensional (1D) geometry are promising candidates for probing fundamental concepts of Luttinger liquid (LL) physics. They can also be exploited for devising applications in quantum information processing and precision measurements. Here, we focus on 1D dipolar Bose gases, where evidence of super-strong coupling behavior has been demonstrated by analyzing the low-energy static and dynamical structures of the fluid at zero temperature by a combined reptation quantum Monte Carlo (RQMC) and bosonization approach. Fingerprints of LL behavior emerge in the whole crossover from the already strongly interacting Tonks-Girardeau at low density to a dipolar density wave regime at high density. We have also shown that a LL framework can be effectively set up and utilized to describe this strongly correlated crossover physics in the case of confined 1D geometries after using the results for the homogeneous system in LL hydrodynamic equations within a local density approximation. This leads to the prediction of observable quantities such as the frequencies of the collective modes of the trapped dipolar gas under the more realistic conditions that could be found in ongoing experiments. The present paper provides a description of the theoretical framework in which the above results have been worked out, making available all the detailed derivations of the hydrodynamic Luttinger equations for the inhomogeneous trapped gas and of the correlation functions for the homogeneous system

  20. Bose-Einstein condensation and study of inelastic collisions due to dipolar interactions

    International Nuclear Information System (INIS)

    Beaufils, Q.

    2009-01-01

    Its large magnetic moment in the ground state makes chromium a good candidate for the study of dipolar interactions in a degenerate gas. We have built an experimental setup for trapping and cooling atoms of "5"2Cr down to Bose-Einstein condensation (BEC). Evaporative cooling takes place in a purely optical trap, which is loaded from the magneto-optical trap using a novel process of continuous accumulation of metastable states. We produce a condensate of typically 15000 atoms in a time of 15 s. We have studied the possibility to bring all the Zeeman substates of a chromium BEC to degeneracy in a non-zero static magnetic field, using a radiofrequency (rf) magnetic field, and demonstrated a new process of rf-assisted dipolar relaxation. We have also studied a narrow Feshbach resonance induced by dipolar interaction, which implies a d-wave collisional channel. We analyzed this resonance in the presence of a rf magnetic field and we reinterpreted rf association of molecules as a mere Feshbach resonance between rf dressed states. Finally, we have set up an optical lattice in the perspective of studying the effects of dipole-dipole interactions in reduced dimension. (author)

  1. Nonlinear localized modes in dipolar Bose-Einstein condensates in optical lattices

    International Nuclear Information System (INIS)

    Rojas-Rojas, S.; Vicencio, R. A.; Molina, M. I.; Abdullaev, F. Kh.

    2011-01-01

    Modulational instability and discrete matter wave solitons in dipolar BECs, loaded into a deep optical lattice, are investigated analytically and numerically. The process of modulational instability of nonlinear plane matter waves in a dipolar nonlinear lattice is studied and the regions of instability are established. The existence and stability of bulk discrete solitons are analyzed analytically and confirmed by numerical simulations. In marked contrast with the usual discrete nonlinear Schroedinger behavior (no dipolar interactions), we found a region where the two fundamental modes are simultaneously unstable, allowing enhanced mobility across the lattice for large norm values. To study the existence and properties of surface discrete solitons, an analysis of the dimer configuration is performed. The properties of symmetric and antisymmetric modes including stability diagrams and bifurcations are investigated in closed form. For the case of a bulk medium, properties of fundamental on-site and intersite localized modes are analyzed. On-site and intersite surface localized modes are studied, and we find that they do not exist when nonlocal interactions predominate with respect to local ones.

  2. Phase transitions to dipolar clusters and charge density waves in high T{sub c} superconductors

    Energy Technology Data Exchange (ETDEWEB)

    Saarela, M., E-mail: Mikko.Saarela@oulu.fi [Department of Physics, University of Oulu, P.O. Box 3000, FIN-90014 (Finland); Kusmartsev, F.V. [Department of Physics, Loughborough University, LE11 3TU (United Kingdom)

    2017-02-15

    We show that doping of hole charge carriers leads to formation of electric dipolar clusters in cuprates. They are created by many-body interactions between the dopant ion outside and holes inside the CuO planes. Because of the two-fold degeneracy holes in the CuO plane cluster into four-particles resonance valence bond plaquettes bound with dopant ions. Such dipoles may order into charge-density waves (CDW) or stripes or form a disordered state depending on doping and temperature. The lowest energy of the ordered system corresponds to a local anti-ferroelectric ordering. The mobility of individual disordered dipoles is very low at low temperatures and they prefer first to bind into dipole-dipole pairs. Electromagnetic radiation interacts strongly with electric dipoles and when the sample is subjected to it the mobility changes significantly. This leads to a fractal growth of dipolar clusters. The existence of electric dipoles and CDW induce two phase transitions with increasing temperature, melting of the ordered state and disappearance of the dipolar state. Ferroelectricity at low doping is a natural consequence of such dipole moments. We develop a theory based on two-level systems and dipole-dipole interaction to explain the behavior of the polarization as a function of temperature and electric field.

  3. Tuning dipolar magnetic interactions by controlling individual silica coating of iron oxide nanoparticles

    Science.gov (United States)

    Rivas Rojas, P. C.; Tancredi, P.; Moscoso Londoño, O.; Knobel, M.; Socolovsky, L. M.

    2018-04-01

    Single and fixed size core, core-shell nanoparticles of iron oxides coated with a silica layer of tunable thickness were prepared by chemical routes, aiming to generate a frame of study of magnetic nanoparticles with controlled dipolar interactions. The batch of iron oxides nanoparticles of 4.5 nm radii, were employed as cores for all the coated samples. The latter was obtained via thermal decomposition of organic precursors, resulting on nanoparticles covered with an organic layer that was subsequently used to promote the ligand exchange in the inverse microemulsion process, employed to coat each nanoparticle with silica. The amount of precursor and times of reaction was varied to obtain different silica shell thicknesses, ranging from 0.5 nm to 19 nm. The formation of the desired structures was corroborated by TEM and SAXS measurements, the core single-phase spinel structure was confirmed by XRD, and superparamagnetic features with gradual change related to dipolar interaction effects were obtained by the study of the applied field and temperature dependence of the magnetization. To illustrate that dipolar interactions are consistently controlled, the main magnetic properties are presented and analyzed as a function of center to center minimum distance between the magnetic cores.

  4. Phase transitions to dipolar clusters and charge density waves in high T_c superconductors

    International Nuclear Information System (INIS)

    Saarela, M.; Kusmartsev, F.V.

    2017-01-01

    We show that doping of hole charge carriers leads to formation of electric dipolar clusters in cuprates. They are created by many-body interactions between the dopant ion outside and holes inside the CuO planes. Because of the two-fold degeneracy holes in the CuO plane cluster into four-particles resonance valence bond plaquettes bound with dopant ions. Such dipoles may order into charge-density waves (CDW) or stripes or form a disordered state depending on doping and temperature. The lowest energy of the ordered system corresponds to a local anti-ferroelectric ordering. The mobility of individual disordered dipoles is very low at low temperatures and they prefer first to bind into dipole-dipole pairs. Electromagnetic radiation interacts strongly with electric dipoles and when the sample is subjected to it the mobility changes significantly. This leads to a fractal growth of dipolar clusters. The existence of electric dipoles and CDW induce two phase transitions with increasing temperature, melting of the ordered state and disappearance of the dipolar state. Ferroelectricity at low doping is a natural consequence of such dipole moments. We develop a theory based on two-level systems and dipole-dipole interaction to explain the behavior of the polarization as a function of temperature and electric field.

  5. Citral derived amides as potent bacterial NorA efflux pump inhibitors

    DEFF Research Database (Denmark)

    Thota, Niranjan; Koul, Surrinder; Reddy, Mallepally V

    2008-01-01

    Monoterpene citral and citronellal have been used as starting material for the preparation of 5,9-dimethyl-deca-2,4,8-trienoic acid amides and 9-formyl-5-methyl-deca-2,4,8-trienoic acid amides. The amides on bioevaluation as efflux pump inhibitors (EPIs) against Staphylococcus aureus 1199 and NorA...

  6. Use of triphenyl phosphate as risk mitigant for metal amide hydrogen storage materials

    Science.gov (United States)

    Cortes-Concepcion, Jose A.; Anton, Donald L.

    2016-04-26

    A process in a resulting product of the process in which a hydrogen storage metal amide is modified by a ball milling process using an additive of TPP. The resulting product provides for a hydrogen storage metal amide having a coating that renders the hydrogen storage metal amide resistant to air, ambient moisture, and liquid water while improving useful hydrogen storage and release kinetics.

  7. 40 CFR 721.720 - Alkoxylated fatty acid amide, alkylsulfate salt.

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Alkoxylated fatty acid amide... Specific Chemical Substances § 721.720 Alkoxylated fatty acid amide, alkylsulfate salt. (a) Chemical... as an alkoxylated fatty acid amide, alkylsulfate salt (PMN P-97-136) is subject to reporting under...

  8. 40 CFR 721.9075 - Quaternary ammonium salt of fluorinated alkylaryl amide.

    Science.gov (United States)

    2010-07-01

    ... fluorinated alkylaryl amide. 721.9075 Section 721.9075 Protection of Environment ENVIRONMENTAL PROTECTION... amide. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as quaternary ammonium salt of fluorinated alkylaryl amide (PMN No. P-92-688) is...

  9. 40 CFR 721.10063 - Halo substituted hydroxy nitrophenyl amide (generic).

    Science.gov (United States)

    2010-07-01

    ... amide (generic). 721.10063 Section 721.10063 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.10063 Halo substituted hydroxy nitrophenyl amide (generic). (a) Chemical... as halo substituted hydroxy nitrophenyl amide (PMN P-04-792) is subject to reporting under this...

  10. 40 CFR 721.10191 - Amides, coco, N-[3-(dibutylamino)propyl].

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Amides, coco, N-[3-(dibutylamino... Specific Chemical Substances § 721.10191 Amides, coco, N-[3-(dibutylamino)propyl]. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as amides, coco...

  11. 40 CFR 721.10176 - Amides, peanut-oil, N-[3-(dimethylamino)propyl].

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Amides, peanut-oil, N-[3... Specific Chemical Substances § 721.10176 Amides, peanut-oil, N-[3-(dimethylamino)propyl]. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as amides...

  12. 40 CFR 721.10192 - Amides, coco, N-[3-(dibutylamino)propyl], acrylates.

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Amides, coco, N-[3-(dibutylamino... Specific Chemical Substances § 721.10192 Amides, coco, N-[3-(dibutylamino)propyl], acrylates. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as amides...

  13. Straightforward uranium-catalyzed dehydration of primary amides to nitriles

    International Nuclear Information System (INIS)

    Enthaler, Stephan

    2011-01-01

    The efficient uranium-catalyzed dehydration of a variety of primary amides, using N-methyl-N-(trimethylsilyl)trifluoroacetamide (MSTFA) as a dehydration reagent, to the corresponding nitriles has been investigated. With this catalyst system, extraordinary catalyst activities and selectivities were feasible. (Copyright copyright 2011 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  14. Method for enhancing amidohydrolase activity of fatty acid amide hydrolase

    Science.gov (United States)

    John, George; Nagarajan, Subbiah; Chapman, Kent; Faure, Lionel; Koulen, Peter

    2017-12-26

    A method for enhancing amidohydrolase activity of Fatty Acid Amide Hydrolase (FAAH) is disclosed. The method comprising administering a phenoxyacyl-ethanolamide that causes the enhanced activity. The enhanced activity can have numerous effects on biological organisms including, for example, enhancing the growth of certain seedlings.

  15. Polyurethanes elastomers with amide chain extenders of uniform length

    NARCIS (Netherlands)

    van der Schuur, J.M.; Noordover, B.A.J.; Noordover, Bart; Gaymans, R.J.

    2006-01-01

    Toluene diisocyanate based polyurethanes with amide extenders were synthesized poly(propylene oxide) with a number average molecular weight of 2000 and endcapped with toluene diisocyanate was used as the polyether segment. The chain extenders were based on poly(hexamethylene terephthalamide):

  16. Polyuretehane elastomers with amide chain extenders of uniform length

    NARCIS (Netherlands)

    Schuur, van der M.; Noordover, B.A.J.; Gaymans, R.J.

    2006-01-01

    Toluene diisocyanate based polyurethanes with amide extenders were synthesized poly(propylene oxide) with a number average molecular weight of 2000 and endcapped with toluene diisocyanate was used as the polyether segment. The chain extenders were based on poly(hexamethylene terephthalamide):

  17. Method for enhancing amidohydrolase activity of fatty acid amide hydrolase

    Science.gov (United States)

    John, George; Nagarajan, Subbiah; Chapman, Kent; Faure, Lionel; Koulen, Peter

    2016-10-25

    A method for enhancing amidohydrolase activity of Fatty Acid Amide Hydrolase (FAAH) is disclosed. The method comprising administering a phenoxyacylethanolamide that causes the enhanced activity. The enhanced activity can have numerous effects on biological organisms including, for example, enhancing the growth of certain seedlings. The subject matter disclosed herein relates to enhancers of amidohydrolase activity.

  18. Unconventional Passerini Reaction toward α-Aminoxy-amides

    NARCIS (Netherlands)

    Chandgude, Ajay L; Dömling, Alexander

    2016-01-01

    The Passerini multicomponent reaction (P-3CR) toward the one-step synthesis of α-aminoxy-amide, by employing for the first time a N-hydroxamic acid component, has been reported. The sonication-accelerated, catalyst-free, simple, fast, and highly efficient Passerini reaction is used for the synthesis

  19. Synthesis, characterization and photo behavior of new poly(amide ...

    African Journals Online (AJOL)

    ... and the interaction between clay and polymeric chains on the properties of nanocomposites films were investigated by using UV-Vis spectroscopy, thermogravimetric analysis (TGA) and water uptake measurements. KEY WORDS: Nanocomposite, Poly(amide-imide), Silicate particle, Polycondensation, Thermal behavior.

  20. Synthesis and characterization of new optically active poly(amide

    African Journals Online (AJOL)

    Preferred Customer

    Six new optically active poly(amide-imide)s (8a-f) were synthesized through the direct ... polyimides are widely used in the semiconductor and electronic packaging ... chiral polymers is of particular interest from the viewpoint of material science ...

  1. Synthesis and quantitation of six phenolic amides in Amaranthus spp

    DEFF Research Database (Denmark)

    Pedersen, Hans; Steffensen, Stine K; Christophersen, Carsten

    2010-01-01

    Cinnamoylphenethylamines are phenolic amides in which cinnamic acid provides the acid moiety and phenethylamine the amine moiety. Single ion monitoring (SIM) in LC-MS was performed on amaranth leaf extracts. Masses corresponding to sets of regioisomers, including previously reported compounds, were...

  2. Amides and Hydrazides from Amine and Hydrazine Hydrochlorides.

    Science.gov (United States)

    Shama, Sami A.; Tran, Thuan L.

    1978-01-01

    This safe and efficient procedure for the synthesis of N-substituted amides and hydrazides is a modification of the Schotten-Bausmann procedure in which the amine or hydrazide is replaced by the corresponding hydrochloride salt, and the use of alkali is eliminated. (Author/BB)

  3. Chiral amides via copper-catalysed enantioselective conjugate addition

    NARCIS (Netherlands)

    Schoonen, Anne K.; Fernández-Ibáñez, M. Ángeles; Fañanás-Mastral, Martín; Teichert, Johannes F.; Feringa, Bernard

    2014-01-01

    A highly enantioselective one pot procedure for the synthesis of beta-substituted amides was developed starting from the corresponding alpha,beta-unsaturated esters. This new methodology is based on the copper-catalysed enantioselective conjugate addition of Grignard reagents to

  4. N-Hydroxyimide Ugi Reaction toward α-Hydrazino Amides

    NARCIS (Netherlands)

    Chandgude, Ajay L; Dömling, Alexander

    2017-01-01

    The Ugi four-component reaction (U-4CR) with N-hydroxyimides as a novel carboxylic acid isostere has been reported. This reaction provides straightforward access to α-hydrazino amides. A broad range of aldehydes, amines, isocyanides and N-hydroxyimides were employed to give products in moderate to

  5. Synthesis, antiproliferative and antibacterial activity of new amides of salinomycin.

    Science.gov (United States)

    Antoszczak, Michał; Maj, Ewa; Stefańska, Joanna; Wietrzyk, Joanna; Janczak, Jan; Brzezinski, Bogumil; Huczyński, Adam

    2014-04-01

    A series of 11 novel amides of salinomycin were synthesized for the first time. All the obtained compounds were found to show potent antiproliferative activity against human cancer cell lines including the drug-resistant cancer cells. Four new salinomycin derivatives revealed good antibacterial activity against clinical isolates of methicillin-resistant Staphylococcus epidermidis (MRSE). Copyright © 2014 Elsevier Ltd. All rights reserved.

  6. Spin Diffusion and Spin Lattice Relaxation of Dipolar Order in Solids Containing Paramagnetic Impurities

    International Nuclear Information System (INIS)

    Furman, G.B.; Panich, A.M.; Goren, S.D.

    1998-01-01

    The phenomena of spin diffusion and spin lattice relaxation of nuclear dipolar order in solids containing paramagnetic impurities (PI) is considered. We show that at the beginning of the relaxation process the diffusion vanishing regime realizes with non-exponential time dependence, R(t) ∼ exp [- (t/T 1d ) α ], where T 1d ∼ C p -1/α , C p is PI's concentration. For a homogeneous distribution of Pis and nuclear spins, α=Q/6, where Q is the sample dimensionality; for an inhomogeneous distribution, the sample is divided into q-dimensional subsystems, each containing one PI, yield- ing α= (Q + q) /6. This result coincides with experimental data for CaF 2 doped with 0.8 - 10 -3 ωt % of Mn 2+ , where the non-exponential decay of the dipolar signal with α= 0.83 has been observed [3]. Fitting the experimental data yields a good agreement with T 1d = 66 ms . For another independent check of the obtained results we use dependence of the relaxation time on impurities concentration. In accordance that 1/α=1.2 , we have T 1d ∼ C p -1 '. 2 . Exactly this dependence on impurity concentration of the relaxation time has been found in the experiment. Then the relaxation regime starts as a non-exponential time dependent, proceed asymptotically to an to an exponential function of time, to so called diffusion limited relaxation regime with relaxation time T 1d D is inversely depends on impurities concentration. This kind of relaxation behavior of the dipolar order takes place in the experiment [2]. Using experimental results [2] from this two regime we can estimate the diffusion coefficient of the nuclear dipolar order in CaF 2 , which gives for typical values of impurity concentration C p ∼ 10 18 cm 3 the diffusion coefficient of dipolar order in the interval D ∼ 10 -11 -i- 10 -12 cm 2 /sec which is coincide to the case of Zeeman energy spin diffusion

  7. Insecticidal, repellent and fungicidal properties of novel trifluoromethylphenyl amides.

    Science.gov (United States)

    Tsikolia, Maia; Bernier, Ulrich R; Coy, Monique R; Chalaire, Katelyn C; Becnel, James J; Agramonte, Natasha M; Tabanca, Nurhayat; Wedge, David E; Clark, Gary G; Linthicum, Kenneth J; Swale, Daniel R; Bloomquist, Jeffrey R

    2013-09-01

    Twenty trifluoromethylphenyl amides were synthesized and evaluated as fungicides and as mosquito toxicants and repellents. Against Aedes aegypti larvae, N-(2,6-dichloro-4-(trifluoromethyl)phenyl)-3,5-dinitrobenzamide (1e) was the most toxic compound (24 h LC50 1940 nM), while against adults N-(2,6-dichloro-4-(trifluoromethyl)phenyl)-2,2,2-trifluoroacetamide (1c) was most active (24 h LD50 19.182 nM, 0.5 μL/insect). However, the 24 h LC50 and LD50 values of fipronil against Ae. aegypti larvae and adults were significantly lower: 13.55 nM and 0.787 × 10(-4) nM, respectively. Compound 1c was also active against Drosophila melanogaster adults with 24 h LC50 values of 5.6 and 4.9 μg/cm(2) for the Oregon-R and 1675 strains, respectively. Fipronil had LC50 values of 0.004 and 0.017 μg/cm(2) against the two strains of D. melanogaster, respectively. In repellency bioassays against female Ae. aegypti, 2,2,2-trifluoro-N-(2-(trifluoromethyl)phenyl)acetamide (4c) had the highest repellent potency with a minimum effective dosage (MED) of 0.039 μmol/cm(2) compared to DEET (MED of 0.091 μmol/cm(2)). Compound N-(2-(trifluoromethyl)phenyl)hexanamide (4a) had an MED of 0.091 μmol/cm(2) which was comparable to DEET. Compound 4c was the most potent fungicide against Phomopsis obscurans. Several trends were discerned between the structural configuration of these molecules and the effect of structural changes on toxicity and repellency. Para- or meta- trifluoromethylphenyl amides with an aromatic ring attached to the carbonyl carbon showed higher toxicity against Ae. aegypti larvae, than ortho- trifluoromethylphenyl amides. Ortho- trifluoromethylphenyl amides with trifluoromethyl or alkyl group attached to the carbonyl carbon produced higher repellent activity against female Ae. aegypti and Anopheles albimanus than meta- or para- trifluoromethylphenyl amides. The presence of 2,6-dichloro- substitution on the phenyl ring of the amide had an influence on larvicidal and repellent

  8. Discovery of competing anaerobic and aerobic pathways in umpolung amide synthesis allows for site-selective amide 18O-labeling

    Science.gov (United States)

    Shackleford, Jessica P.; Shen, Bo; Johnston, Jeffrey N.

    2012-01-01

    The mechanism of umpolung amide synthesis was probed by interrogating potential sources for the oxygen of the product amide carbonyl that emanates from the α-bromo nitroalkane substrate. Using a series of 18O-labeled substrates and reagents, evidence is gathered to advance two pathways from the putative tetrahedral intermediate. Under anaerobic conditions, a nitro-nitrite isomerization delivers the amide oxygen from nitro oxygen. The same homolytic nitro-carbon fragmentation can be diverted by capture of the carbon radical intermediate with oxygen gas (O2) to deliver the amide oxygen from O2. This understanding was used to develop a straightforward protocol for the preparation of 18O-labeled amides in peptides by simply performing the umpolung amide synthesis reaction under an atmosphere of . PMID:22184227

  9. Amide Bond Formation Assisted by Vicinal Alkylthio Migration in Enaminones: Metal- and CO-Free Synthesis of α,β-Unsaturated Amides.

    Science.gov (United States)

    Liu, Zhuqing; Huang, Fei; Wu, Ping; Wang, Quannan; Yu, Zhengkun

    2018-05-18

    Amide bond formation is one of the most important transformations in organic synthesis, drug development, and materials science. Efficient construction of amides has been among the most challenging tasks for organic chemists. Herein, we report a concise methodology for amide bond (-CONH-) formation assisted by vicinal group migration in alkylthio-functionalized enaminones (α-oxo ketene N, S-acetals) under mild conditions. Simple treatment of such enaminones with PhI(OAc) 2 at ambient temperature in air afforded diverse multiply functionalized α,β-unsaturated amides including β-cyclopropylated acrylamides, in which a wide array of functional groups such as aryl, (hetero)aryl, alkenyl, and alkyl can be conveniently introduced to a ketene moiety. The reaction mechanism was investigated by exploring the origins of the amide oxygen and carbon atoms as well as isolation and structural characterization of the reaction intermediates. The amide bond formation reactions could also be efficiently performed under solventless mechanical milling conditions.

  10. Porphyrin amino acids-amide coupling, redox and photophysical properties of bis(porphyrin) amides.

    Science.gov (United States)

    Melomedov, Jascha; Wünsche von Leupoldt, Anica; Meister, Michael; Laquai, Frédéric; Heinze, Katja

    2013-07-14

    New trans-AB2C meso-substituted porphyrin amino acid esters with meso-substituents of tunable electron withdrawing power (B = mesityl, 4-C6H4F, 4-C6H4CF3, C6F5) were prepared as free amines 3a-3d, as N-acetylated derivatives Ac-3a-Ac-3d and corresponding zinc(II) complexes Zn-Ac-3a-Zn-Ac-3d. Several amide-linked bis(porphyrins) with a tunable electron density at each porphyrin site were obtained from the amino porphyrin precursors by condensation reactions (4a-4d) and mono- and bis(zinc(II)) complexes Zn(2)-4d and Zn(1)Zn(2)-4d were prepared. The electronic interaction between individual porphyrin units in bis(porphyrins) 4 is probed by electrochemical experiments (CV, EPR), electronic absorption spectroscopy, steady-state and time-resolved fluorescence spectroscopy in combination with DFT/PCM calculations on diamagnetic neutral bis(porphyrins) 4 and on respective charged mixed-valent radicals 4(+/-). The interaction via the -C6H4-NHCO-C6H4- bridge, the site of oxidation and reduction and the lowest excited singlet state S1, is tuned by the substituents on the individual porphyrins and the metalation state.

  11. Segmented poly(ether ester)s and poly(ether ester amide)s for use in tissue engineering

    OpenAIRE

    Deschamps, A.A.

    2002-01-01

    The objective of the studies described in this thesis is to investigate the applicability of these slowly degradable thermoplastic elastomers as scaffolds for tissue engineering, with emphasis on their phase separation and degradation properties. A second thermoplastic elastomer in which the terephthalic moieties have been replaced by ester-amide segments, is also investigated for use in scaffolding.

  12. Carryover potassium amide in cracker at HWP, Hazira - a case study (Paper No. 1.5)

    International Nuclear Information System (INIS)

    Anon.

    1992-01-01

    The liquid ammonia fed to cracker is made available from potassium amide catalyst recovery unit, where catalyst potassium amide is separated by distillation. Extreme care is taken to ensure that ammonia is totally free from potassium. Also the gas used for catalyst heating during start up, should be free of any possible amide contamination and should be pure and dry as moisture is a poison for the catalyst. In order to prevent the recurrence of amide carryover to cracker tubes from start up gas line, certain modifications were carried out besides removal of amide from pipings. Details are discussed. (author)

  13. Nine of 16 stereoisomeric polyhydroxylated proline amides are potent β-N-acetylhexosaminidase inhibitors.

    Science.gov (United States)

    Ayers, Benjamin J; Glawar, Andreas F G; Martínez, R Fernando; Ngo, Nigel; Liu, Zilei; Fleet, George W J; Butters, Terry D; Nash, Robert J; Yu, Chu-Yi; Wormald, Mark R; Nakagawa, Shinpei; Adachi, Isao; Kato, Atsushi; Jenkinson, Sarah F

    2014-04-18

    All 16 stereoisomeric N-methyl 5-(hydroxymethyl)-3,4-dihydroxyproline amides have been synthesized from lactones accessible from the enantiomers of glucuronolactone. Nine stereoisomers, including all eight with a (3R)-hydroxyl configuration, are low to submicromolar inhibitors of β-N-acetylhexosaminidases. A structural correlation between the proline amides is found with the ADMDP-acetamide analogues bearing an acetamidomethylpyrrolidine motif. The proline amides are generally more potent than their ADMDP-acetamide equivalents. β-N-Acetylhexosaminidase inhibition by an azetidine ADMDP-acetamide analogue is compared to an azetidine carboxylic acid amide. None of the amides are good α-N-acetylgalactosaminidase inhibitors.

  14. Semi-catalytic reduction of secondary amides to imines and aldehydes.

    Science.gov (United States)

    Lee, Sun-Hwa; Nikonov, Georgii I

    2014-06-21

    Secondary amides can be reduced by silane HSiMe2Ph into imines and aldehydes by a two-stage process involving prior conversion of amides into iminoyl chlorides followed by catalytic reduction mediated by the ruthenium complex [Cp(i-Pr3P)Ru(NCCH3)2]PF6 (1). Alkyl and aryl amides bearing halogen, ketone, and ester groups were converted with moderate to good yields under mild reaction conditions to the corresponding imines and aldehydes. This procedure does not work for substrates bearing the nitro-group and fails for heteroaromatic amides. In the case of cyano substituted amides, the cyano group is reduced to imine.

  15. Solvent Exchange Rates of Side-chain Amide Protons in Proteins

    International Nuclear Information System (INIS)

    Rajagopal, Ponni; Jones, Bryan E.; Klevit, Rachel E.

    1998-01-01

    Solvent exchange rates and temperature coefficients for Asn/Gln side-chain amide protons have been measured in Escherichia coli HPr. The protons of the eight side-chain amide groups (two Asn and six Gln) exhibit varying exchange rates which are slower than some of the fast exchanging backbone amide protons. Differences in exchange rates of the E and Z protons of the same side-chain amide group are obtained by measuring exchange rates at pH values > 8. An NOE between a side-chain amide proton and a bound water molecule was also observed

  16. Discovery of novel N-(5-(arylcarbonyl)thiazol-2-yl)amides and N-(5-(arylcarbonyl)thiophen-2-yl)amides as potent RORγt inhibitors.

    Science.gov (United States)

    Wang, Yonghui; Cai, Wei; Zhang, Guifeng; Yang, Ting; Liu, Qian; Cheng, Yaobang; Zhou, Ling; Ma, Yingli; Cheng, Ziqiang; Lu, Sijie; Zhao, Yong-Gang; Zhang, Wei; Xiang, Zhijun; Wang, Shuai; Yang, Liuqing; Wu, Qianqian; Orband-Miller, Lisa A; Xu, Yan; Zhang, Jing; Gao, Ruina; Huxdorf, Melanie; Xiang, Jia-Ning; Zhong, Zhong; Elliott, John D; Leung, Stewart; Lin, Xichen

    2014-01-15

    Novel series of N-(5-(arylcarbonyl)thiazol-2-yl)amides and N-(5-(arylcarbonyl)thiophen-2-yl)amides were discovered as potent retinoic acid receptor-related orphan receptor-gamma-t (RORγt) inhibitors. SAR studies of the RORγt HTS hit 6a led to identification of thiazole ketone amide 8h and thiophene ketone amide 9g with high binding affinity and inhibitory activity of Th17 cell differentiation. Compound 8h showed in vivo efficacy in both mouse experimental autoimmune encephalomyelitis (EAE) and collagen induced arthritis (CIA) models via oral administration. Copyright © 2013 Elsevier Ltd. All rights reserved.

  17. Adsorption equilibrium of uranium from seawater on chelating resin containing amide oxime group

    International Nuclear Information System (INIS)

    Hori, Takahiro; Saito, Kyoichi; Furusaki, Shintaro; Sugo, Takanobu; Okamoto, Jiro.

    1987-01-01

    Chelating resins containing amide oxime group were synthesized by radiation-induced graft polymerization. The amount of the amide oxime groups was controlled below about 0.1 mol per kg of base polymer. The adsorption equilibrium of uranium from seawater on this resin was investigated. It was suggested that two neighboring amide oxime groups on the grafted chain captured one uranyl ion, and that single amide oxime ligand had little capacity for the adsorption of uranium. The adsorption equilibrium was correlated by a Langmuir-type equation. The content of neighboring amide oxime groups was 0.406 x 10 -3 mol per kg of base polymer, which corresponded to 0.39 % of the total amount of amide oxime groups. The apparent stoichiometric stability constant for the complex of uranyl ion with the neighboring amide oxime groups in seawater was calculated to be 10 -21.7 . (author)

  18. Quasi-parallel whistler mode waves observed by THEMIS during near-earth dipolarizations

    Directory of Open Access Journals (Sweden)

    O. Le Contel

    2009-06-01

    Full Text Available We report on quasi-parallel whistler emissions detected by the near-earth satellites of the THEMIS mission before, during, and after local dipolarization. These emissions are associated with an electron temperature anisotropy α=Te/T||e>1 consistent with the linear theory of whistler mode anisotropy instability. When the whistler mode emissions are observed the measured electron anisotropy varies inversely with β||e (the ratio of the electron parallel pressure to the magnetic pressure as predicted by Gary and Wang (1996. Narrow band whistler emissions correspond to the small α existing before dipolarization whereas the broad band emissions correspond to large α observed during and after dipolarization. The energy in the whistler mode is leaving the current sheet and is propagating along the background magnetic field, towards the Earth. A simple time-independent description based on the Liouville's theorem indicates that the electron temperature anisotropy decreases with the distance along the magnetic field from the equator. Once this variation of α is taken into account, the linear theory predicts an equatorial origin for the whistler mode. The linear theory is also consistent with the observed bandwidth of wave emissions. Yet, the anisotropy required to be fully consistent with the observations is somewhat larger than the measured one. Although the discrepancy remains within the instrumental error bars, this could be due to time-dependent effects which have been neglected. The possible role of the whistler waves in the substorm process is discussed.

  19. Different approaches to analyze the dipolar interaction effects on diluted and concentrated granular superparamagnetic systems

    Energy Technology Data Exchange (ETDEWEB)

    Moscoso-Londoño, O., E-mail: omoscoso@ifi.unicamp.br [Instituto de Física ‘Gleb Wataghin’, Universidade Estadual de Campinas (UNICAMP), CEP13083-859 Campinas, São Paulo (Brazil); Tancredi, P. [Laboratorio de Sólidos Amorfos, INTECIN, Facultad de Ingeniería, Universidad de Buenos Aires (UBA), CONICET, C1063ACV Buenos Aires (Argentina); Muraca, D. [Instituto de Física ‘Gleb Wataghin’, Universidade Estadual de Campinas (UNICAMP), CEP13083-859 Campinas, São Paulo (Brazil); Centro de Ciencias Naturais e Humanas, Universidade Federal do ABC (UFABC), Av. Dos Estados, 5001, Santo André, SP (Brazil); Mendoza Zélis, P.; Coral, D.; Fernández van Raap, M.B. [Instituto de Física, Universidad Nacional de La Plata (UNLP), CONICET, CC.67, 1900 La Plata, Buenos Aires (Argentina); Wolff, U.; Neu, V.; Damm, C. [IFW Dresden, Leibniz Institute for Solid State and Materials Research, Dresden, Helmholtzstrasse 20, 01069 Dresden (Germany); Oliveira, C.L.P. de [Instituto de Física, Universidade de São Paulo, São Paulo 05314970 (Brazil); Pirota, K.R. [Instituto de Física ‘Gleb Wataghin’, Universidade Estadual de Campinas (UNICAMP), CEP13083-859 Campinas, São Paulo (Brazil); and others

    2017-04-15

    Controlled magnetic granular materials with different concentrations of magnetite nanoparticles immersed in a non-conducting polymer matrix were synthesized and, their macroscopic magnetic observables analyzed in order to advance towards a better understanding of the magnetic dipolar interactions and its effects on the obtained magnetic parameters. First, by means of X-ray diffraction, transmission electron microscopy, small angle X-ray scattering and X-ray absorption fine structure an accurate study of the structural properties was carried out. Then, the magnetic properties were analyzed by means of different models, including those that consider the magnetic interactions through long-range dipolar forces as: the Interacting Superparamagnetic Model (ISP) and the Vogel-Fulcher law (V-F). In systems with larger nanoparticle concentrations, magnetic results clearly indicate that the role played by the dipolar interactions affects the magnetic properties, giving rise to obtaining magnetic and structural parameters without physical meaning. Magnetic parameters as the effective anisotropic constant, magnetic moment relaxation time and mean blocking temperature, extracted from the application of the ISP model and V-F Law, were used to simulate the zero-field-cooling (ZFC) and field-cooling curves (FC). A comparative analysis of the simulated, fitted and experimental ZFC/FC curves suggests that the current models depict indeed our dilute granular systems. Notwithstanding, for concentrated samples, the ISP model infers that clustered nanoparticles are being interpreted as single entities of larger magnetic moment and volume, effect that is apparently related to a collective and complex magnetic moment dynamics within the cluster. - Highlights: • Nanoparticle architecture into matrices determines the composite magnetic response. • Magnetically diluted or compacted systems are useful to study magnetism at nanoscale. • Particle aggregation into the matrices was examined

  20. Ultrafast responses of dipolar and octupolar compounds with dipicolinate as an electron acceptor

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Yaochuan, E-mail: ycwang@dlmu.edu.cn [Department of Physics, Dalian Maritime University, Dalian 116026 (China); State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116024 (China); Liu, Siyuan; Liu, Dajun; Wang, Guiqiu [Department of Physics, Dalian Maritime University, Dalian 116026 (China); Xiao, Haibo [Department of Chemistry, Shanghai Normal University, Shanghai 200234 (China)

    2016-11-01

    Two dipolar compounds with dipicolinate as electron acceptor group named trans-dimethyl-4-[4’-(N,N-dimethylamino)-styry1]-pyridin-2,6-dicarboxylate (M-1), trans-dimethyl-4-[4'-(N,N-diphenylamino)-styry1]-pyridin-2,6-dicarboxylate (P-1) as well as a P-1 based multi-branched octupolar compound {4-[(E)-2-(2,6-dimethoxycarbonylpyridin-4-yl) vinyl]}-N,N-bis{4-[(E)-2-(2,6-dimethoxycarbonylpyridin-4-yl)vinylphenyl]} aniline (P-3) with intense two-photon fluorescence emission properties are systematically investigated by using steady-state absorption and fluorescence spectroscopy, Z-scan, and two-photon excited fluorescence (TPF) method. The two-photon absorption cross section of octupolar compound P-3 in THF solution is determined to be 376 GM, which is approximately 12 times greater than that of dipolar counterpart P-1 (32 GM). Transient absorption spectroscopy is employed to investigate the excited state dynamics of the dipolar and octupolar compounds. The formation and relaxation lifetimes of the intra-molecular charge transfer (ICT) state are determined to be in the ranges of several picoseconds and several-hundreds of picoseconds, respectively, for all the three compounds in THF solutions. An extended π-conjugated system and increased intra-molecular cooperative effect are responsible for the observed large two-photon absorption character. - Highlights: • Octupolar compound gain 12-fold enhancement of two photon absorption. • Dynamic properties of intra-molecular charge transfer state are determined. • Cooperative effect is responsible for great increase of two photon character.

  1. Off-equatorial current-driven instabilities ahead of approaching dipolarization fronts

    Science.gov (United States)

    Zhang, Xu; Angelopoulos, V.; Pritchett, P. L.; Liu, Jiang

    2017-05-01

    Recent kinetic simulations have revealed that electromagnetic instabilities near the ion gyrofrequency and slightly away from the equatorial plane can be driven by a current parallel to the magnetic field prior to the arrival of dipolarization fronts. Such instabilities are important because of their potential contribution to global electromagnetic energy conversion near dipolarization fronts. Of the several instabilities that may be consistent with such waves, the most notable are the current-driven electromagnetic ion cyclotron instability and the current-driven kink-like instability. To confirm the existence and characteristics of these instabilities, we used observations by two Time History of Events and Macroscale Interactions during Substorms satellites, one near the neutral sheet observing dipolarization fronts and the other at the boundary layer observing precursor waves and currents. We found that such instabilities with monochromatic signatures are rare, but one of the few cases was selected for further study. Two different instabilities, one at about 0.3 Hz and the other at a much lower frequency, 0.02 Hz, were seen in the data from the off-equatorial spacecraft. A parallel current attributed to an electron beam coexisted with the waves. Our instability analysis attributes the higher-frequency instability to a current-driven ion cyclotron instability and the lower frequency instability to a kink-like instability. The current-driven kink-like instability we observed is consistent with the instabilities observed in the simulation. We suggest that the currents needed to excite these low-frequency instabilities are so intense that the associated electron beams are easily thermalized and hence difficult to observe.

  2. An Efficient Computational Model to Predict Protonation at the Amide Nitrogen and Reactivity along the C–N Rotational Pathway

    Science.gov (United States)

    Szostak, Roman; Aubé, Jeffrey

    2015-01-01

    N-protonation of amides is critical in numerous biological processes, including amide bonds proteolysis and protein folding, as well as in organic synthesis as a method to activate amide bonds towards unconventional reactivity. A computational model enabling prediction of protonation at the amide bond nitrogen atom along the C–N rotational pathway is reported. Notably, this study provides a blueprint for the rational design and application of amides with a controlled degree of rotation in synthetic chemistry and biology. PMID:25766378

  3. Diverse amide analogs of sulindac for cancer treatment and prevention.

    Science.gov (United States)

    Mathew, Bini; Hobrath, Judith V; Connelly, Michele C; Kiplin Guy, R; Reynolds, Robert C

    2017-10-15

    Sulindac is a non-steroidal anti-inflammatory drug (NSAID) that has shown significant anticancer activity. Sulindac sulfide amide (1) possessing greatly reduced COX-related inhibition relative to sulindac displayed in vivo antitumor activity that was comparable to sulindac in a human colon tumor xenograft model. Inspired by these observations, a panel of diverse sulindac amide derivatives have been synthesized and their activity probed against three cancer cell lines (prostate, colon and breast). A neutral analog, compound 79 was identified with comparable potency relative to lead 1 and activity against a panel of lymphoblastic leukemia cell lines. Several new series also show good activity relative to the parent (1), including five analogs that also possess nanomolar inhibitory potencies against acute lymphoblastic leukemia cells. Several new analogs identified may serve as anticancer lead candidates for further development. Copyright © 2017 The Author(s). Published by Elsevier Ltd.. All rights reserved.

  4. Simple Amides of Oleanolic Acid as Effective Penetration Enhancers

    Science.gov (United States)

    Bednarczyk-Cwynar, Barbara; Partyka, Danuta; Zaprutko, Lucjusz

    2015-01-01

    Transdermal transport is now becoming one of the most convenient and safe pathways for drug delivery. In some cases it is necessary to use skin penetration enhancers in order to allow for the transdermal transport of drugs that are otherwise insufficiently skin-permeable. A series of oleanolic acid amides as potential transdermal penetration enhancers was formed by multistep synthesis and the synthesis of all newly prepared compounds is presented. The synthetized amides of oleanolic acid were tested for their in vitro penetration promoter activity. The above activity was evaluated by means of using the Fürst method. The relationships between the chemical structure of the studied compounds and penetration activity are presented. PMID:26010090

  5. Fine structure of the amide i band in acetanilide

    Science.gov (United States)

    Careri, G.; Gratton, E.; Shyamsunder, E.

    1988-05-01

    Their absorption spectrum of both single crystals and powdered samples of acetanilide (a model system for proteins) has been studied in the amide i region, where a narrow band has been identified as a highly trapped soliton state. The powder-sample spectra have been decomposed using four Lorentzian bands. A strong temperature dependence has been found for the intensity of two of the subbands, which also show a complementary behavior. Polarization studies performed on thin crystals have shown that the subbands have the same polarization. Low-temperature spectra of partially deuterated samples show the presence of the subbands at the same absorption frequencies found using the fitting procedure in the spectra of nondeuterated samples. The soliton model currently proposed to explain the origin of the anomalous amide i component at 1650 cm-1 still holds, but some modification of the model is required to account for the new features revealed by this study.

  6. Coumarin amide derivatives as fluorescence chemosensors for cyanide anions

    Energy Technology Data Exchange (ETDEWEB)

    Wu, Qianqian [School of Material Science and Engineering, Shandong Provincial Key Laboratory of Preparation and Measurement of Building Materials, University of Jinan, Jinan 250022, Shandong (China); Liu, Zhiqiang [State Key Laboratory of Crystal Materials, Shandong University, Jinan 250100, Shandong (China); Cao, Duxia, E-mail: duxiacao@ujn.edu.cn [School of Material Science and Engineering, Shandong Provincial Key Laboratory of Preparation and Measurement of Building Materials, University of Jinan, Jinan 250022, Shandong (China); Guan, Ruifang, E-mail: mse_guanrf@ujn.edu.cn [School of Material Science and Engineering, Shandong Provincial Key Laboratory of Preparation and Measurement of Building Materials, University of Jinan, Jinan 250022, Shandong (China); Wang, Kangnan; Shan, Yanyan; Xu, Yongxiao; Ma, Lin [School of Material Science and Engineering, Shandong Provincial Key Laboratory of Preparation and Measurement of Building Materials, University of Jinan, Jinan 250022, Shandong (China)

    2015-07-01

    Four coumarin amide derivatives with 4-methyl coumarin or pyrene as terminal group have been synthesized. Their photophysical properties and recognition properties for cyanide anions have been examined. The results indicate that the compounds can recognize cyanide anions with obvious absorption and fluorescence spectra change, at the same time, obvious color and fluorescence change can be observed by naked eye. The in situ hydrogen nuclear magnetic resonance spectra and photophysical properties change confirm that Michael additions between the chemosensors and cyanide anions take place at the 4-position of coumarin. - Highlights: • Four coumarin amide derivatives with 4-methyl coumarin or pyrene as terminal group were synthesized. • The compounds can recognize cyanide anions with obvious absorption and fluorescence spectra change. • Michael additions between the chemosensors and cyanide anions take place at the 4-position of coumarin.

  7. Simple amides of oleanolic acid as effective penetration enhancers.

    Science.gov (United States)

    Bednarczyk-Cwynar, Barbara; Partyka, Danuta; Zaprutko, Lucjusz

    2015-01-01

    Transdermal transport is now becoming one of the most convenient and safe pathways for drug delivery. In some cases it is necessary to use skin penetration enhancers in order to allow for the transdermal transport of drugs that are otherwise insufficiently skin-permeable. A series of oleanolic acid amides as potential transdermal penetration enhancers was formed by multistep synthesis and the synthesis of all newly prepared compounds is presented. The synthetized amides of oleanolic acid were tested for their in vitro penetration promoter activity. The above activity was evaluated by means of using the Fürst method. The relationships between the chemical structure of the studied compounds and penetration activity are presented.

  8. Absolute carrier phase effects in the two-color excitation of dipolar molecules

    International Nuclear Information System (INIS)

    Brown, Alex; Meath, W.J.; Kondo, A.E.

    2002-01-01

    The pump-probe excitation of a two-level dipolar (d≠0) molecule, where the pump frequency is tuned to the energy level separation while the probe frequency is extremely small, is examined theoretically as an example of absolute phase control of excitation processes. The state populations depend on the probe field's absolute carrier phase but are independent of the pump field's absolute carrier phase. Interestingly, the absolute phase effects occur for pulse durations much longer and field intensities much weaker than those required to see such effects in single pulse excitation

  9. Fluctuation-dissipation theorem in an isolated system of quantum dipolar bosons after a quench.

    Science.gov (United States)

    Khatami, Ehsan; Pupillo, Guido; Srednicki, Mark; Rigol, Marcos

    2013-08-02

    We examine the validity of fluctuation-dissipation relations in isolated quantum systems taken out of equilibrium by a sudden quench. We focus on the dynamics of trapped hard-core bosons in one-dimensional lattices with dipolar interactions whose strength is changed during the quench. We find indications that fluctuation-dissipation relations hold if the system is nonintegrable after the quench, as well as if it is integrable after the quench if the initial state is an equilibrium state of a nonintegrable Hamiltonian. On the other hand, we find indications that they fail if the system is integrable both before and after quenching.

  10. Synthesis and 1,3-Dipolar Cycloaddition Reactions of Chiral Maleimides

    Directory of Open Access Journals (Sweden)

    Lubor Fisera

    1997-02-01

    Full Text Available New routes to the synthesis of various novel chiral maleimides are described. The oxabicyclic anhydride 2 readily available exo-Diels-Alder adduct of furan and maleic anhydride was used as a vehicle, which in turn reacted with hydrochlorides of amino acids 3a-f in the presence of Et3N with release of furan to give the requisite novel chiral imides 4a-f in good to moderate yields. The stereoselectivity of 1,3-dipolar cycloaddition of nitrile oxides with prepared chiral imides 4a-f is investigated.

  11. Synthesis of 1,4-naphthoquinone derivatives using 1,3-dipolar cycloaddition and Sonogashira reactions

    Directory of Open Access Journals (Sweden)

    Wilson Silva do Nascimento

    2010-04-01

    Full Text Available Naphthoquinones are known according to their important bio-activities, such as their antitumoral and topoisomerase inhibition properties. From 2-azido (3 or 2,3-diacetylene-1,4-naphthoquinone (4 it was possible to obtain triazole derivatives (naphthoquinonic. This work describes the synthesis of two novel molecules, with triazole groups linked to 1,4-naphthoquinone using the 1,3-dipolar cycloaddition and Sonogashira reactions. The synthetic strategy followed two routes (Scheme 1. First, we synthesized the 2-bromo-1,4-naphthoquinone (2, yield 98% by using Br2 and CH3CO2H, and then used it to obtain 2-azido-1,4-naphthoquinone (3, yield 62% from compound 1, along with ethanolic solution (reflux and NaN3. Finally, we prepared 1,2,3-triazole compounds (4a, b by 1,3-dipolar cycloaddition, involving compound (3 and terminal acetylenes (phenylacetylene, a and glycoside (b using Cu(OAc2 and ascorbate, under argon atmosphere. During the second step, 2,3-dibromo-1,4-naphthoquinone was prepared using Br2/CH2Cl2 at room temperature. From compound (5 it was possible to synthesize (6, catalyzed by Pd(PPh32Cl2/CuI/Et3N, under argon atmosphere, in 40% yield. The 1,3-dipolar cycloaddition reactions involving 2-azido-1,4-naphthoquinone (3 and alkynes (a, yield 23% and b, yield 30% were conducted using the solvent system, (1:1 terc-BuOH/H2O/r.t/ 20 mol% of Cu(OAc2 and sodium ascorbate, under stirring during 24 hours. The reaction involving 2,3-dibromo-1,4-naphthoquinone (5, yield 65% and phenylacetylene was prepared using the solvent mixture (2:1 DMSO/CHCl3 and catalytic amount of CuI/Pd(PPh32Cl2. The final products were characterized by elemental analysis and spectrometric techniques (IR, NMR 1H and 13C. Two novel triazole compounds were synthesized from naphthoquinones by 1,3-dipolar cycloaddition from suitable 1,4-naphthoquinones obtained by Sonogashira couplings.

  12. Triazol-substituted titanocenes by strain-driven 1,3-dipolar cycloadditions

    Directory of Open Access Journals (Sweden)

    Andreas Gansäuer

    2014-07-01

    Full Text Available An operationally simple, convenient, and mild strategy for the synthesis of triazole-substituted titanocenes via strain-driven 1,3-dipolar cycloadditions between azide-functionalized titanocenes and cyclooctyne has been developed. It features the first synthesis of titanocenes containing azide groups. These compounds constitute ‘second-generation’ functionalized titanocene building blocks for further synthetic elaboration. Our synthesis is modular and large numbers of the complexes can in principle be prepared in short periods of time. Some of the triazole-substituted titanocenes display high cyctotoxic activity against BJAB cells. Comparison of the most active complexes allows the identification of structural features essential for biological activity.

  13. Characteristics of ion distribution functions in dipolarizing flux bundles: Event studies

    Science.gov (United States)

    Runov, A.; Angelopoulos, V.; Artemyev, A.; Birn, J.; Pritchett, P. L.; Zhou, X.-Z.

    2017-06-01

    Taking advantage of multipoint observations from a repeating configuration of the five Time History of Events and Macroscale Interactions during Substorms (THEMIS) probes separated by 1 to 2 Earth radii (RE) along X, Y, and Z in the geocentric solar magnetospheric system (GSM), we study ion distribution functions collected by the probes during three dipolarizing flux bundle (DFB) events observed at geocentric distances 9 energy and twice the thermal energy, although the distribution in the ambient plasma sheet was isotropic. The anisotropic ion distribution in DFBs injected toward the inner magnetosphere may provide the free energy for waves and instabilities, which are important elements of particle energization.

  14. Characterization of surfactant liquid crystal phases suitable for molecular alignment and measurement of dipolar couplings

    International Nuclear Information System (INIS)

    Barrientos, Laura G.; Dolan, Caroline; Gronenborn, Angela M.

    2000-01-01

    Media employed for imparting partial alignment onto solute molecules have recently attracted considerable attention, since they permit the measurement of NMR parameters for solute biomolecules commonly associated with solid state NMR. Here we characterize a medium which is based on a quasi-ternary surfactant system comprising cetylpyridinium bromide/hexanol/sodium bromide. We demonstrate that dilute solutions of this system can exist in liquid crystalline phases which orient in the magnetic field and allow the measurement of residual dipolar couplings under a variety of conditions. The present system is extremely versatile and robust, tolerating different buffer conditions, temperature ranges and concentrations

  15. Dipolar oscillations in a quantum degenerate Fermi-Bose atomic mixture

    International Nuclear Information System (INIS)

    Ferlaino, F; Brecha, R J; Hannaford, P; Riboli, F; Roati, G; Modugno, G; Inguscio, M

    2003-01-01

    We study the dynamics of coupled dipolar oscillations in a Fermi-Bose mixture of 40 K and 87 Rb atoms. This low-energy collective mode is strongly affected by the interspecies interactions. Measurements are performed in the classical and quantum degenerate regimes and reveal the crucial role of the statistical properties of the mixture. At the onset of quantum degeneracy, we investigate the role of Pauli blocking and superfluidity for K and Rb atoms, respectively, resulting in a change in the collisional interactions

  16. Fluctuation and dipolar interaction effects on the pinning of domain walls

    International Nuclear Information System (INIS)

    Chui, S.T.

    2001-01-01

    We discuss the effect of the dipolar interaction on the pinning of domain walls. Domain walls are usually pinned near the boundaries between grains. Magnetic charges accumulated at the domain wall make the wall more unstable and easier to depin. We discuss how the grain-orientation and thermal fluctuations affect these magnetic charges and hence the depinning of the domain walls. Our results are illustrated by finite temperature Monte Carlo simulation on periodic arrays of large cells separated by walls consisting of faces of pyramids

  17. New fluorescent dipolar pyrazine derivatives for non-doped red organic light-emitting diodes

    International Nuclear Information System (INIS)

    Gao Baoxiang; Zhou Quanguo; Geng Yanhou; Cheng Yanxiang; Ma Dongge; Xie Zhiyuan; Wang Lixiang; Wang Fosong

    2006-01-01

    Dipolar fluorescent compounds containing electron-accepting pyrazine-2,3-dicarbonitrile and electron-donating arylamine moiety have been designed and synthesized. The optical and electrochemical properties of these compounds can be adjusted by changing π-bridge length and the donor (D) strength. Organic light-emitting devices based on these compounds are fabricated. Saturated red emission of (0.67, 0.33) and the external quantum efficiency as high as 1.41% have been demonstrated for one of these compounds

  18. Anisotropic properties of phase separation in two-component dipolar Bose-Einstein condensates

    Science.gov (United States)

    Wang, Wei; Li, Jinbin

    2018-03-01

    Using Crank-Nicolson method, we calculate ground state wave functions of two-component dipolar Bose-Einstein condensates (BECs) and show that, due to dipole-dipole interaction (DDI), the condensate mixture displays anisotropic phase separation. The effects of DDI, inter-component s-wave scattering, strength of trap potential and particle numbers on the density profiles are investigated. Three types of two-component profiles are present, first cigar, along z-axis and concentric torus, second pancake (or blood cell), in xy-plane, and two non-uniform ellipsoid, separated by the pancake and third two dumbbell shapes.

  19. T. thermophila group I introns that cleave amide bonds

    Science.gov (United States)

    Joyce, Gerald F. (Inventor)

    1997-01-01

    The present invention relates to nucleic acid enzymes or enzymatic RNA molecules that are capable of cleaving a variety of bonds, including phosphodiester bonds and amide bonds, in a variety of substrates. Thus, the disclosed enzymatic RNA molecules are capable of functioning as nucleases and/or peptidases. The present invention also relates to compositions containing the disclosed enzymatic RNA molecule and to methods of making, selecting, and using such enzymes and compositions.

  20. Enzymatically and reductively degradable α-amino acid-based poly(ester amide)s: Synthesis, cell compatibility, and intracellular anticancer drug delivery

    NARCIS (Netherlands)

    Sun, H.; Cheng, Ru; Deng, Chao; Meng, Fenghua; Dias, Aylvin A.; Hendriks, Marc; Feijen, Jan; Zhong, Zhiyuan

    2015-01-01

    A novel and versatile family of enzymatically and reductively degradable α-amino acid-based poly(ester amide)s (SS-PEAs) were developed from solution polycondensation of disulfide-containing di-p-toluenesulfonic acid salts of bis-l-phenylalanine diesters (SS-Phe-2TsOH) with di-p-nitrophenyl adipate

  1. Composition of amino acid using carbon monoxide. Amide carbonylation reaction

    Energy Technology Data Exchange (ETDEWEB)

    Izawa, Kunisuke (Ajinomoto Co., Inc., Tokyo (Japan))

    1989-02-01

    Amide carbonylation reaction is a method to compose N-acyl-{alpha}-amino acid from aldehyde, carboxylic acid amide, and carbon monoxide in a phase and with high yield. Unlike the conventional Strecker reaction, this method does not use HCN which is in question on public pollution and does not require hydrolysis. This amide carbonylation reaction was discovered by Wakamatsu and others of Ajinomoto Co.,Ltd. Present application examples of this method are the composition of N-acetyl amino acid from the aldehyde class, the composition of N-Acyl amino acid from olefin, the composition of N-acyl or acetyl amino acid from the raw material of alcohol and the halide class, the composition of N-acyl or acetyl amino acid via the isomerization of epoxide and allyl alcohol, the composition of amino dicarboxylic acid, applying deoxidation of ring acid anhydride, the composition of N-acyl amino acid from the raw material of the amine class, the stereoselective composition of -substitution ring-{alpha}-amino acid, and the composition of amino aldehyde. 24 refs., 2 figs., 2 tabs.

  2. Equilibrium amide hydrogen exchange and protein folding kinetics

    International Nuclear Information System (INIS)

    Bai Yawen

    1999-01-01

    The classical Linderstrom-Lang hydrogen exchange (HX) model is extended to describe the relationship between the HX behaviors (EX1 and EX2) and protein folding kinetics for the amide protons that can only exchange by global unfolding in a three-state system including native (N), intermediate (I), and unfolded (U) states. For these slowly exchanging amide protons, it is shown that the existence of an intermediate (I) has no effect on the HX behavior in an off-pathway three-state system (I↔U↔N). On the other hand, in an on-pathway three-state system (U↔I↔N), the existence of a stable folding intermediate has profound effect on the HX behavior. It is shown that fast refolding from the unfolded state to the stable intermediate state alone does not guarantee EX2 behavior. The rate of refolding from the intermediate state to the native state also plays a crucial role in determining whether EX1 or EX2 behavior should occur. This is mainly due to the fact that only amide protons in the native state are observed in the hydrogen exchange experiment. These new concepts suggest that caution needs to be taken if one tries to derive the kinetic events of protein folding from equilibrium hydrogen exchange experiments

  3. Supercritical fluid extraction of uranium and thorium employing dialkyl amides

    International Nuclear Information System (INIS)

    Rao, Ankita; Kumar, Pradeep

    2014-01-01

    Extraction and purification of actinides from different matrices is of utmost importance to the nuclear industry. In recent decades, supercritical fluid extraction (SFE) has emerged as a promising alternative to solvent extraction owing to its inherent potential of minimization of liquid waste generation. N,N-dialkyl aliphatic amides have been proposed to be an alternative to TBP in the reprocessing of spent nuclear fuel due to several attractive features like innocuous nature of degradation products (mainly carboxylic acids/ amines), possibility of complete incineration of the used extractant leading to reduction in volume of secondary waste. Also, physico-chemical properties of this class of extractants can be tuned by the judicious choice of alkyl groups. In the present work, N,N-dialkyl aliphatic amides with varying alkyl groups viz. N,N-dibutyl-2-ethylhexanamide (DBEHA), N,N-dibutyl-3,3-dimethylbutanamide (DBDMBA), N,N-dihexyloctanamide (DHOA), N,N-disecbutylpentamide (DBPA), N,N-dibutyloctanamide (DBOA), have been evaluated for supercritical fluid extraction (SFE) of uranium and thorium from nitric acid medium as well as tissue paper matrix. Amides were obtained from Department of Chemistry, Delhi University and were used as such. This fact could be exploited for separation of thorium and uranium

  4. Residual dipolar couplings in sup 3 sup 1 P MAS spectra of PPh sub 3 substituted cobalt complexes

    CERN Document Server

    Szalontai, G

    2002-01-01

    Residual dipolar couplings between sup 3 sup 1 P- sup 5 sup 9 Co spin pairs were studied in sup 3 sup 1 P MAS spectra of mono- and dinuclear cobalt-triphenylphosphine complexes. These spectra can provide important information such as the scalar coupling between the dipolar phosphorus and the quadrupolar cobalt nuclei normally not available from solution phase studies. In case of complementary (NQR or x-ray) data even the relative orientation of the interacting shielding, dipolar, scalar couplings, and electric field gradient tensors or internuclear distances can be determined. Examples are shown both for well resolved and practically unresolved cases, factors which possibly control the spectral resolution are discussed in detail. (author)

  5. Induced alignment and measurement of dipolar couplings of an SH2 domain through direct binding with filamentous phage

    International Nuclear Information System (INIS)

    Dahlke Ojennus, Deanna; Mitton-Fry, Rachel M.; Wuttke, Deborah S.

    1999-01-01

    Large residual 15 N- 1 H dipolar couplings have been measured in a Src homology II domain aligned at Pf1 bacteriophage concentrations an order of magnitude lower than used for induction of a similar degree of alignment of nucleic acids and highly acidic proteins. An increase in 1 H and 15 N protein linewidths and a decrease in T 2 and T 1 ρ relaxation time constants implicates a binding interaction between the protein and phage as the mechanism of alignment. However, the associated increased linewidth does not preclude the accurate measurement of large dipolar couplings in the aligned protein. A good correlation is observed between measured dipolar couplings and predicted values based on the high resolution NMR structure of the SH2 domain. The observation of binding-induced protein alignment promises to broaden the scope of alignment techniques by extending their applicability to proteins that are able to interact weakly with the alignment medium

  6. Pain and beyond: fatty acid amides and fatty acid amide hydrolase inhibitors in cardiovascular and metabolic diseases.

    Science.gov (United States)

    Pillarisetti, Sivaram; Alexander, Christopher W; Khanna, Ish

    2009-12-01

    Fatty acid amide hydrolase (FAAH) is responsible for the hydrolysis of several important endogenous fatty acid amides (FAAs), including anandamide, oleoylethanolamide and palmitoylethanolamide. Because specific FAAs interact with cannabinoid and vanilloid receptors, they are often referred to as 'endocannabinoids' or 'endovanilloids'. Initial interest in this area, therefore, has focused on developing FAAH inhibitors to augment the actions of FAAs and reduce pain. However, recent literature has shown that these FAAs - through interactions with unique receptors (extracellular and intracellular) - can induce a diverse array of effects that include appetite suppression, modulation of lipid and glucose metabolism, vasodilation, cardiac function and inflammation. This review gives an overview of FAAs and diverse FAAH inhibitors and their potential therapeutic utility in pain and non-pain indications.

  7. A zinc enolate of amide: Preparation and application in reformasky-like reaction leading to β-hydroxy amides

    Energy Technology Data Exchange (ETDEWEB)

    Cho, Hyun Hee; Kim, Seung Hoi [Dept. of Chemistry, Dankook University, Cheonan (Korea, Republic of)

    2015-04-15

    One of the best known functionalized organic complexes is the β-hydroxy carbonyl compound. This unique functionality has been frequently found in naturally occurring bioactive derivatives. The cross-coupling reaction of A with aldehydes were carried out in the absence of any catalyst and completed in most cases within 1.0 h at room temperature. We have developed an efficient synthetic route for the preparation of β-hydroxy amides. The method involved the preparation of room-temperature-stable organo zinc reagents (A, B, and C) in THF and their subsequent coupling reactions with various carbonyl derivatives under mild conditions. Significantly, this approach using zinc enolate of amides could expand the scope of Reformatsky-like reactions. Further studies to elucidate this synthetic protocol are currently under way in our laboratory.

  8. Dispersion characteristics of electromagnetic waves in dipolar (m=±1) modes travelling along a magnetized plasma column

    International Nuclear Information System (INIS)

    Benova, E.; Ghanashev, I.; Zhelyazkov, I.

    1992-01-01

    The modelling of isotropic plasma columns sustained by travelling electromagnetic waves in the dipolar mode (angular dependence exp imφ, m=±1) shows that the m=±1 modes have identical dispersion characteristics. In the presence of an external static magnetic field, however, the modes behave rather differently. This observation arose in studying the axial structures of magnetized plasma columns surrounded by vacuum and produced by travelling electromagnetic waves in the dipolar modes. We examine the propagation of electromagnetic waves along a homogeneous cold plasma column of radius R and electron number density n immersed in an axial constant magnetic field. (author) 3 refs., 3 figs

  9. Accurate determination of interfacial protein secondary structure by combining interfacial-sensitive amide I and amide III spectral signals.

    Science.gov (United States)

    Ye, Shuji; Li, Hongchun; Yang, Weilai; Luo, Yi

    2014-01-29

    Accurate determination of protein structures at the interface is essential to understand the nature of interfacial protein interactions, but it can only be done with a few, very limited experimental methods. Here, we demonstrate for the first time that sum frequency generation vibrational spectroscopy can unambiguously differentiate the interfacial protein secondary structures by combining surface-sensitive amide I and amide III spectral signals. This combination offers a powerful tool to directly distinguish random-coil (disordered) and α-helical structures in proteins. From a systematic study on the interactions between several antimicrobial peptides (including LKα14, mastoparan X, cecropin P1, melittin, and pardaxin) and lipid bilayers, it is found that the spectral profiles of the random-coil and α-helical structures are well separated in the amide III spectra, appearing below and above 1260 cm(-1), respectively. For the peptides with a straight backbone chain, the strength ratio for the peaks of the random-coil and α-helical structures shows a distinct linear relationship with the fraction of the disordered structure deduced from independent NMR experiments reported in the literature. It is revealed that increasing the fraction of negatively charged lipids can induce a conformational change of pardaxin from random-coil to α-helical structures. This experimental protocol can be employed for determining the interfacial protein secondary structures and dynamics in situ and in real time without extraneous labels.

  10. Decarbonylative Phosphorylation of Amides by Palladium and Nickel Catalysis: The Hirao Cross-Coupling of Amide Derivatives.

    Science.gov (United States)

    Liu, Chengwei; Szostak, Michal

    2017-10-02

    Considering the ubiquity of organophosphorus compounds in organic synthesis, pharmaceutical discovery agrochemical crop protection and materials chemistry, new methods for their construction hold particular significance. A conventional method for the synthesis of C-P bonds involves cross-coupling of aryl halides and dialkyl phosphites (the Hirao reaction). We report a catalytic deamidative phosphorylation of a wide range of amides using a palladium or nickel catalyst giving aryl phosphonates in good to excellent yields. The present method tolerates a wide range of functional groups. The reaction constitutes the first example of a transition-metal-catalyzed generation of C-P bonds from amides. This redox-neutral protocol can be combined with site-selective conventional cross-coupling for the regioselective synthesis of potential pharmacophores. Mechanistic studies suggest an oxidative addition/transmetallation pathway. In light of the importance of amides and phosphonates as synthetic intermediates, we envision that this Pd and Ni-catalyzed C-P bond forming method will find broad application. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Energy conversion and dissipation at dipolarization fronts: Theory, modeling and MMS observations

    Science.gov (United States)

    Sitnov, M. I.; Motoba, T.; Merkin, V. G.; Ohtani, S.; Cohen, I. J.; Mauk, B.; Vines, S. K.; Anderson, B. J.; Moore, T. E.; Torbert, R. B.; Giles, B. L.; Burch, J. L.

    2017-12-01

    Magnetic reconnection is one of the most important energy conversion mechanisms in space plasmas. In the classical picture it converts the energy of antiparallel magnetic fields into the kinetic and thermal energy of accelerated plasma particles in reconnection exhausts. It also involves energy dissipation near the X-line. This classical picture may be substantially modified in real space plasma configurations, such as the dayside magnetopause and the magnetotail. In particular, in the magnetotail the flows of accelerated particles may be strongly asymmetric along the tail with the domination of earthward flows. At the same time, strong energy conversion and even dissipation may occur away from the X-line, in particular, at dipolarization fronts. Here we present a theoretical picture of spontaneous magnetotail reconnection based on 3-D PIC simulations with the focus on plasma bulk flows, energy conversion and dissipation. This picture is compared with some observations from the MMS tail season. An important finding from these observations is that dipolarizations fronts may not only be regions of the total energy conversion with jE>0, but they may also be the sites of energy dissipation, both positive (jE'>0, E' is the electric field E in the system moving with one of the plasma species) and negative (jE'braking).

  12. Dipolar flow theory of the universe in relation to astronomical observations and universe axis

    International Nuclear Information System (INIS)

    Mullick, U.P.

    1975-01-01

    An attempt has been made to establish Dipolar continuous flow theory of the universe through corroborations from astronomical observations of the positions of nebulae made earlier by astronomers. It is shown that the line through groups of nebulae in Nubecula Major in Southern Sky Region 5, passing through Earth points towards the near side pole A of the universe. Also the angles the plane parallel to universe polar plane x-x and passing through Earth, makes with the Milky Way disc is about 70 0 towards universe pole B, and about 110 0 towards nearside universe pole A. It is also shown that the two nebulae M 31 and M 33 and the groups of nebulae in Megallenic clouds, in Nebecula Major are between planes passing through universe equatorial axis y-y and plant Ysub(E)-Ysub(E) passing through Earth and parallel to universe equatorial plane Y-Y. Besides, the huge red star Betelgeux and the great Nebula in Orion in sky Region 9 are also between these two planes. These observations the author claims accord with his Dipolar Theory. (author)

  13. Ground-state and dynamical properties of two-dimensional dipolar Fermi liquids

    International Nuclear Information System (INIS)

    Abedinpour, Saeed H.; Asgari, Reza; Tanatar, B.; Polini, Marco

    2014-01-01

    We study the ground-state properties of a two-dimensional spin-polarized fluid of dipolar fermions within the Euler–Lagrange Fermi-hypernetted-chain approximation. Our method is based on the solution of a scattering Schrödinger equation for the “pair amplitude” √(g(r)), where g(r) is the pair distribution function. A key ingredient in our theory is the effective pair potential, which includes a bosonic term from Jastrow–Feenberg correlations and a fermionic contribution from kinetic energy and exchange, which is tailored to reproduce the Hartree–Fock limit at weak coupling. Very good agreement with recent results based on quantum Monte Carlo simulations is achieved over a wide range of coupling constants up to the liquid-to-crystal quantum phase transition. Using the fluctuation–dissipation theorem and a static approximation for the effective inter-particle interactions, we calculate the dynamical density–density response function, and furthermore demonstrate that an undamped zero-sound mode exists for any value of the interaction strength, down to infinitesimally weak couplings. -- Highlights: •We have studied the ground state properties of a strongly correlated two-dimensional fluid of dipolar fermions. •We have calculated the effective inter-particle interaction and the dynamical density–density response function. •We have shown that an undamped zero sound mode exists at any value of the interaction strength

  14. Dipolar local field in homogeneously magnetized quasi-two-dimensional crystals

    International Nuclear Information System (INIS)

    Leon, H; Estevez-Rams, E

    2009-01-01

    A formalism to calculate the dipolar local field in homogeneously magnetized quasi-two-dimensional (Q2D) crystals is comprehensively presented. Two fundamental tests for this formalism are accomplished: the transition from the Q2D quantities to the corresponding 3D ones; and the recovering of the macroscopic quantities of the 3D continuum theory. The additive separation between lattice and shape contributions to the local field allows an unambiguous interpretation of the respective effects. Calculated demagnetization tensors for square and circular lateral geometries of dipole layers show that for a single crystal layer an extremely thin film, but still with a finite thickness, is a better physical representation than a strictly 2D plane. Distinct close-packed structures are simulated and calculations of the local field at the nodes of the stacked 2D lattices allow one to establish the number of significantly coupled dipole layers, depending on the ratio between the interlayer distance and the 2D lattice constant. The conclusions drawn are of interest for the study of the dipolar interaction in magnetic ultrathin films and other nanostructured materials, where magnetic nanoparticles are embedded in non-magnetic matrices.

  15. Effect of simple solutes on the long range dipolar correlations in liquid water

    Energy Technology Data Exchange (ETDEWEB)

    Baul, Upayan, E-mail: upayanb@imsc.res.in; Anishetty, Ramesh, E-mail: ramesha@imsc.res.in; Vemparala, Satyavani, E-mail: vani@imsc.res.in [The Institute of Mathematical Sciences, C.I.T. Campus, Taramani, Chennai 600113 (India); Kanth, J. Maruthi Pradeep, E-mail: jmpkanth@gmail.com [Vectra LLC, Mount Road, Chennai 600006 (India)

    2016-03-14

    Intermolecular correlations in liquid water at ambient conditions have generally been characterized through short range density fluctuations described through the atomic pair distribution functions. Recent numerical and experimental results have suggested that such a description of order or structure in liquid water is incomplete and there exist considerably longer ranged orientational correlations in water that can be studied through dipolar correlations. In this study, using large scale classical, atomistic molecular dynamics simulations using TIP4P-Ew and TIP3P models of water, we show that salts such as sodium chloride (NaCl), potassium chloride (KCl), caesium chloride (CsCl), and magnesium chloride (MgCl{sub 2}) have a long range effect on the dipolar correlations, which cannot be explained by the notion of structure making and breaking by dissolved ions. Observed effects are explained through orientational stratification of water molecules around ions and their long range coupling to the global hydrogen bond network by virtue of the sum rule for water. The observations for single hydrophilic solutes are contrasted with the same for a single methane (CH{sub 4}) molecule. We observe that even a single small hydrophobe can result in enhancement of long range orientational correlations in liquid water, contrary to the case of dissolved ions, which have been observed to have a reducing effect. The observations from this study are discussed in the context of hydrophobic effect.

  16. Effect of Dipolar Interactions on the Magnetization of Single-Molecule Magnets in a cubic lattice

    Science.gov (United States)

    Alcantara Ortigoza, Marisol

    2005-03-01

    Since the one-body tunnel picture of single-molecule magnets (SMM) is not always sufficient to explain the fine structure of experimental hysteresis loops, the effect of intermolecular dipolar interactions has been investigated on an ensemble of 100 3D-systems of 5X5X4 particles, each with spin S = 5, arranged in a cubic lattice. We have solved the Landau-Lifshitz-Gilbert equation for several values of the damping constant, the field sweep rate and the lattice constant. We find that the smaller the damping constant is, the stronger the maximum field needs to be to produce hysteresis. Furthermore, the shape of the hysteresis loops also depends on the damping constant. We also find that the system magnetizes and demagnetizes faster with decreasing sweep rates, resulting in smaller hysteresis loops. Variations of the lattice constant within realistic values (1.5nm and 2.5nm) show that the dipolar interaction plays an important role in magnetic hysteresis by controlling the relaxation process. Examination of temperature dependencies (0.1K and 0.7K) of the above will be presented and compared with recent experimental data on SMM.

  17. Characteristics of high-latitude precursor flows ahead of dipolarization fronts

    Science.gov (United States)

    Li, Jia-Zheng; Zhou, Xu-Zhi; Runov, Andrei; Angelopoulos, Vassilis; Liu, Jiang; Pan, Dong-Xiao; Zong, Qiu-Gang

    2017-05-01

    Dipolarization fronts (DFs), earthward propagating structures in the magnetotail current sheet characterized by sharp enhancements of northward magnetic field, are capable of converting electromagnetic energy into particle kinetic energy. The ions previously accelerated and reflected at the DFs can contribute to plasma flows ahead of the fronts, which have been identified as DF precursor flows in both the near-equatorial plasma sheet and far from it, near the plasma sheet boundary. Using observations from the THEMIS (Time History of Events and Macroscale Interactions during Substorms) spacecraft, we show that the earthward particle and energy flux enhancements ahead of DFs are statistically larger farther away from the neutral sheet (at high latitudes) than in the near-equatorial region. High-latitude particle and energy fluxes on the DF dawnside are found to be significantly greater than those on the duskside, which is opposite to the dawn-dusk asymmetries previously found near the equatorial region. Using forward and backward tracing test-particle simulations, we then explain and reproduce the observed latitude-dependent characteristics of DF precursor flows, providing a better understanding of ion dynamics associated with dipolarization fronts.

  18. Supra Arcade Downflows with XRT Informed by Dipolarization Fronts with THEMIS

    Science.gov (United States)

    Kobelski, Adam; Savage, Sabrina L.; Malaspina, David M.

    2016-01-01

    Magnetic reconnection can rapidly reconfigure the magnetic field of the corona, accelerating plasma through the site of reconnection. Ambiguities due to the nature of remote sensing have complicated the interpretation of observations of the inflowing and outflowing plasma in reconnecting regions. In particular, the interpretation of sunward moving density depletions above flare arcades (known as Supra Arcade Downflows - SADs) is still debated. Hinode/XRT has provided a wealth of observations for SADs and helped inform our current understanding of these structures. SADs have been interpreted as wakes behind newly reconnected and outflowing loops (Supra Arcade Downflowing Loops - SADLs). Models have shown the plausibility of this interpretation, though this interpretation has not yet been fully accepted. We present here observations of newly reconnected outflowing loops observed via in situ instruments in the magnetosphere. These observations, provided by five THEMIS spacecraft, show that around retracting loops (dipolarization fronts in this context) similar dynamic temperature and density structures are found as seen in SADs. We compare data from multiple SADs and dipolarization fronts to show that the observational signatures implied in the corona can be directly observed in similar plasma regimes in the magnetosphere, strongly favoring the interpretation of SADs as wakes behind retracting loops.

  19. Binary and ternary cocrystals of sulfa drug acetazolamide with pyridine carboxamides and cyclic amides

    OpenAIRE

    Bolla, Geetha; Nangia, Ashwini

    2016-01-01

    A novel design strategy for cocrystals of a sulfonamide drug with pyridine carboxamides and cyclic amides is developed based on synthon identification as well as size and shape match of coformers. Binary adducts of acetazolamide (ACZ) with lactams (valerolactam and caprolactam, VLM, CPR), cyclic amides (2-pyridone, labeled as 2HP and its derivatives MeHP, OMeHP) and pyridine amides (nicotinamide and picolinamide, NAM, PAM) were obtained by manual grinding, and their single crystals by solutio...

  20. Synthesis of new fatty acids amides from aminolysis of fatty acid methyl esters (FAMEs)

    International Nuclear Information System (INIS)

    Lopes, Carolina R.; Montes D'Oca, Caroline da Ros; Duarte, Rodrigo da C.; Kurz, Marcia H.S.; Primel, Ednei G.; Clementin, Rosilene M.; Villarreyes, Joaquin Ariel M.; Montes D'Oca, Marcelo G.

    2010-01-01

    Recent biochemical and pharmacological studies have led to the characterization of different fatty acid amides as a new family of biologically active lipids. Here, we describe the synthesis of new amides from C16:0, 18:0, 18:1 and 18:1, OH fatty acids (FFA) families with cyclic and acyclic amines and demonstrate for the first time that these compounds produce cytotoxic effects. Application of this method to the synthesis of fatty acid amides was performed using the esters aminolysis as a key step and various carboxylic amides were prepared in good yield from fatty acid methyl esters (FAMEs). (author)

  1. FMRF-amide-like immunoreactivity in brain and pituitary of the hagfish Eptatretus burgeri (Cyclostomata)

    DEFF Research Database (Denmark)

    Jirikowski, G; Erhart, G; Grimmelikhuijzen, C J

    1984-01-01

    Paraffin sections of brain and pituitary of the hagfish Eptatretus burgeri were immunostained with an antiserum to FMRF-amide. Immunoreactivity was visible in a large number of neurons in the posterior part of the ventromedial hypothalamus and in long neuronal processes extending cranially from...... the hypothalamus to the olfactory system and caudally to the medulla oblongata. FMRF-amide-like immunoreactivity was also found in cells of the adenohypophysis. These observations suggest that the hagfish possesses a brain FMRF-amide-like transmitter system and pituitary cells containing FMRF-amide-like material...

  2. Copper(II)-catalyzed amidations of alkynyl bromides as a general synthesis of ynamides and Z-enamides. An intramolecular amidation for the synthesis of macrocyclic ynamides.

    Science.gov (United States)

    Zhang, Xuejun; Zhang, Yanshi; Huang, Jian; Hsung, Richard P; Kurtz, Kimberly C M; Oppenheimer, Jossian; Petersen, Matthew E; Sagamanova, Irina K; Shen, Lichun; Tracey, Michael R

    2006-05-26

    A general and efficient method for the coupling of a wide range of amides with alkynyl bromides is described here. This novel amidation reaction involves a catalytic protocol using copper(II) sulfate-pentahydrate and 1,10-phenanthroline to direct the sp-C-N bond formation, leading to a structurally diverse array of ynamides including macrocyclic ynamides via an intramolecular amidation. Given the surging interest in ynamide chemistry, this atom economical synthesis of ynamides should invoke further attention from the synthetic organic community.

  3. Dynamic effects of dipolar interactions on the magnetic behavior of magnetite nanoparticles

    Science.gov (United States)

    Allia, Paolo; Tiberto, Paola

    2011-12-01

    Isothermal magnetization and initial dc susceptibility of spheroidal, nearly monodisperse magnetite nanoparticles (typical diameter: 8 nm) prepared by a standard thermo-chemical route have been measured between 10 and 300 K. The samples contained magnetite nanoparticles in the form of either a dried powder (each nanoparticle being surrounded by a stable oleic acid shell as a result of the preparation procedure) or a solid dispersion in PEGDA-600 polymer; different nanoparticle (NP) concentrations in the polymer were studied. In all samples the NPs were not tightly agglomerated nor their ferromagnetic cores were directly touching. The high-temperature inverse magnetic susceptibility is always found to follow a linear law as a function of T, crossing the horizontal axis at negative temperatures ranging from 175 to about 1,000 K. The deviation from the standard superparamagnetic behavior is related to dipolar interaction among NPs; however, a careful analysis makes it hard to conclude that such a behavior originates from a dominant antiferromagnetic character of the interaction. The results are well explained considering that the studied samples are in the interacting superparamagnetic (ISP) regime. The ISP model is basically a mean field theory which allows one to straightforwardly account for the role of magnetic dipolar interaction in a NP system. The model predicts the existence of specific scaling laws for the reduced magnetization which have been confirmed in all studied samples. The interaction of each magnetic dipole moment with the local, random dipolar field produced by the other dipoles results in the presence of a large fluctuating energy term whose magnitude is comparable to the static barrier for magnetization reversal/rotation related to magnetic anisotropy. On the basis of the existing theories on thermal crossing of a barrier whose height randomly fluctuates in time it is predicted that the rate of barrier crossing is substantially driven by the rate

  4. Amides are novel protein modifications formed by physiological sugars.

    Science.gov (United States)

    Glomb, M A; Pfahler, C

    2001-11-09

    The Maillard reaction, or nonenzymatic browning, proceeds in vivo, and the resulting protein modifications (advanced glycation end products) have been associated with various pathologies. Despite intensive research only very few structures have been established in vivo. We report here for the first time N(6)-[2-[(5-amino-5-carboxypentyl)amino]-2-oxoethyl]lysine (GOLA) and N(6)-glycoloyllysine (GALA) as prototypes for novel amide protein modifications produced by reducing sugars. Their identity was confirmed by independent synthesis and coupled liquid chromatography/mass spectrometry. Model reactions with N(alpha)-t-butoxycarbonyl-lysine showed that glyoxal and glycolaldehyde are immediate precursors, and reaction pathways are directly linked to N(epsilon)-carboxymethyllysine via glyoxal-imine structures. GOLA, the amide cross-link, and 1,3-bis(5-amino-5-carboxypentyl)imidazolium salt (GOLD), the imidazolium cross-link, share a common intermediate. The ratio of GOLA to GOLD is greater when glyoxal levels are low at constant lysine concentrations. GOLA and GALA formation from the Amadori product of glucose and lysine depends directly upon oxidation. With the advanced glycation end product inhibitors aminoguanidine and pyridoxamine we were able to dissect oxidative fragmentation of the Amadori product as a second mechanism of GOLA formation exactly coinciding with N(epsilon)-carboxymethyllysine synthesis. In contrast, the formation of GALA appears to depend solely upon glyoxal-imines. After enzymatic hydrolysis GOLA was found at 66 pmol/mg of brunescent lens protein. This suggests amide protein modifications as important markers of pathophysiological processes.

  5. Quantitative structure-cytotoxicity relationship of phenylpropanoid amides.

    Science.gov (United States)

    Shimada, Chiyako; Uesawa, Yoshihiro; Ishihara, Mariko; Kagaya, Hajime; Kanamoto, Taisei; Terakubo, Shigemi; Nakashima, Hideki; Takao, Koichi; Saito, Takayuki; Sugita, Yoshiaki; Sakagami, Hiroshi

    2014-07-01

    A total of 12 phenylpropanoid amides were subjected to quantitative structure-activity relationship (QSAR) analysis, based on their cytotoxicity, tumor selectivity and anti-HIV activity, in order to investigate on their biological activities. Cytotoxicity against four human oral squamous cell carcinoma (OSCC) cell lines and three human oral normal cells was determined by the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) method. Tumor selectivity was evaluated by the ratio of the mean CC50 (50% cytotoxic concentration) against normal oral cells to that against OSCC cell lines. Anti-HIV activity was evaluated by the ratio of CC50 to EC50 (50% cytoprotective concentration from HIV infection). Physicochemical, structural, and quantum-chemical parameters were calculated based on the conformations optimized by the LowModeMD method followed by density functional theory (DFT) method. Twelve phenylpropanoid amides showed moderate cytotoxicity against both normal and OSCC cell lines. N-Caffeoyl derivatives coupled with vanillylamine and tyramine exhibited relatively higher tumor selectivity. Cytotoxicity against normal cells was correlated with descriptors related to electrostatic interaction such as polar surface area and chemical hardness, whereas cytotoxicity against tumor cells correlated with free energy, surface area and ellipticity. The tumor-selective cytotoxicity correlated with molecular size (surface area) and electrostatic interaction (the maximum electrostatic potential). The molecular size, shape and ability for electrostatic interaction are useful parameters for estimating the tumor selectivity of phenylpropanoid amides. Copyright© 2014 International Institute of Anticancer Research (Dr. John G. Delinassios), All rights reserved.

  6. Analytical applications of resins containing amide and polyamine functional groups

    International Nuclear Information System (INIS)

    Orf, G.M.

    1977-01-01

    Resins are prepared by chemically bonding N,N-dialkylamides and polyamine functional groups to Amberlite XAD-4. These resins are applied to the concentration of metal ions from dilute aqueous solution and the rapid separation of metal ions by high-speed liquid chromatography with continuous on-line detection of the eluent stream. A dibutyl amide resin is used for the separation of uranium(VI), thorium(IV), and zirconium(IV) from each other and several other metal ions. Uranium(VI) and thorium(IV) are determined in the presence of large excesses of foreign metal ions and anions. A practical application of the amide resin is studied by determining uranium in low grade uranium ores. The amide resin is also used for the selective concentration of gold(III) from seawater. A triethylenetetramine resin is used for the separation of copper(II) from equal molar amounts and large excesses of nickel(II), cobalt(II), zinc(II), cadmium(II), iron(III) and aluminum(III). Copper(II), nickel(II), zinc(II), cobalt(II) and cadmium(II) are determined in the presence of large excesses of calcium(II) and magnesium(II). The resin was found to be selective for silver(I) and mercury(II) at low pH values and a rapid separation of equal molar amounts of copper(II) and silver(I) was performed. The resin was also found to have an affinity for anionic metal complexes such as iron(III)-tartrate when the resin is in the hydrogen form. A study of the retention of the anions chromium(III)-tartrate and dichromate at various pH values was performed to better understand the anion exchange properties of the resin. Triethylenetetramine resins were also prepared from polystyrene gel to make a resin with higher capacities for copper

  7. Asymmetric 1,3-Dipolar Cycloadditions to 5-(R)-Menthyloxy-2(5H)-Furanone

    NARCIS (Netherlands)

    Rispens, Minze T.; Keller, Erik; Lange, Ben de; Zijlstra, Robert W.J.; Feringa, Bernard

    Various diazo compounds, nitrile oxides, nitrones and azomethine ylides were examined in 1,3-dipolar cycloadditions to enantiomerically pure 5-(R)-menthyloxy-2(5H)-furanone 1a. Pyrazoline 9 was obtained in 100% c.y. as a mixture of 2 diastereoisomers in ratios up to 72 : 28, whereas pyrazoline 16

  8. Minute splitting of magnetic excitations in CsFeCl{sub 3} due to dipolar interaction observed by polarised neutrons

    Energy Technology Data Exchange (ETDEWEB)

    Dorner, B [Institut Max von Laue - Paul Langevin (ILL), 38 - Grenoble (France); Baehr, M [HMI, Berlin (Germany); Petitgrand, D [Laboratoire Leon Brillouin (LLB) - Centre d` Etudes de Saclay, 91 - Gif-sur-Yvette (France)

    1997-04-01

    Using inelastic neutron scattering with polarisation analysis it was possible, for the first time, to observe simultaneously the two magnetic modes split due to dipolar interaction. This would not have been possible with energy resolution only. An analysis of eigenvectors was also performed. (author). 4 refs.

  9. Inclusion Compound Based Approach to Forming Arrays of Artificial Dipolar Molecular Rotors: A Search for Optimal Rotor Structures

    Czech Academy of Sciences Publication Activity Database

    Kobr, L.; Zhao, K.; Shen, X.; Shoemaker, R. K.; Rogers, C. T.; Michl, Josef

    2013-01-01

    Roč. 25, č. 3 (2013), s. 443-448 ISSN 0935-9648 EU Projects: European Commission(XE) 227756 - DIPOLAR ROTOR ARRAY Grant - others:NSF(US) CHE 0848663 Institutional support: RVO:61388963 Keywords : inclusion compounds * molecular rotors * ferroelectricity * two-dimensional arrays Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 15.409, year: 2013

  10. Using the phase shift to asymptotically characterize the dipolar mixed modes in post-main-sequence stars

    DEFF Research Database (Denmark)

    Jiang, C.; Christensen-Dalsgaard, J.; Cunha, M.

    2018-01-01

    from the eigenvalue condition for mixed modes as a tool to characterize dipolar mixed modes from the theoretical as well as the practical point of view. Unlike the coupling strength, whose variation in a given star is very small over the relevant frequency range, the phase shifts vary significantly...

  11. Bulk functionalization of graphene using diazonium compounds and amide reaction

    Science.gov (United States)

    Peng, Chang; Xiong, Yuzi; Liu, Zhibo; Zhang, Fan; Ou, Encai; Qian, Jiangtao; Xiong, Yuanqin; Xu, Weijian

    2013-09-01

    An efficient and convenient method is applied to introduce varieties of simple functionalities onto the graphene surface for the bulk preparation, which begins with pristine graphite that does not require initial oxidative damage of the graphene basal planes. Diazonium compounds functionalized reaction is demonstrated and it successfully prevented the aggregation of graphene for which providing solubility in high polar organic media or even in volatile solvents such as ethanol and acetone. This approach is complemented by the phenyl carboxylic diazonium salt functionalized graphene (PCFG) attachment of a symmetrically substituted zinc phthalocyanine (PCFG-Pc) using the amide reaction, which is used for the covalent introduction of a complex phthalocyanine molecule.

  12. Antifungal activity of natural and synthetic amides from Piper species

    Energy Technology Data Exchange (ETDEWEB)

    Marques, Joaquim V.; Oliveira, Alberto de; Kato, Massuo J., E-mail: majokato@iq.usp.b [Universidade de Sao Paulo (IQ/USP), SP (Brazil). Inst. de Quimica; Raggi, Ludmila; Young, Maria C. [Instituto de Botanica, Sao Paulo, SP (Brazil). Secao de Fisiologia e Bioquimica de Plantas

    2010-07-01

    The antifungal leaves extract from Piper scutifolium was submitted to bioactivity-guided chromatographic separation against Cladosporium cladosporioides and C. sphaerospermum yielding piperine, piperlonguminine and corcovadine as the active principles which displayed a detection limit of 1 {mu}g. Structure-activity relationships were investigated with the preparation of twelve analogs having differences in the number of unsaturations, aromatic ring substituents and in the amide moiety. Analogs having a single double-bond and no substituent in the aromatic ring displayed higher activity, while N,N,-diethyl analogs displayed higher dose-dependent activity. (author)

  13. Identification of nitrogen compounds and amides from spent hydroprocessing catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Choi, J.H.K.; Gray, M.R. (University of Alberta, Edmonton, AB (Canada). Dept. of Chemical Engineering)

    1991-06-01

    A spent commercial naphtha hydrotreating catalyst was analyzed to identify compounds which had accumulated on the catalyst surface during its active life. The catalyst was extracted with methylene chloride, methanol and pyridine to remove adsorbed organic material, which was rich in nitrogen and oxygen. A series of quinolones were identified in the methanol extract after enrichment with HCl-modified silica gel adsorption and subsequent silica gel chromatography. Tetra- and hexahydroquinolones with alkyl substituents up to C{sub 3} were identified. Similar amides have been identified in asphaltenes, and are very resistant to hydrogenation. Tetrahydroquinolines and piperidines were detected in the pyridine extract. 36 refs., 8 figs., 2 tabs.

  14. Antiproliferative activity of synthetic fatty acid amides from renewable resources.

    Science.gov (United States)

    dos Santos, Daiane S; Piovesan, Luciana A; D'Oca, Caroline R Montes; Hack, Carolina R Lopes; Treptow, Tamara G M; Rodrigues, Marieli O; Vendramini-Costa, Débora B; Ruiz, Ana Lucia T G; de Carvalho, João Ernesto; D'Oca, Marcelo G Montes

    2015-01-15

    In the work, the in vitro antiproliferative activity of a series of synthetic fatty acid amides were investigated in seven cancer cell lines. The study revealed that most of the compounds showed antiproliferative activity against tested tumor cell lines, mainly on human glioma cells (U251) and human ovarian cancer cells with a multiple drug-resistant phenotype (NCI-ADR/RES). In addition, the fatty methyl benzylamide derived from ricinoleic acid (with the fatty acid obtained from castor oil, a renewable resource) showed a high selectivity with potent growth inhibition and cell death for the glioma cell line-the most aggressive CNS cancer. Copyright © 2014 Elsevier Ltd. All rights reserved.

  15. Coordination compounds of cobalt and cadmium with isobutyric acid amide

    International Nuclear Information System (INIS)

    Tsivadze, A.Yu.; Ivanova, I.S.; Solovkina, O.A.

    1983-01-01

    Coordination compounds of cobalt and cadmium with isobutyric acid amide (IBAA) of Co(NCS) 2 x(IBAA) 2 (H 2 O) 2 , CoCl 2 (IBAA) 4 , CoI 2 (IBAA) 8 (H 2 O) 2 , CdI 2 (IBAA) 2 composition have been synthesized and characterized. Their infrared absorption spectra (200-400 cm -1 ), electron reflection spectra (200-750 nm) were studied. It is shown that in all compounds there are IBAA molecUles coordinated through an oxygen atom. Thiocyanogroups are coordinated throUgh nitrogen atoms

  16. Efficient dipolar double quantum filtering under magic angle spinning without a (1)H decoupling field.

    Science.gov (United States)

    Courtney, Joseph M; Rienstra, Chad M

    2016-08-01

    We present a systematic study of dipolar double quantum (DQ) filtering in (13)C-labeled organic solids over a range of magic-angle spinning rates, using the SPC-n recoupling sequence element with a range of n symmetry values from 3 to 11. We find that efficient recoupling can be achieved for values n⩾7, provided that the (13)C nutation frequency is on the order of 100kHz or greater. The decoupling-field dependence was investigated and explicit heteronuclear decoupling interference conditions identified. The major determinant of DQ filtering efficiency is the decoupling interference between (13)C and (1)H fields. For (13)C nutation frequencies greater than 75kHz, optimal performance is observed without an applied (1)H field. At spinning rates exceeding 20kHz, symmetry conditions as low as n=3 were found to perform adequately. Copyright © 2016 Elsevier Inc. All rights reserved.

  17. Density functional theory investigation of two-dimensional dipolar fermions in a harmonic trap

    International Nuclear Information System (INIS)

    Ustunel, Hande; Abedinpour, Saeed H; Tanatar, B

    2014-01-01

    We investigate the behavior of polarized dipolar fermions in a two-dimensional harmonic trap in the framework of the density functional theory (DFT) formalism using the local density approximation. We treat only a few particles interacting moderately. Important results were deduced concerning key characteristics of the system such as total energy and particle density. Our results indicate that, at variance with Coulombic systems, the exchange- correlation component was found to provide a large contribution to the total energy for a large range of interaction strengths and particle numbers. In addition, the density profiles of the dipoles are shown to display important features around the origin that is not possible to capture by earlier, simpler treatments of such systems

  18. High electronegativity multi-dipolar electron cyclotron resonance plasma source for etching by negative ions

    DEFF Research Database (Denmark)

    Stamate, Eugen; Draghici, M.

    2012-01-01

    A large area plasma source based on 12 multi-dipolar ECR plasma cells arranged in a 3 x 4 matrix configuration was built and optimized for silicon etching by negative ions. The density ratio of negative ions to electrons has exceeded 300 in Ar/SF6 gas mixture when a magnetic filter was used...... to reduce the electron temperature to about 1.2 eV. Mass spectrometry and electrostatic probe were used for plasma diagnostics. The new source is free of density jumps and instabilities and shows a very good stability for plasma potential, and the dominant negative ion species is F-. The magnetic field...... in plasma volume is negligible and there is no contamination by filaments. The etching rate by negative ions measured in Ar/SF6/O-2 mixtures was almost similar with that by positive ions reaching 700 nm/min. (C) 2012 American Institute of Physics...

  19. Dipolar magnetism in ordered and disordered low-dimensional nanoparticle assemblies

    DEFF Research Database (Denmark)

    Varón, M.; Beleggia, M; Kasama, T

    2013-01-01

    order at ambient temperature in assemblies of closely-spaced nanoparticles with magnetic moments of ≥ 100 μ(B). Here we use electron holography with sub-particle resolution to reveal the correlation between particle arrangement and magnetic order in self-assembled 1D and quasi-2D arrangements of 15 nm...... cobalt nanoparticles. In the initial states, we observe dipolar ferromagnetism, antiferromagnetism and local flux closure, depending on the particle arrangement. Surprisingly, after magnetic saturation, measurements and numerical simulations show that overall ferromagnetic order exists in the present...... nanoparticle assemblies even when their arrangement is completely disordered. Such direct quantification of the correlation between topological and magnetic order is essential for the technological exploitation of magnetic quasi-2D nanoparticle assemblies....

  20. Singular Value Decomposition Method to Determine Distance Distributions in Pulsed Dipolar Electron Spin Resonance.

    Science.gov (United States)

    Srivastava, Madhur; Freed, Jack H

    2017-11-16

    Regularization is often utilized to elicit the desired physical results from experimental data. The recent development of a denoising procedure yielding about 2 orders of magnitude in improvement in SNR obviates the need for regularization, which achieves a compromise between canceling effects of noise and obtaining an estimate of the desired physical results. We show how singular value decomposition (SVD) can be employed directly on the denoised data, using pulse dipolar electron spin resonance experiments as an example. Such experiments are useful in measuring distances and their distributions, P(r) between spin labels on proteins. In noise-free model cases exact results are obtained, but even a small amount of noise (e.g., SNR = 850 after denoising) corrupts the solution. We develop criteria that precisely determine an optimum approximate solution, which can readily be automated. This method is applicable to any signal that is currently processed with regularization of its SVD analysis.

  1. Simulation study of localization of electromagnetic waves in two-dimensional random dipolar systems

    International Nuclear Information System (INIS)

    Wang, Ken Kang-Hsin; Ye Zhen

    2003-01-01

    We study the propagation and scattering of electromagnetic waves by random arrays of dipolar cylinders in a uniform medium. A set of self-consistent equations, incorporating all orders of multiple scattering of the electromagnetic waves, is derived from first principles and then solved numerically for electromagnetic fields. For certain ranges of frequencies, spatially localized electromagnetic waves appear in such a simple but realistic disordered system. Dependence of localization on the frequency, radiation damping, and filling factor is shown. The spatial behavior of the total, coherent, and diffusive waves is explored in detail, and found to comply with a physical intuitive picture. A phase diagram characterizing localization is presented, in agreement with previous investigations on other systems

  2. Simulation study of localization of electromagnetic waves in two-dimensional random dipolar systems.

    Science.gov (United States)

    Wang, Ken Kang-Hsin; Ye, Zhen

    2003-12-01

    We study the propagation and scattering of electromagnetic waves by random arrays of dipolar cylinders in a uniform medium. A set of self-consistent equations, incorporating all orders of multiple scattering of the electromagnetic waves, is derived from first principles and then solved numerically for electromagnetic fields. For certain ranges of frequencies, spatially localized electromagnetic waves appear in such a simple but realistic disordered system. Dependence of localization on the frequency, radiation damping, and filling factor is shown. The spatial behavior of the total, coherent, and diffusive waves is explored in detail, and found to comply with a physical intuitive picture. A phase diagram characterizing localization is presented, in agreement with previous investigations on other systems.

  3. Dynamical Properties of a Diluted Dipolar-Interaction Heisenberg Spin Glass

    International Nuclear Information System (INIS)

    Zhang Kai-Cheng; Liu Yong; Chi Feng

    2014-01-01

    Up to now the chirality is seldom studied in the diluted spin glass although many investigations have been performed on the site-ordered Edwards—Anderson model. By simulation, we investigate the dynamical properties of both the spin-glass and the chiral-glass phases in a diluted dipolar system, which was manifested to have a spin-glass transition by recent numerical study. By scaling we find that both phases have the same aging behavior and closer aging parameter μ. Similarly, the domains grow in the same way and both phases have a closer barrier exponent Ψ. It means that both the spins and the chirality have the same dynamical properties and they may freeze at the same temperature. (condensed matter: electronic structure, electrical, magnetic, and optical properties)

  4. Magnetospheric Multiscale (MMS) Observations of Energetic Ion Response to Magnetotail Dipolarization Events

    Science.gov (United States)

    Cohen, I. J.; Mauk, B.; Anderson, B. J.; Sitnov, M. I.; Motoba, T.; Ohtani, S.; Gkioulidou, M.; Fuselier, S. A.; Giles, B. L.; Strangeway, R. J.; Torbert, R. B.; Burch, J. L.

    2017-12-01

    Observations from the Energetic Ion Spectrometer (EIS) instruments aboard MMS have shown angular (pitch, elevation, azimuthal) asymmetries of energetic (>10s of keV) ions corresponding to dipolarization events in the near-Earth and distant magnetotail. In particular, EIS distinguishes the species composition of these ions (protons, helium, oxygen) and reveals apparent species-based differences in their response. This study presents analysis of the dynamic injection and mass-dependent response of energetic ions that likely result from the kinetic response of the ions to the time-varying electric and magnetic fields associated with injection process. Analysis is focused on discriminating between truly kinetic responses to the dynamics and the features that arise from large gyro-radii particles in the vicinity of strong spatial gradients. The study will focus on EIS measurements and include supplementary data from the FIELDS, FPI, and HPCA instruments.

  5. Mutual capture of dipolar molecules at low and very low energies. I. Approximate analytical treatment.

    Science.gov (United States)

    Nikitin, E E; Troe, J

    2010-09-16

    Approximate analytical expressions are derived for the low-energy rate coefficients of capture of two identical dipolar polarizable rigid rotors in their lowest nonresonant (j(1) = 0 and j(2) = 0) and resonant (j(1) = 0,1 and j(2) = 1,0) states. The considered range extends from the quantum, ultralow energy regime, characterized by s-wave capture, to the classical regime described within fly wheel and adiabatic channel approaches, respectively. This is illustrated by the table of contents graphic (available on the Web) that shows the scaled rate coefficients for the mutual capture of rotors in the resonant state versus the reduced wave vector between the Bethe zero-energy (left arrows) and classical high-energy (right arrow) limits for different ratios δ of the dipole-dipole to dispersion interaction.

  6. Long-range transverse Ising model built with dipolar condensates in two-well arrays

    International Nuclear Information System (INIS)

    Li, Yongyao; Pang, Wei; Xu, Jun; Lee, Chaohong; Malomed, Boris A; Santos, Luis

    2017-01-01

    Dipolar Bose–Einstein condensates in an array of double-well potentials realize an effective transverse Ising model with peculiar inter-layer interactions, that may result under proper conditions in an anomalous first-order ferromagnetic–antiferromagnetic phase transition, and non-trivial phases due to frustration. The considered setup allows as well for the study of Kibble–Zurek defect formation, whose kink statistics follows that expected from the universality class of the mean-field one-dimensional transverse Ising model. Furthermore, random occupation of each layer of the stack leads to random effective Ising interactions and local transverse fields, that may lead to the Anderson-like localization of imbalance perturbations. (paper)

  7. Compressibility, zero sound, and effective mass of a fermionic dipolar gas at finite temperature

    International Nuclear Information System (INIS)

    Kestner, J. P.; Das Sarma, S.

    2010-01-01

    The compressibility, zero-sound dispersion, and effective mass of a gas of fermionic dipolar molecules is calculated at finite temperature for one-, two-, and three-dimensional uniform systems, and in a multilayer quasi-two-dimensional system. The compressibility is nonmonotonic in the reduced temperature, T/T F , exhibiting a maximum at finite temperature. This effect might be visible in a quasi-low-dimensional experiment, providing a clear signature of the onset of many-body quantum degeneracy effects. The collective mode dispersion and effective mass show similar nontrivial temperature and density dependence. In a quasi-low-dimensional system, the zero-sound mode may propagate at experimentally attainable temperatures.

  8. Influence of static and dynamic dipolar fields in bulk YIG/thin film NiFe systems probed via spin rectification effect

    Energy Technology Data Exchange (ETDEWEB)

    Soh, Wee Tee, E-mail: a0046479@u.nus.edu [Center for Superconducting and Magnetic Materials, Department of Physics, National University of Singapore, 2 Science Drive 3, Singapore 117551 (Singapore); Tay, Z.J. [Center for Superconducting and Magnetic Materials, Department of Physics, National University of Singapore, 2 Science Drive 3, Singapore 117551 (Singapore); Yakovlev, N.L. [Institute of Materials Research and Engineering, A*STAR (Agency for Science, Technology and Research), 3 Research Link, Singapore 117602 (Singapore); Peng, Bin [State Key Laboratory of Electronic Thin Films and Integrated Devices, University of Electronic Science and Technology of China, Chengdu 610054 (China); Ong, C.K. [Center for Superconducting and Magnetic Materials, Department of Physics, National University of Singapore, 2 Science Drive 3, Singapore 117551 (Singapore); Temasek Laboratories, National University of Singapore, 5A Engineering Drive 2, Singapore 117411 (Singapore)

    2017-03-15

    The characteristics of the static and dynamic components of the dipolar fields originating from a bulk polycrystalline yttrium iron garnet (YIG) substrate are probed by depositing a NiFe (Permalloy) layer on it, which acts as a detector. By measuring dc voltages generated via spin rectification effect (SRE) within the NiFe layer under microwave excitation, we characterize the influence of dipolar fields from bulk YIG on the NiFe layer. It is found that the dynamic YIG dipolar fields modify the self-SRE of NiFe, driving its own rectification voltages within the NiFe layer, an effect we term as non-local SRE. This non-local SRE only occurs near the simultaneous resonance of both YIG and NiFe. On the other hand, the static dipolar field from YIG manifests itself as a negative anisotropy in the NiFe layer which shifts the latter’s ferromagnetic resonance frequency. - Highlights: • We demonstrate the quantification of both the static and dynamic components of the dipolar fields due to a YIG slab. • The detection and characterisation of such dipolar fields are important in many magnetic applications such as magnonics. • The dipolar fields can pose potential pitfalls if not properly considered in certain spin-electronics systems.

  9. Stacking of purines in water: the role of dipolar interactions in caffeine.

    Science.gov (United States)

    Tavagnacco, L; Di Fonzo, S; D'Amico, F; Masciovecchio, C; Brady, J W; Cesàro, A

    2016-05-11

    During the last few decades it has been ascertained that base stacking is one of the major contributions stabilizing nucleic acid conformations. However, the understanding of the nature of the interactions involved in the stacking process remains under debate and it is a subject of theoretical and experimental studies. Structural similarity between purine bases (guanine and adenine) in DNA and the caffeine molecule makes caffeine an excellent model for the purine bases. The present study clearly shows that dipolar interactions play a fundamental role in determining stacking of purine molecules in solution. In order to reach this achievement, polarized ultraviolet Raman resonant scattering experiments have been carried out on caffeine aqueous solutions as a function of concentration and temperature. The investigation pointed out at the aggregation and solvation properties, particularly at elevated temperatures. Kubo-Anderson theory was used as a framework to investigate the non-coincidence effect (NCE) occurring in the totally symmetric breathing modes of the purine rings, and in the bending modes of the methyl groups of caffeine. The NCE concentration dependence shows that caffeine aggregation at 80 °C occurs by planar stacking of the hydrophobic faces. The data clearly indicate that dipolar interactions determine the reorientational motion of the molecules in solution and are the driving force for the stacking of caffeine. In parallel, the observed dephasing times imply a change in caffeine interactions as a function of temperature and concentration. A decrease, at low water content, of the dephasing time for the ring breathing vibration mode indicates that self-association alters the solvation structure that is detectable at low concentration. These results are in agreement with simulation predictions and serve as an important validation of the models used in those calculations.

  10. Ordering and thermal excitations in dipolar coupled single domain magnet arrays (Presentation Recording)

    Science.gov (United States)

    Östman, Erik; Arnalds, Unnar; Kapaklis, Vassilios; Hjörvarsson, Björgvin

    2015-09-01

    For a small island of a magnetic material the magnetic state of the island is mainly determined by the exchange interaction and the shape anisotropy. Two or more islands placed in close proximity will interact through dipolar interactions. The state of a large system will thus be dictated by interactions at both these length scales. Enabling internal thermal fluctuations, e.g. by the choice of material, of the individual islands allows for the study of thermal ordering in extended nano-patterned magnetic arrays [1,2]. As a result nano-magnetic arrays represent an ideal playground for the study of physical model systems. Here we present three different studies all having used magneto-optical imaging techniques to observe, in real space, the order of the systems. The first study is done on a square lattice of circular islands. The remanent magnetic state of each island is a magnetic vortex structure and we can study the temperature dependence of the vortex nucleation and annihilation fields [3]. The second are long chains of dipolar coupled elongated islands where the magnetization direction in each island only can point in one of two possible directions. This creates a system which in many ways mimics the Ising model [4] and we can relate the correlation length to the temperature. The third one is a spin ice system where elongated islands are placed in a square lattice. Thermal excitations in such systems resemble magnetic monopoles [2] and we can investigate their properties as a function of temperature and lattice parameters. [1] V. Kapaklis et al., New J. Phys. 14, 035009 (2012) [2] V. Kapaklis et al., Nature Nanotech 9, 514(2014) [3] E. Östman et al.,New J. Phys. 16, 053002 (2014) [4] E. Östman et al.,Thermal ordering in mesoscopic Ising chains, In manuscript.

  11. Nuclear magnetic relaxation by the dipolar EMOR mechanism: Multi-spin systems

    Science.gov (United States)

    Chang, Zhiwei; Halle, Bertil

    2017-08-01

    In aqueous systems with immobilized macromolecules, including biological tissues, the longitudinal spin relaxation of water protons is primarily induced by exchange-mediated orientational randomization (EMOR) of intra- and intermolecular magnetic dipole-dipole couplings. Starting from the stochastic Liouville equation, we have previously developed a rigorous EMOR relaxation theory for dipole-coupled two-spin and three-spin systems. Here, we extend the stochastic Liouville theory to four-spin systems and use these exact results as a guide for constructing an approximate multi-spin theory, valid for spin systems of arbitrary size. This so-called generalized stochastic Redfield equation (GSRE) theory includes the effects of longitudinal-transverse cross-mode relaxation, which gives rise to an inverted step in the relaxation dispersion profile, and coherent spin mode transfer among solid-like spins, which may be regarded as generalized spin diffusion. The GSRE theory is compared to an existing theory, based on the extended Solomon equations, which does not incorporate these phenomena. Relaxation dispersion profiles are computed from the GSRE theory for systems of up to 16 protons, taken from protein crystal structures. These profiles span the range from the motional narrowing limit, where the coherent mode transfer plays a major role, to the ultra-slow motion limit, where the zero-field rate is closely related to the strong-collision limit of the dipolar relaxation rate. Although a quantitative analysis of experimental data is beyond the scope of this work, it is clear from the magnitude of the predicted relaxation rate and the shape of the relaxation dispersion profile that the dipolar EMOR mechanism is the principal cause of water-1H low-field longitudinal relaxation in aqueous systems of immobilized macromolecules, including soft biological tissues. The relaxation theory developed here therefore provides a basis for molecular-level interpretation of endogenous soft

  12. Low temperature structural transitions in dipolar hard spheres: The influence on magnetic properties

    International Nuclear Information System (INIS)

    Ivanov, A.O.; Kantorovich, S.S.; Rovigatti, L.; Tavares, J.M.; Sciortino, F.

    2015-01-01

    We investigate the structural chain-to-ring transition at low temperature in a gas of dipolar hard spheres (DHS). Due to the weakening of entropic contribution, ring formation becomes noticeable when the effective dipole–dipole magnetic interaction increases. It results in the redistribution of particles from usually observed flexible chains into flexible rings. The concentration (ρ) of DHS plays a crucial part in this transition: at a very low ρ only chains and rings are observed, whereas even a slight increase of the volume fraction leads to the formation of branched or defect structures. As a result, the fraction of DHS aggregated in defect-free rings turns out to be a non-monotonic function of ρ. The average ring size is found to be a slower increasing function of ρ when compared to that of chains. Both theory and computer simulations confirm the dramatic influence of the ring formation on the ρ-dependence of the initial magnetic susceptibility (χ) when the temperature decreases. The rings due to their zero total dipole moment are irresponsive to a weak magnetic field and drive to the strong decrease of the initial magnetic susceptibility. - Highlights: • Found structural chain-to-ring transition at low temperature sheds the light on the no-man's-land of the phase diagram of dipolar hard sphere gas. • Particle concentration plays a crucial part: at high dilution only chains and rings are observed, otherwise different branched structures occur. • The dramatic influence of the ring formation on the concentration dependence of the initial magnetic susceptibility when temperature decreases

  13. Complexation of di-amides of dipicolinic acid with neodymium

    Energy Technology Data Exchange (ETDEWEB)

    Lapka, J.L.; Paulenova, A. [Department of Chemistry, Oregon State University: 100 Radiation Center, Corvallis, OR 97331 (United States)

    2013-07-01

    Di-amides have undergone significant studies as possible ligands for use in the partitioning of trivalent minor actinides and lanthanides. The binding affinities of three isomeric ligands with neodymium in acetonitrile solution have been investigated. The stability constants of the metal-ligand complexes formed between different isomers of N,N'-diethyl-N,N'- ditolyl-di-picolinamide (EtTDPA) and trivalent neodymium in acetonitrile have been determined by spectrophotometric and calorimetric methods. Each isomer of EtTDPA has been found to be capable of forming three complexes with trivalent neodymium, Nd(EtTDPA), Nd(EtTDPA){sub 2}, and Nd(EtTDPA){sub 3}. Values from spectrophotometric and calorimetric titrations are within reasonable agreement with each other. The order of stability constants for each metal:ligand complex decreases in the order Et(m)TDPA > Et(p)TDPA > Et(o)TDPA. The obtained values are comparable to other di-amidic ligands obtained under similar system conditions and mirror previously obtained solvent extraction data for EtTDPA at low ionic strengths. (authors.

  14. Poly(ester amide)s based on (L)-lactic acid oligomers and α-amino acids: influence of the α-amino acid side chain in the poly(ester amide)s properties.

    Science.gov (United States)

    Fonseca, Ana C; Coelho, Jorge F J; Valente, Joana F A; Correia, Tiago R; Correia, Ilídio J; Gil, Maria H; Simões, Pedro N

    2013-01-01

    Novel biodegradable and low cytotoxic poly(ester amide)s (PEAs) based on α-amino acids and (L)-lactic acid (L-LA) oligomers were successfully synthesized by interfacial polymerization. The chemical structure of the new polymers was confirmed by spectroscopic analyses. Further characterization suggests that the α-amino acid plays a critical role on the final properties of the PEA. L-phenylalanine provides PEAs with higher glass transition temperature, whereas glycine enhances the crystallinity. The hydrolytic degradation in PBS (pH = 7.4) at 37 °C also depends on the α-amino acid, being faster for glycine-based PEAs. The cytotoxic profiles using fibroblast human cells indicate that the PEAs did not elicit an acute cytotoxic effect. The strategy presented in this work opens the possibility of synthesizing biodegradable PEAs with low citotoxicity by an easy and fast method. It is worth to mention also that the properties of these materials can be fine-tuned only by changing the α-amino acid.

  15. Quantitative structure-cytotoxicity relationship of piperic acid amides.

    Science.gov (United States)

    Shimada, Chiyako; Uesawa, Yoshihiro; Ishihara, Mariko; Kagaya, Hajime; Kanamoto, Taisei; Terakubo, Shigemi; Nakashima, Hideki; Takao, Koichi; Miyashiro, Takaki; Sugita, Yoshiaki; Sakagami, Hiroshi

    2014-09-01

    A total of 12 piperic acid amides, including piperine, were subjected to quantitative structure-activity relationship (QSAR) analysis, based on their cytotoxicity, tumor selectivity and anti-HIV activity, in order to find new biological activities. Cytotoxicity against four human oral squamous cell carcinoma (OSCC) cell lines and three human oral normal cells was determined by the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) method. Tumor selectivity was evaluated by the ratio of the mean 50% cytotoxic concentration (CC50) against normal oral cells to that against OSCC cell lines. Anti-HIV activity was evaluated by the ratio of the CC50 to 50% HIV infection-cytoprotective concentration (EC50). Physicochemical, structural, and quantum-chemical parameters were calculated based on the conformations optimized by LowModeMD method followed by density functional theory method. All compounds showed low-to-moderate tumor selectivity, but no anti-HIV activity. N-Piperoyldopamine ( 8: ) which has a catechol moiety, showed the highest tumor selectivity, possibly due to its unique molecular shape and electrostatic interaction, especially its largest partial equalization of orbital electronegativities and vsurf descriptors. The present study suggests that molecular shape and ability for electrostatic interaction are useful parameters for estimating the tumor selectivity of piperic acid amides. Copyright© 2014 International Institute of Anticancer Research (Dr. John G. Delinassios), All rights reserved.

  16. AMID: Accurate Magnetic Indoor Localization Using Deep Learning

    Directory of Open Access Journals (Sweden)

    Namkyoung Lee

    2018-05-01

    Full Text Available Geomagnetic-based indoor positioning has drawn a great attention from academia and industry due to its advantage of being operable without infrastructure support and its reliable signal characteristics. However, it must overcome the problems of ambiguity that originate with the nature of geomagnetic data. Most studies manage this problem by incorporating particle filters along with inertial sensors. However, they cannot yield reliable positioning results because the inertial sensors in smartphones cannot precisely predict the movement of users. There have been attempts to recognize the magnetic sequence pattern, but these attempts are proven only in a one-dimensional space, because magnetic intensity fluctuates severely with even a slight change of locations. This paper proposes accurate magnetic indoor localization using deep learning (AMID, an indoor positioning system that recognizes magnetic sequence patterns using a deep neural network. Features are extracted from magnetic sequences, and then the deep neural network is used for classifying the sequences by patterns that are generated by nearby magnetic landmarks. Locations are estimated by detecting the landmarks. AMID manifested the proposed features and deep learning as an outstanding classifier, revealing the potential of accurate magnetic positioning with smartphone sensors alone. The landmark detection accuracy was over 80% in a two-dimensional environment.

  17. Evaluation of amides and centrifugation temperature in boar semen cryopreservation.

    Science.gov (United States)

    Bianchi, I; Calderam, K; Maschio, E F; Madeira, E M; da Rosa Ulguim, R; Corcini, C D; Bongalhardo, D C; Corrêa, E K; Lucia, T; Deschamps, J C; Corrêa, M N

    2008-03-15

    Two experiments were conducted to evaluate the use of amides as cryoprotectants and two centrifugation temperatures (15 or 24 degrees C) in boar semen cryopreservation protocols. Semen was diluted in BTS, cooled centrifuged, added to cooling extenders, followed by the addition of various cryoprotectants. In experiment 1, mean (+/-S.E.M.) sperm motility for 5% dimethylformamide (DMF; 50.6+/-1.9%) and 5% dimethylacetamide (DMA; 53.8+/-1.7%) were superior (P0.05). In experiment 2, we tested MF, DMF, and DMA at 3, 5, and 7%. Sperm motility and membrane integrity were higher for 5% DMA (53.8+/-1.7 and 50.9+/-1.9%) and 5% DMF (50.6+/-1.9 and 47.9+/-2.1%), in comparison with 7% DMF and all MF concentrations (P0.05). In conclusion, boar semen was successfully cryopreserved by replacement of glycerol with amides (especially 5% DMA) and centrifugation at 15 degrees C, with benefits for post-thaw sperm motility and membrane integrity.

  18. Cross-Coupling of Amides with Alkylboranes via Nickel-Catalyzed C–N Bond Cleavage

    KAUST Repository

    Liu, Xiangqian; Hsiao, Chien-Chi; Guo, Lin; Rueping, Magnus

    2018-01-01

    A protocol for the nickel-catalyzed alkylation of amides was established. The use of alkylboranes as nucleophilic partners allowed the use of mild reaction conditions and compatibility of various functional groups with respect to both coupling partners. The catalytic alkylation proceeded selectively at the amides in the presence of other functional groups as well as other carboxylic acid derived moieties.

  19. Cross-Coupling of Amides with Alkylboranes via Nickel-Catalyzed C–N Bond Cleavage

    KAUST Repository

    Liu, Xiangqian

    2018-05-09

    A protocol for the nickel-catalyzed alkylation of amides was established. The use of alkylboranes as nucleophilic partners allowed the use of mild reaction conditions and compatibility of various functional groups with respect to both coupling partners. The catalytic alkylation proceeded selectively at the amides in the presence of other functional groups as well as other carboxylic acid derived moieties.

  20. Hydrophilic segmented block copolymers based on poly(ethylene oxide) and monodisperse amide segments

    NARCIS (Netherlands)

    Husken, D.; Feijen, Jan; Gaymans, R.J.

    2007-01-01

    Segmented block copolymers based on poly(ethylene oxide) (PEO) flexible segments and monodisperse crystallizable bisester tetra-amide segments were made via a polycondensation reaction. The molecular weight of the PEO segments varied from 600 to 4600 g/mol and a bisester tetra-amide segment (T6T6T)

  1. Shear and dielectric responses of propylene carbonate, tripropylene glycol, and a mixture of two secondary amides

    DEFF Research Database (Denmark)

    Gainaru, Catalin; Hecksher, Tina; Olsen, Niels Boye

    2012-01-01

    Propylene carbonate and a mixture of two secondary amides, N-ethylformamide and Nethylacetamide, are investigated by means of broadband dielectric and mechanical shear spectroscopy. The similarities between the rheological and the dielectric responses of these liquids and of the previously invest...... in the secondary amides. In addition, the predictions of the shoving model are confirmed for the investigated liquids...

  2. Uranyl Photocleavage of Phosphopeptides Yields Truncated C-Terminally Amidated Peptide Products

    DEFF Research Database (Denmark)

    Elnegaard, Rasmus L B; Møllegaard, Niels Erik; Zhang, Qiang

    2017-01-01

    photocleavage reaction of a tetraphosphorylated β-casein model peptide. We show that the primary photocleavage products of the uranyl-catalysed reaction are C-terminally amidated. This could be of great interest to the pharmaceutical industry, as efficient peptide amidation reactions are one of the top...

  3. Solvent and conformation dependence of amide I vibrations in peptides and proteins containing proline

    NARCIS (Netherlands)

    Roy, Santanu; Lessing, Joshua; Meisl, Georg; Ganim, Ziad; Tokmakoff, Andrei; Knoester, Jasper; Jansen, Thomas L. C.

    2011-01-01

    We present a mixed quantum-classical model for studying the amide I vibrational dynamics (predominantly CO stretching) in peptides and proteins containing proline. There are existing models developed for determining frequencies of and couplings between the secondary amide units. However, these are

  4. Metal-Free N-Arylation of Secondary Amides at Room Temperature

    OpenAIRE

    Tinnis, Fredrik; Stridfeldt, Elin; Lundberg, Helena; Adolfsson, Hans; Olofsson, Berit

    2015-01-01

    The arylation of secondary acyclic amides has been achieved with diaryliodonium salts under mild and metal-free conditions. The methodology has a wide scope, allows synthesis of tertiary amides with highly congested aryl moieties, and avoids the regioselectivity problems observed in reactions with (diacetoxyiodo)benzene.

  5. A Convenient Approach to Synthesizing Peptide C-Terminal N-Alkyl Amides

    Science.gov (United States)

    Fang, Wei-Jie; Yakovleva, Tatyana; Aldrich, Jane V.

    2014-01-01

    Peptide C-terminal N-alkyl amides have gained more attention over the past decade due to their biological properties, including improved pharmacokinetic and pharmacodynamic profiles. However, the synthesis of this type of peptide on solid phase by current available methods can be challenging. Here we report a convenient method to synthesize peptide C-terminal N-alkyl amides using the well-known Fukuyama N-alkylation reaction on a standard resin commonly used for the synthesis of peptide C-terminal primary amides, the PAL-PEG-PS (Peptide Amide Linker-polyethylene glycol-polystyrene) resin. The alkylation and oNBS deprotection were conducted under basic conditions and were therefore compatible with this acid labile resin. The alkylation reaction was very efficient on this resin with a number of different alkyl iodides or bromides, and the synthesis of model enkephalin N-alkyl amide analogs using this method gave consistently high yields and purities, demonstrating the applicability of this methodology. The synthesis of N-alkyl amides was more difficult on a Rink amide resin, especially the coupling of the first amino acid to the N-alkyl amine, resulting in lower yields for loading the first amino acid onto the resin. This method can be widely applied in the synthesis of peptide N-alkyl amides. PMID:22252422

  6. Comparing Amide-Forming Reactions Using Green Chemistry Metrics in an Undergraduate Organic Laboratory

    Science.gov (United States)

    Fennie, Michael W.; Roth, Jessica M.

    2016-01-01

    In this laboratory experiment, upper-division undergraduate chemistry and biochemistry majors investigate amide-bond-forming reactions from a green chemistry perspective. Using hydrocinnamic acid and benzylamine as reactants, students perform three types of amide-forming reactions: an acid chloride derivative route; a coupling reagent promoted…

  7. 1H NMR spectra. Part 30(+): 1H chemical shifts in amides and the magnetic anisotropy, electric field and steric effects of the amide group.

    Science.gov (United States)

    Abraham, Raymond J; Griffiths, Lee; Perez, Manuel

    2013-03-01

    The (1)H spectra of 37 amides in CDCl(3) solvent were analysed and the chemical shifts obtained. The molecular geometries and conformational analysis of these amides were considered in detail. The NMR spectral assignments are of interest, e.g. the assignments of the formamide NH(2) protons reverse in going from CDCl(3) to more polar solvents. The substituent chemical shifts of the amide group in both aliphatic and aromatic amides were analysed using an approach based on neural network data for near (≤3 bonds removed) protons and the electric field, magnetic anisotropy, steric and for aromatic systems π effects of the amide group for more distant protons. The electric field is calculated from the partial atomic charges on the N.C═O atoms of the amide group. The magnetic anisotropy of the carbonyl group was reproduced with the asymmetric magnetic anisotropy acting at the midpoint of the carbonyl bond. The values of the anisotropies Δχ(parl) and Δχ(perp) were for the aliphatic amides 10.53 and -23.67 (×10(-6) Å(3)/molecule) and for the aromatic amides 2.12 and -10.43 (×10(-6) Å(3)/molecule). The nitrogen anisotropy was 7.62 (×10(-6) Å(3)/molecule). These values are compared with previous literature values. The (1)H chemical shifts were calculated from the semi-empirical approach and also by gauge-independent atomic orbital calculations with the density functional theory method and B3LYP/6-31G(++) (d,p) basis set. The semi-empirical approach gave good agreement with root mean square error of 0.081 ppm for the data set of 280 entries. The gauge-independent atomic orbital approach was generally acceptable, but significant errors (ca. 1 ppm) were found for the NH and CHO protons and also for some other protons. Copyright © 2013 John Wiley & Sons, Ltd.

  8. Food emulsions with amidated pectin from celery (Apium graveolens var. rapaceum D.C. tubers

    Directory of Open Access Journals (Sweden)

    Iv. Petrova

    2017-09-01

    Full Text Available Abstract. Hydrocolloids, especially polysaccharides from traditional plant sources and their derivatives possessed significant emulsifying properties. Pectin was isolated from celery tubers by accelerated “green” method for extraction based on ultrasonic irradiation. Further chemical modification of celery pectin was performed with 4 mol/L NH The amidated celery pectin was obtained with the following characteristics: the degree of esterification (DE 31%, the degree of 3. amidation (DA 16%, degree of acetylation (DAc 2% and anhydrouronic acid content (AUAC 68%. This modified pectin was incorporated in preparation of model 30, 40 and 50% oil-in-water emulsions. The effect of amidation of celery pectin on the stability of emulsions was investigated. The results showed that amidation increased the emulsifying properties of pectic polysaccharides. It affected also the rheological characteristics of model emulsion. The current study demonstrated preparation of emulsion with low-caloric amidated pectin as proper alternative to the traditional emulsifiers.

  9. Synthesis of amide-functionalized cellulose esters by olefin cross-metathesis.

    Science.gov (United States)

    Meng, Xiangtao; Edgar, Kevin J

    2015-11-05

    Cellulose esters with amide functionalities were synthesized by cross-metathesis (CM) reaction of terminally olefinic esters with different acrylamides, catalyzed by Hoveyda-Grubbs 2nd generation catalyst. Chelation by amides of the catalyst ruthenium center caused low conversions using conventional solvents. The effects of both solvent and structure of acrylamide on reaction conversion were investigated. While the inherent tendency of acrylamides to chelate Ru is governed by the acrylamide N-substituents, employing acetic acid as a solvent significantly improved the conversion of certain acrylamides, from 50% to up to 99%. Homogeneous hydrogenation using p-toluenesulfonyl hydrazide successfully eliminated the α,β-unsaturation of the CM products to give stable amide-functionalized cellulose esters. The amide-functionalized product showed higher Tg than its starting terminally olefinic counterpart, which may have resulted from strong hydrogen bonding interactions of the amide functional groups. Copyright © 2015 Elsevier Ltd. All rights reserved.

  10. Nickel-catalysed retro-hydroamidocarbonylation of aliphatic amides to olefins

    Science.gov (United States)

    Hu, Jiefeng; Wang, Minyan; Pu, Xinghui; Shi, Zhuangzhi

    2017-05-01

    Amide and olefins are important synthetic intermediates with complementary reactivity which play a key role in the construction of natural products, pharmaceuticals and manmade materials. Converting the normally highly stable aliphatic amides into olefins directly is a challenging task. Here we show that a Ni/NHC-catalytic system has been established for decarbonylative elimination of aliphatic amides to generate various olefins via C-N and C-C bond cleavage. This study not only overcomes the acyl C-N bond activation in aliphatic amides, but also encompasses distinct chemical advances on a new type of elimination reaction called retro-hydroamidocarbonylation. This transformation shows good functional group compatibility and can serve as a powerful synthetic tool for late-stage olefination of amide groups in complex compounds.

  11. Biomimetic L-aspartic acid-derived functional poly(ester amide)s for vascular tissue engineering.

    Science.gov (United States)

    Knight, Darryl K; Gillies, Elizabeth R; Mequanint, Kibret

    2014-08-01

    Functionalization of polymeric biomaterials permits the conjugation of cell signaling molecules capable of directing cell function. In this study, l-phenylalanine and l-aspartic acid were used to synthesize poly(ester amide)s (PEAs) with pendant carboxylic acid groups through an interfacial polycondensation approach. Human coronary artery smooth muscle cell (HCASMC) attachment, spreading and proliferation was observed on all PEA films. Vinculin expression at the cell periphery suggested that HCASMCs formed focal adhesions on the functional PEAs, while the absence of smooth muscle α-actin (SMαA) expression implied the cells adopted a proliferative phenotype. The PEAs were also electrospun to yield nanoscale three-dimensional (3-D) scaffolds with average fiber diameters ranging from 130 to 294nm. Immunoblotting studies suggested a potential increase in SMαA and calponin expression from HCASMCs cultured on 3-D fibrous scaffolds when compared to 2-D films. X-ray photoelectron spectroscopy and immunofluorescence demonstrated the conjugation of transforming growth factor-β1 to the surface of the functional PEA through the pendant carboxylic acid groups. Taken together, this study demonstrates that PEAs containing aspartic acid are viable biomaterials for further investigation in vascular tissue engineering. Copyright © 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

  12. 40 CFR 721.6183 - Amides, from ammonium hydroxide - maleic anhydride polymer and hydrogenated tallow alkyl amines...

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Amides, from ammonium hydroxide... Substances § 721.6183 Amides, from ammonium hydroxide - maleic anhydride polymer and hydrogenated tallow... subject to reporting. (1) The chemical substance identified as amides, from ammonium hydroxide - maleic...

  13. CXL-1020, a Novel Nitroxyl (HNO Prodrug, Is More Effective than Milrinone in Models of Diastolic Dysfunction—A Cardiovascular Therapeutic: An Efficacy and Safety Study in the Rat

    Directory of Open Access Journals (Sweden)

    Steve R. Roof

    2017-11-01

    Full Text Available The nitroxyl (HNO prodrug, CXL-1020, induces vasorelaxation and improves cardiac function in canine models and patients with systolic heart failure (HF. HNO's unique mechanism of action may be applicable to a broader subset of cardiac patients. This study investigated the load-independent safety and efficacy of CXL-1020 in two rodent (rat models of diastolic heart failure and explored potential drug interactions with common HF background therapies. In vivo left-ventricular hemodynamics/pressure-volume relationships assessed before/during a 30 min IV infusion of CXL-1020 demonstrated acute load-independent positive inotropic, lusitropic, and vasodilatory effects in normal rats. In rats with only diastolic dysfunction due to bilateral renal wrapping (RW or pronounced diastolic and mild systolic dysfunction due to 4 weeks of chronic isoproterenol exposure (ISO, CXL-1020 attenuated the elevated LV filling pressures, improved the end diastolic pressure volume relationship, and accelerated relaxation. CXL-1020 facilitated Ca2+ re-uptake and enhanced myocyte relaxation in isolated cardiomyocytes from ISO rats. Compared to milrinone, CXL-1020 more effectively improved Ca2+ reuptake in ISO rats without concomitant chronotropy, and did not enhance Ca2+ entry via L-type Ca2+ channels nor increase myocardial arrhythmias/ectopic activity. Acute-therapy with CXL-1020 improved ventricular relaxation and Ca2+ cycling, in the setting of chronic induced diastolic dysfunction. CXL-1020's lusitropic effects were greater than those seen with the cAMP-dependent agent milrinone, and unlike milrinone it did not produce chronotropy or increased ectopy. HNO is a promising new potential therapy for both systolic and diastolic heart failure.

  14. Ground-State Distortion in N-Acyl-tert-butyl-carbamates (Boc) and N-Acyl-tosylamides (Ts): Twisted Amides of Relevance to Amide N-C Cross-Coupling.

    Science.gov (United States)

    Szostak, Roman; Shi, Shicheng; Meng, Guangrong; Lalancette, Roger; Szostak, Michal

    2016-09-02

    Amide N-C(O) bonds are generally unreactive in cross-coupling reactions employing low-valent transition metals due to nN → π*C═O resonance. Herein we demonstrate that N-acyl-tert-butyl-carbamates (Boc) and N-acyl-tosylamides (Ts), two classes of acyclic amides that have recently enabled the development of elusive amide bond N-C cross-coupling reactions with organometallic reagents, are intrinsically twisted around the N-C(O) axis. The data have important implications for the design of new amide cross-coupling reactions with the N-C(O) amide bond cleavage as a key step.

  15. Investigation of uranyl phosphite interaction with some amides

    International Nuclear Information System (INIS)

    Avduevskaya, K.A.; Ragulina, N.B.; Rozanov, I.A.; Mukhajlov, Yu.N.; Kanishcheva, A.S.; Grevtseva, T.G.

    1981-01-01

    Uranyl (amide) phosphitocomplexes of [UO 2 HPO 3 H 2 OAA]xH 2 O, [UO 2 HPO 3 (AA) 2 ], [UO 2 HPO 3 H 2 O DMC], [UO 2 HPO 3 H 2 ODMFA], [UO 2 HPO 3 DAMA] and UO 2 HPO 3 x2FAxH 2 O compositions, where AA-acetamide; DMC-N, N-dimetyl carbamide, DMFA-dimetyl formamide; DAMA-diamide of malonic acid; FA-formamide, are separated, identified and investigated. Derivatives of mono substituted uranyl phosphite of UO 2 (H 2 PO 3 ) 2 x2FA and [UO 2 (H 2 PO 3 ) 2 H 2 O]x2TMC composition (where TMC-tetramethyl carbamide), are synthesized. Structures of complexes with DAMA, TMC, DMFA and acid dimethyl-ammonium diphosphitouranylate-(CH 3 ] 2 NH 2 x[UO 2 (HPO 3 ) 3 (H 2 PO 3 )] are investigated [ru

  16. Synthesis and antifungal evaluation of PCA amide analogues.

    Science.gov (United States)

    Qin, Chuan; Yu, Di-Ya; Zhou, Xu-Dong; Zhang, Min; Wu, Qing-Lai; Li, Jun-Kai

    2018-04-18

    To improve the physical and chemical properties of phenazine-1-carboxylic acid (PCA) and find higher antifungal compounds, a series of PCA amide analogues were designed and synthesized and their structures were confirmed by 1 H NMR, HRMS, and X-ray. Most compounds showed some antifungal activities in vitro. Particularly, compound 3d exhibited inhibition effect against Pyriculariaoryzac Cavgra with EC 50 value of 28.7 μM and compound 3q exhibited effect against Rhizoctonia solani with EC 50 value of 24.5 μM, more potently active than that of the positive control PCA with its EC 50 values of 37.3 μM (Pyriculariaoryzac Cavgra) and 33.2 μM (Rhizoctonia solani), respectively.

  17. Proposed Chevron Tengiz venture stalls amid Soviet political squabble

    International Nuclear Information System (INIS)

    Anon.

    1991-01-01

    This paper reports on the status of foreign investment in Soviet oil and gas joint ventures which has reached a critical juncture. Just as the U.S. is considering granting most favored nation trade status to the U.S.S.R., the joint venture petroleum deal seen as the litmus test for such deals-Chevron Corp.'s proposed addition of supergiant Tengiz oil field to its Caspian Sea joint venture-has stalled amid controversy. Unconfirmed reports from Soviet officials and other foreign joint venture participants in the U.S.S.R. have Chevron pulling out of the long negotiated, multibillion dollar project after the Soviets rejected the company's terms. Chevron, however, insists the project is still alive

  18. Three new amides from streptomyces sp. H7372

    Energy Technology Data Exchange (ETDEWEB)

    Cheenpracha, Sarot; Borris, Robert P.; Tran, Tammy T.; Chang, Leng Chee, E-mail: lengchee@hawaii.ed [University of Hawaii Hilo, HI (United States). College of Pharmacy. Dept. of Pharmaceutical Sciences; Jee, Jap Meng; Seow, Heng Fong; Cheah, Hwen-Yee [Universiti Putra Malaysia, Selangor (Malaysia). Faculty of Medicine and Health Sciences. Department of Pathology. bImmunology Unit; Hoc, Coy Choke [University Malaysia Sabah (Malaysia). School of Science and Technology. Biotechnology Program

    2011-07-01

    Three new amides, methyl phenatate A (1), actiphenamide (2) and actiphenol 1-beta-D-glucopyranoside (3), along with thirteen known compounds, were isolated from the organic extract of a fermentation culture of Streptomyces sp. H7372. The structures were elucidated by spectroscopic methods including 1D- and 2D-NMR techniques, and MS analyses. Cycloheximide (6) and cyclo({Delta}Ala-L-Val) (8) gave a clear zone of inhibition of Ras-Raf-1 interaction in the yeast two hybrid assay which showed high potency with 10 and 25 mm clear ZOIs on SD His{sup -} and inactive on SD His{sup +} at 2.5 mug per disk, respectively. (author)

  19. Coordination compounds of cobalt and cadmium with isobutyric acid amide

    Energy Technology Data Exchange (ETDEWEB)

    Tsivadze, A.Yu.; Ivanova, I.S.; Solovkina, O.A. (AN SSSR, Moscow. Inst. Obshchej i Neorganicheskoj Khimii)

    1983-06-01

    Coordination compounds of cobalt and cadmium with isobutyric acid amide (IBAA) of Co(NCS)/sub 2/x(IBAA)/sub 2/(H/sub 2/O)/sub 2/, CoCl/sub 2/(IBAA)/sub 4/, CoI/sub 2/(IBAA)/sub 8/(H/sub 2/O)/sub 2/, CdI/sub 2/(IBAA)/sub 2/ composition have been synthesized and characterized. Their infrared absorption spectra (200-400 cm/sup -1/), electron reflection spectra (200-750 nm) were studied. It is shown that in all compounds there are IBAA molecUles coordinated through an oxygen atom. Thiocyanogroups are coordinated through nitrogen atoms.

  20. Amides and neolignans from the aerial parts of Piper bonii.

    Science.gov (United States)

    Ding, Duo-Duo; Wang, Yue-Hu; Chen, Ya-Hui; Mei, Ren-Qiang; Yang, Jun; Luo, Ji-Feng; Li, Yan; Long, Chun-Lin; Kong, Yi

    2016-09-01

    Six amides, piperbonamides A-F, three neolignans piperbonins A-C, and 11 known compounds were isolated from the aerial parts of Piper bonii (Piperaceae). The structures of piperbonamides A-F and piperbonins A-C were elucidated based on the analysis of 1D and 2D NMR and MS data. Piperbonin A, (+)-trans-acuminatin, (+)-cis-acuminatin, (+)-kadsurenone, and pipernonaline showed weak activity against platelet aggregation with IC50 values of 118.2, 108.5, 90.02, 107.3, and 116.3 μM, respectively, as compared with the positive control, tirofiban, with an IC50 value of 5.24 μM. Piperbonamides A-F were inactive against five tumor cell lines at concentrations up to 40 μM. Copyright © 2016. Published by Elsevier Ltd.

  1. Dielectric relaxation studies of dilute solutions of amides

    Energy Technology Data Exchange (ETDEWEB)

    Malathi, M.; Sabesan, R.; Krishnan, S

    2003-11-15

    The dielectric constants and dielectric losses of formamide, acetamide, N-methyl acetamide, acetanilide and N,N-dimethyl acetamide in dilute solutions of 1,4-dioxan/benzene have been measured at 308 K using 9.37 GHz, dielectric relaxation set up. The relaxation time for the over all rotation {tau}{sub (1)} and that for the group rotation {tau}{sub (2)} of (the molecules were determined using Higasi's method. The activation energies for the processes of dielectric relaxation and viscous flow were determined by using Eyring's rate theory. From relaxation time behaviour of amides in non-polar solvent, solute-solvent and solute-solute type of molecular association is proposed.

  2. Synthesis and proapoptotic activity of oleanolic acid derived amides.

    Science.gov (United States)

    Heller, Lucie; Knorrscheidt, Anja; Flemming, Franziska; Wiemann, Jana; Sommerwerk, Sven; Pavel, Ioana Z; Al-Harrasi, Ahmed; Csuk, René

    2016-10-01

    Thirty-one different 3-O-acetyl-OA derived amides have been prepared and screened for their cytotoxic activity. In the SRB assays nearly all the carboxamides displayed good cytotoxicity in the low μM range for several human tumor cell lines. Low EC50 values were obtained especially for the picolinylamides 14-16, for a N-[2-(dimethylamino)-ethyl] derivative 27 and a N-[2-(pyrrolinyl)-ethyl] carboxamide 28. These compounds were submitted to an extensive biological testing and proved compound 15 to act mainly by an arrest of the tumor cells in the S phase of the cell cycle. Cell death occurred by autophagy while compounds 27 and 28 triggered apoptosis. Copyright © 2016 Elsevier Inc. All rights reserved.

  3. Lithium amide (LiNH2) under pressure.

    Science.gov (United States)

    Prasad, Dasari L V K; Ashcroft, N W; Hoffmann, Roald

    2012-10-11

    Static high pressure lithium amide (LiNH(2)) crystal structures are predicted using evolutionary structure search methodologies and intuitive approaches. In the process, we explore the relationship of the structure and properties of solid LiNH(2) to its molecular monomer and dimer, as well as its valence-isoelectronic crystalline phases of methane, water, and ammonia all under pressure. A NaNH(2) (Fddd) structure type is found to be competitive for the ground state of LiNH(2) above 6 GPa with the P = 1 atm I4[overline] phase. Three novel phases emerge at 11 (P4[overline]2(1)m), 13 (P4(2)/ncm), and 46 GPa (P2(1)2(1)2(1)), still containing molecular amide anions, which begin to form N-H···N hydrogen bonds. The P2(1)2(1)2(1) phase remains stable over a wide pressure range. This phase and another Pmc2(1) structure found at 280 GPa have infinite ···(H)N···H···N(H)···H polymeric zigzag chains comprising symmetric N···H···N hydrogen bonds with one NH bond kept out of the chain, an interesting general feature found in many of our high pressure (>280 GPa) LiNH(2) structures, with analogies in high pressure H(2)O-ices. All the predicted low enthalpy LiNH(2) phases are calculated to be enthalpically stable with respect to their elements but resist metallization with increasing pressure up to several TPa. The possibility of Li sublattice melting in the intermediate pressure range structures is raised.

  4. Conformational analysis of amide extractants by NMR in organic phase

    International Nuclear Information System (INIS)

    Berthon, C.

    1993-08-01

    This study deals with nuclear fuel reprocessing. We have essentially used NMR spectroscopy. We want to understand which kind of conformational parameters control selectivity and efficiency of amide extractant. The symmetric monoamides used are DOBA (C 3 H 7 CON (CH 2 CH(C 2 H 5 ) C 4 H 9 ) 2 ), DOiBA ((CH 3 ) 2 CCHON (CH 2 CH(C 2 H 5 )C 4 H 9 ) 2 ) and DOTA ((CH 3 ) 3 CCH 2 CON(CH 2 CH(C 2 H 5 )C 4 H 9 ) 2 ). Each gives two quasi equivalent conformers (cis and trans) in organic phases. The selected malonamide DMDBTDMA ((C 4 H 9 (CH 3 )NCO) 2 CHC 14 H 29 ) has four conformers because of its twice disymmetric amide functions. Weak interactions between monoamides which yield to dimer formation. The malonamide also gives dimers but forms aggregates too. Nitric acid extraction is due to the competitive formation of six species L, L 2 , L 2 (HNO 3 ), L(HNO 3 ), L(HNO 3 ) 2 , L(HNO 3 ) 3 (L: monoamide). Complexation between lanthanides (III) and monoamides yields to the stoichiometries L 3 Ln(NO 3 ) 3 and L 2 Ln(NO 3 ) 3 . Their ratio depend of steric hindrance on the carbonyl and the metal ionic radius. The same thing is observed of Pu 4+ and Th 4+ extraction in non acidic media. L 2 An(NO 3 ) 4 is the main stoichiometric except for the Th 4+ - DOBA system where the species (DOBA) 3 Th(NO 3 ) 4 appear. Exchange rates between the ligand and the complex are pointed out. The monoamide conformations obtained with lanthanide and plutonium nitrate can explain the difference in extracting power of this molecule between An 4+ and Ln 3+ . (author). 162 refs., 87 figs., 44 tabs., 7 annexes

  5. Accurate measurement of heteronuclear dipolar couplings by phase-alternating R-symmetry (PARS) sequences in magic angle spinning NMR spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Hou, Guangjin, E-mail: hou@udel.edu, E-mail: tpolenov@udel.edu; Lu, Xingyu, E-mail: luxingyu@udel.edu, E-mail: lexvega@comcast.net; Vega, Alexander J., E-mail: luxingyu@udel.edu, E-mail: lexvega@comcast.net; Polenova, Tatyana, E-mail: hou@udel.edu, E-mail: tpolenov@udel.edu [Department of Chemistry and Biochemistry, University of Delaware, Newark, Delaware 19716, USA and Pittsburgh Center for HIV Protein Interactions, University of Pittsburgh School of Medicine, 1051 Biomedical Science Tower 3, 3501 Fifth Ave., Pittsburgh, Pennsylvania 15261 (United States)

    2014-09-14

    We report a Phase-Alternating R-Symmetry (PARS) dipolar recoupling scheme for accurate measurement of heteronuclear {sup 1}H-X (X = {sup 13}C, {sup 15}N, {sup 31}P, etc.) dipolar couplings in MAS NMR experiments. It is an improvement of conventional C- and R-symmetry type DIPSHIFT experiments where, in addition to the dipolar interaction, the {sup 1}H CSA interaction persists and thereby introduces considerable errors in the dipolar measurements. In PARS, phase-shifted RN symmetry pulse blocks applied on the {sup 1}H spins combined with π pulses applied on the X spins at the end of each RN block efficiently suppress the effect from {sup 1}H chemical shift anisotropy, while keeping the {sup 1}H-X dipolar couplings intact. Another advantage over conventional DIPSHIFT experiments, which require the signal to be detected in the form of a reduced-intensity Hahn echo, is that the series of π pulses refocuses the X chemical shift and avoids the necessity of echo formation. PARS permits determination of accurate dipolar couplings in a single experiment; it is suitable for a wide range of MAS conditions including both slow and fast MAS frequencies; and it assures dipolar truncation from the remote protons. The performance of PARS is tested on two model systems, [{sup 15}N]-N-acetyl-valine and [U-{sup 13}C,{sup 15}N]-N-formyl-Met-Leu-Phe tripeptide. The application of PARS for site-resolved measurement of accurate {sup 1}H-{sup 15}N dipolar couplings in the context of 3D experiments is presented on U-{sup 13}C,{sup 15}N-enriched dynein light chain protein LC8.

  6. DipoCoup: A versatile program for 3D-structure homology comparison based on residual dipolar couplings and pseudocontact shifts

    International Nuclear Information System (INIS)

    Meiler, Jens; Peti, Wolfgang; Griesinger, Christian

    2000-01-01

    A program, DipoCoup, is presented that allows to search the protein data bank for proteins which have a three dimensional fold that is at least partially homologous to a protein under investigation. The three dimensional homology search uses secondary structure alignment based on chemical shifts and dipolar couplings or pseudocontact shifts for the three dimensional orientation of secondary structure elements. Moreover, the program offers additional tools for handling and analyzing dipolar couplings

  7. Synthesis with Perfect Atom Economy: Generation of Furan Derivatives by 1,3-Dipolar Cycloaddition of Acetylenedicarboxylates at Cyclooctynes

    Directory of Open Access Journals (Sweden)

    Klaus Banert

    2014-09-01

    Full Text Available Cyclooctyne and cycloocten-5-yne undergo, at room temperature, a 1,3-dipolar cycloaddition with dialkyl acetylenedicarboxylates 1a,b to generate furan-derived short-lived intermediates 2, which can be trapped by two additional equivalents of 1a,b or alternatively by methanol, phenol, water or aldehydes to yield polycyclic products 3b–d, orthoesters 4a–c, ketones 5 or epoxides 6a,b, respectively. Treatment of bis(trimethylsilyl acetylenedicarboxylate (1c with cyclooctyne leads to the ketone 7 via retro-Brook rearrangement of the dipolar intermediate 2c. In all cases, the products are formed with perfect atom economy.

  8. Dipolar-induced interplay between inter-level physics and macroscopic phase transitions in triple-well potentials

    International Nuclear Information System (INIS)

    Zhang Aixia; Xue Jukui

    2012-01-01

    We propose a scheme to reveal the interplay between dipole–dipole interaction (DDI), inter-level coupling and macroscopic phase transitions in dipolar condensates. By considering a macroscopic sample of dipolar bosons in triple-well potentials, DDI-induced coupling between the inter-level physics and the macroscopic phase transitions is presented. When the DDI exceeds certain thresholds, the degeneracy of the two lowest energy levels and the excitation of new eigenstates occur, respectively. Interestingly, these thresholds give the boundaries of various quantum phase transitions. That is, the quantum phase transitions are the consequence of the levels' degeneracy and the new eigenstates' excitation. Furthermore, DDI-induced long-range macroscopic Josephson oscillations are observed and long-range coherent quantum transportation is achieved. Our results give clear proof of the interplay between the multi-level physics and quantum phase transitions, and also provide a way for designing the long-range coherent quantum transportation. (paper)

  9. A Refined Model for the Structure of Acireductone Dioxygenase from Klebsiella ATCC 8724 Incorporating Residual Dipolar Couplings

    Energy Technology Data Exchange (ETDEWEB)

    Pochapsky, Thomas C., E-mail: pochapsk@brandeis.edu; Pochapsky, Susan S.; Ju Tingting [Brandeis University, Department of Chemistry (United States); Hoefler, Chris [Brandeis University, Department of Biochemistry (United States); Liang Jue [Brandeis University, Department of Chemistry (United States)

    2006-02-15

    Acireductone dioxygenase (ARD) from Klebsiella ATCC 8724 is a metalloenzyme that is capable of catalyzing different reactions with the same substrates (acireductone and O{sub 2}) depending upon the metal bound in the active site. A model for the solution structure of the paramagnetic Ni{sup 2+}-containing ARD has been refined using residual dipolar couplings (RDCs) measured in two media. Additional dihedral restraints based on chemical shift (TALOS) were included in the refinement, and backbone structure in the vicinity of the active site was modeled from a crystallographic structure of the mouse homolog of ARD. The incorporation of residual dipolar couplings into the structural refinement alters the relative orientations of several structural features significantly, and improves local secondary structure determination. Comparisons between the solution structures obtained with and without RDCs are made, and structural similarities and differences between mouse and bacterial enzymes are described. Finally, the biological significance of these differences is considered.

  10. The MMS observation of an off-equatorial dipolarization front and associated wave characteristics in the near-Earth magnetotail

    Science.gov (United States)

    Li, H.; Guo, L.; Zhou, M.; Cheng, Q.; Yu, X.; Huang, S.; Pang, Y.

    2017-12-01

    In this paper, we report the observation of the off-equatorial depolarization front structures by Magnetospheric Multiscale (MMS) mission at around X -8Re in the Earth's magnetotail. The dipolarization front was located at the flow rebounce region associated with a parallel electron beam. A large lower frequency electromagnetic wave fluctuation at the depolarization front is observed with the frequency near the ion gyrofrequency, left-handed polarization and a parallel propagation. A parallel current attributed to an electron beam coexist with the wave. The wave is believed to be generated by the current-driven ion cyclotron instability. Such instability is important because of its potential contribution to global electromagnetic energy conversion at the dipolarization front.

  11. Amides are excellent mimics of phosphate internucleoside linkages and are well tolerated in short interfering RNAs.

    Science.gov (United States)

    Mutisya, Daniel; Selvam, Chelliah; Lunstad, Benjamin D; Pallan, Pradeep S; Haas, Amanda; Leake, Devin; Egli, Martin; Rozners, Eriks

    2014-06-01

    RNA interference (RNAi) has become an important tool in functional genomics and has an intriguing therapeutic potential. However, the current design of short interfering RNAs (siRNAs) is not optimal for in vivo applications. Non-ionic phosphate backbone modifications may have the potential to improve the properties of siRNAs, but are little explored in RNAi technologies. Using X-ray crystallography and RNAi activity assays, the present study demonstrates that 3'-CH2-CO-NH-5' amides are excellent replacements for phosphodiester internucleoside linkages in RNA. The crystal structure shows that amide-modified RNA forms a typical A-form duplex. The amide carbonyl group points into the major groove and assumes an orientation that is similar to the P-OP2 bond in the phosphate linkage. Amide linkages are well hydrated by tandem waters linking the carbonyl group and adjacent phosphate oxygens. Amides are tolerated at internal positions of both the guide and passenger strand of siRNAs and may increase the silencing activity when placed near the 5'-end of the passenger strand. As a result, an siRNA containing eight amide linkages is more active than the unmodified control. The results suggest that RNAi may tolerate even more extensive amide modification, which may be useful for optimization of siRNAs for in vivo applications. © The Author(s) 2014. Published by Oxford University Press on behalf of Nucleic Acids Research.

  12. Characteristic conformation of Mosher's amide elucidated using the cambridge structural database.

    Science.gov (United States)

    Ichikawa, Akio; Ono, Hiroshi; Mikata, Yuji

    2015-07-16

    Conformations of the crystalline 3,3,3-trifluoro-2-methoxy-2-phenylpropanamide derivatives (MTPA amides) deposited in the Cambridge Structural Database (CSD) were examined statistically as Racid-enantiomers. The majority of dihedral angles (48/58, ca. 83%) of the amide carbonyl groups and the trifluoromethyl groups ranged from -30° to 0° with an average angle θ1 of -13°. The other conformational properties were also clarified: (1) one of the fluorine atoms was antiperiplanar (ap) to the amide carbonyl group, forming a staggered conformation; (2) the MTPA amides prepared from primary amines showed a Z form in amide moieties; (3) in the case of the MTPA amide prepared from a primary amine possessing secondary alkyl groups (i.e., Mosher-type MTPA amide), the dihedral angles between the methine groups and the carbonyl groups were syn and indicative of a moderate conformational flexibility; (4) the phenyl plane was inclined from the O-Cchiral bond of the methoxy moiety with an average dihedral angle θ2 of +21°; (5) the methyl group of the methoxy moiety was ap to the ipso-carbon atom of the phenyl group.

  13. Synthesis of 3H-3-azido-salicyl-N-(n-decyl) amide

    International Nuclear Information System (INIS)

    Lu Bin; Xu Jianxing; Chen Shizhi

    2000-01-01

    A novel method for the synthesis of molecular probe of ubiquinone-binding protein is described. With 3-nitrosalicylic acid and decylamine as initial compounds and under the existence of DCC, the 3-nitro-salicyl-N-(n-decyl)amide is synthesized at room temperature. Then, 3-nitro-salicyl-N-(n-decyl)amide is reduced by hydrogen with 5 % Pd/C as catalyst to form 3-amino-salicyl-N-(n-decyl)amide which is exchanged with tritium to be 3 H-3-amino-salicyl-N-(n-decyl)amide. At the temperature below 5 degree C, 3 H-3-amino-salicyl-N-(n-decyl)amide reacts with NaNO 2 and HCl, and the 3-diazo-salicyl-N-(n-decyl)amide is formed in an ice salt bath. As soon as the reaction is completed, NaN 3 is added to the mixture and stirred for 3 h at the temperature between 0 - 5 degree C and in the dark, the molecular probe of studying ubiquinone-binding protein, i. e., 3 H-3-azido-salicyl-N-(n-decyl)amide is produced

  14. Structural study of salt forms of amides; paracetamol, benzamide and piperine

    Science.gov (United States)

    Kennedy, Alan R.; King, Nathan L. C.; Oswald, Iain D. H.; Rollo, David G.; Spiteri, Rebecca; Walls, Aiden

    2018-02-01

    Single crystal x-ray diffraction has been used to investigate the structures of six complexes containing O-atom protonated cations derived from the pharmaceutically relevant amides benzamide (BEN), paracetamol (PAR) and piperine (PIP). The structures of the salt forms [PAR(H)][SO3C6H4Cl], [BEN(H)][O3SC6H4Cl] and [BEN(H)][Br]·H2O are reported along with those of the hemi-halide salt forms [PAR(H)][I3]. PAR, [PIP(H)][I3]·PIP and [PIP(H)][I3]0·5[I]0.5. PIP. The structure of the cocrystal BEN. HOOCCH2Cl is also presented for comparison. The geometry of the amide group is found to systematically change upon protonation, with the Cdbnd O distance increasing and the Csbnd N distance decreasing. The hemi-halide species all feature strongly hydrogen bonded amide(H)/amide pairs. The amide group Cdbnd O and Csbnd N distances for both elements of each such pair are intermediate between those found for simple neutral amide and protonated amide forms. It was found that crystallising paracetamol from aqueous solutions containing Ba2+ ions gave orthorhombic paracetamol.

  15. Amides are excellent mimics of phosphate internucleoside linkages and are well tolerated in short interfering RNAs

    Science.gov (United States)

    Mutisya, Daniel; Selvam, Chelliah; Lunstad, Benjamin D.; Pallan, Pradeep S.; Haas, Amanda; Leake, Devin; Egli, Martin; Rozners, Eriks

    2014-01-01

    RNA interference (RNAi) has become an important tool in functional genomics and has an intriguing therapeutic potential. However, the current design of short interfering RNAs (siRNAs) is not optimal for in vivo applications. Non-ionic phosphate backbone modifications may have the potential to improve the properties of siRNAs, but are little explored in RNAi technologies. Using X-ray crystallography and RNAi activity assays, the present study demonstrates that 3′-CH2-CO-NH-5′ amides are excellent replacements for phosphodiester internucleoside linkages in RNA. The crystal structure shows that amide-modified RNA forms a typical A-form duplex. The amide carbonyl group points into the major groove and assumes an orientation that is similar to the P–OP2 bond in the phosphate linkage. Amide linkages are well hydrated by tandem waters linking the carbonyl group and adjacent phosphate oxygens. Amides are tolerated at internal positions of both the guide and passenger strand of siRNAs and may increase the silencing activity when placed near the 5′-end of the passenger strand. As a result, an siRNA containing eight amide linkages is more active than the unmodified control. The results suggest that RNAi may tolerate even more extensive amide modification, which may be useful for optimization of siRNAs for in vivo applications. PMID:24813446

  16. Synthesis of novel naphthoquinone aliphatic amides and esters and their anticancer evaluation.

    Science.gov (United States)

    Kongkathip, Boonsong; Akkarasamiyo, Sunisa; Hasitapan, Komkrit; Sittikul, Pichamon; Boonyalai, Nonlawat; Kongkathip, Ngampong

    2013-02-01

    Fourteen new naphthoquinone aliphatic amides and seventeen naphthoquinone aliphatic esters were synthesized in nine to ten steps from 1-hydroxy-2-naphthoic acid with 9-25% overall yield for the amides, and 16-21% overall yield for the esters. The key step of the amide synthesis is a coupling reaction between amine and various aliphatic acids using 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride (DMTMM) as a coupling agent while for the ester synthesis, DCC/DMAP or CDI was used as the coupling reagent between aliphatic acids and naphthoquinone alcohol. Both naphthoquinone amides and esters were evaluated for their anticancer activity against KB cells. It was found that naphthoquinone aliphatic amides showed stronger anticancer activity than those of the esters when the chains are longer than 7-carbon atoms. The optimum chain of amides is expected to be 16-carbon atoms. In addition, naphthoquinone aliphatic esters with α-methyl on the ester moiety possessed much stronger anticancer activity than the straight chains. Decatenation assay revealed that naphthoquinone amide with 16-carbon atoms chain at 15 μM and 20 μM can completely inhibit hTopoIIα activity while at 10 μM the enzyme activity was moderately inhibited. Molecular docking result also showed the same trend as the cytotoxicity and decatenation assay. Copyright © 2012 Elsevier Masson SAS. All rights reserved.

  17. Van-der-Waals interaction of atoms in dipolar Rydberg states

    Science.gov (United States)

    Kamenski, Aleksandr A.; Mokhnenko, Sergey N.; Ovsiannikov, Vitaly D.

    2018-02-01

    An asymptotic expression for the van-der-Waals constant C 6( n) ≈ -0.03 n 12 K p ( x) is derived for the long-range interaction between two highly excited hydrogen atoms A and B in their extreme Stark states of equal principal quantum numbers n A = n B = n ≫ 1 and parabolic quantum numbers n 1(2) = n - 1, n 2(1) = m = 0 in the case of collinear orientation of the Stark-state dipolar electric moments and the interatomic axis. The cubic polynomial K 3( x) in powers of reciprocal values of the principal quantum number x = 1/ n and quadratic polynomial K 2( y) in powers of reciprocal values of the principal quantum number squared y = 1/ n 2 were determined on the basis of the standard curve fitting polynomial procedure from the calculated data for C 6( n). The transformation of attractive van-der-Waals force ( C 6 > 0) for low-energy states n < 23 into repulsive force ( C 6 < 0) for all higher-energy states of n ≥ 23, is observed from the results of numerical calculations based on the second-order perturbation theory for the operator of the long-range interaction between neutral atoms. This transformation is taken into account in the asymptotic formulas (in both cases of p = 2, 3) by polynomials K p tending to unity at n → ∞ ( K p (0) = 1). The transformation from low- n attractive van-der-Waals force into high- n repulsive force demonstrates the gradual increase of the negative contribution to C 6( n) from the lower-energy two-atomic states, of the A(B)-atom principal quantum numbers n'A(B) = n-Δ n (where Δ n = 1, 2, … is significantly smaller than n for the terms providing major contribution to the second-order series), which together with the states of n″B(A) = n+Δ n make the joint contribution proportional to n 12. So, the hydrogen-like manifold structure of the energy spectrum is responsible for the transformation of the power-11 asymptotic dependence C 6( n) ∝ n 11of the low-angular-momenta Rydberg states in many-electron atoms into the power

  18. Nuclear magnetic resonance studies of quadrupolar nuclei and dipolar field effects

    International Nuclear Information System (INIS)

    Urban, Jeffry Todd

    2004-01-01

    Experimental and theoretical research conducted in two areas in the field of nuclear magnetic resonance (NMR) spectroscopy is presented: (1) studies of the coherent quantum-mechanical control of the angular momentum dynamics of quadrupolar (spin I > 1/2) nuclei and its application to the determination of molecular structure; and (2) applications of the long-range nuclear dipolar field to novel NMR detection methodologies.The dissertation is organized into six chapters. The first two chapters and associated appendices are intended to be pedagogical and include an introduction to the quantum mechanical theory of pulsed NMR spectroscopy and the time dependent theory of quantum mechanics. The third chapter describes investigations of the solid-state multiple-quantum magic angle spinning (MQMAS) NMR experiment applied to I 5/2 quadrupolar nuclei. This work reports the use of rotary resonance-matched radiofrequency irradiation for sensitivity enhancement of the I = 5/2 MQMAS experiment. These experiments exhibited certain selective line narrowing effects which were investigated theoretically.The fourth chapter extends the discussion of multiple quantum spectroscopy of quadrupolar nuclei to a mostly theoretical study of the feasibility of enhancing the resolution of nitrogen-14 NMR of large biomolecules in solution via double-quantum spectroscopy. The fifth chapter continues to extend the principles of multiple quantum NMR spectroscopy of quadrupolar nuclei to make analogies between experiments in NMR/nuclear quadrupolar resonance (NQR) and experiments in atomic/molecular optics (AMO). These analogies are made through the Hamiltonian and density operator formalism of angular momentum dynamics in the presence of electric and magnetic fields.The sixth chapter investigates the use of the macroscopic nuclear dipolar field to encode the NMR spectrum of an analyte nucleus indirectly in the magnetization of a sensor nucleus. This technique could potentially serve as an encoding

  19. Nuclear magnetic resonance studies of quadrupolar nuclei and dipolar field effects

    Energy Technology Data Exchange (ETDEWEB)

    Urban, Jeffry Todd [Univ. of California, Berkeley, CA (United States)

    2004-01-01

    Experimental and theoretical research conducted in two areas in the field of nuclear magnetic resonance (NMR) spectroscopy is presented: (1) studies of the coherent quantum-mechanical control of the angular momentum dynamics of quadrupolar (spin I > 1/2) nuclei and its application to the determination of molecular structure; and (2) applications of the long-range nuclear dipolar field to novel NMR detection methodologies.The dissertation is organized into six chapters. The first two chapters and associated appendices are intended to be pedagogical and include an introduction to the quantum mechanical theory of pulsed NMR spectroscopy and the time dependent theory of quantum mechanics. The third chapter describes investigations of the solid-state multiple-quantum magic angle spinning (MQMAS) NMR experiment applied to I = 5/2 quadrupolar nuclei. This work reports the use of rotary resonance-matched radiofrequency irradiation for sensitivity enhancement of the I = 5/2 MQMAS experiment. These experiments exhibited certain selective line narrowing effects which were investigated theoretically.The fourth chapter extends the discussion of multiple quantum spectroscopy of quadrupolar nuclei to a mostly theoretical study of the feasibility of enhancing the resolution of nitrogen-14 NMR of large biomolecules in solution via double-quantum spectroscopy. The fifth chapter continues to extend the principles of multiple quantum NMR spectroscopy of quadrupolar nuclei to make analogies between experiments in NMR/nuclear quadrupolar resonance (NQR) and experiments in atomic/molecular optics (AMO). These analogies are made through the Hamiltonian and density operator formalism of angular momentum dynamics in the presence of electric and magnetic fields.The sixth chapter investigates the use of the macroscopic nuclear dipolar field to encode the NMR spectrum of an analyte nucleus indirectly in the magnetization of a sensor nucleus. This technique could potentially serve as an

  20. Dipolar sources of the early scalp somatosensory evoked potentials to upper limb stimulation. Effect of increasing stimulus rates.

    Science.gov (United States)

    Valeriani, M; Restuccia, D; Di Lazzaro, V; Le Pera, D; Barba, C; Tonali, P; Mauguiere, F

    1998-06-01

    Brain electrical source analysis (BESA) of the scalp electroencephalographic activity is well adapted to distinguish neighbouring cerebral generators precisely. Therefore, we performed dipolar source modelling in scalp medium nerve somatosensory evoked potentials (SEPs) recorded at 1.5-Hz stimulation rate, where all the early components should be identifiable. We built a four-dipole model, which was issued from the grand average, and applied it also to recordings from single individuals. Our model included a dipole at the base of the skull and three other perirolandic dipoles. The first of the latter dipoles was tangentially oriented and was active at the same latencies as the N20/P20 potential and, with opposite polarity, the P24/N24 response. The second perirolandic dipole showed an initial peak of activity slightly earlier than that of the N20/P20 dipolar source and, later, it was active at the same latency as the central P22 potential. Lastly, the third perirolandic dipole explaining the fronto-central N30 potential scalp distribution was constantly more posterior than the first one. In order to evaluate the effect of an increasing repetition frequency on the activity of SEP dipolar sources, we applied the model built from 1.5-Hz SEPs to traces recorded at 3-Hz and 10-Hz repetition rates. We found that the 10-Hz stimulus frequency reduced selectively the later of the two activity phases of the first perirolandic dipole. The decrement in strength of this dipolar source can be explained if we assume that: (a) the later activity of the first perirolandic dipole can represent the inhibitory phase of a "primary response"; (b) two different clusters of cells generate the opposite activities of the tangential perirolandic dipole. An additional finding in our model was that two different perirolandic dipoles contribute to the centro-parietal N20 potential generation.

  1. Evidence of magnetic dipolar interaction in micrometric powders of the Fe50Mn10Al40 system: Melted alloys

    International Nuclear Information System (INIS)

    Pérez Alcázar, G.A.; Zamora, L.E.; Tabares, J.A.; Piamba, J.F.; González, J.M.; Greneche, J.M.; Martinez, A.; Romero, J.J.; Marco, J.F.

    2013-01-01

    Powders of melted disordered Fe 50 Mn 10 Al 40 alloy were separated at different mean particle sizes as well as magnetically and structurally characterized. All the samples are BCC and show the same nanostructure. Particles larger than 250 μm showed a lamellar shape compared to smaller particles, which exhibited a more regular form. All the samples are ferromagnetic at room temperature and showed reentrant spin-glass (RSG) and superparamagnetic (SP)-like behaviors between 30 and 60 K and 265 and > 280 K, respectively, as a function of frequency and particle size. The freezing temperature increases with increasing particle size while the blocking one decreases with particle size. The origin of these magnetic phenomena relies in the internal disordered character of samples and the competitive interaction of Fe and Mn atoms. The increase of their critical freezing temperature with increasing mean particle size is due to the increase of the magnetic dipolar interaction between the magnetic moment of each particle with the field produced by the other magnetic moments of their surrounding particles. - Highlights: ► The effect of particle size in microsized powders of Fe 50 Mn 10 Al 40 melted disordered alloy is studied. ► Dipolar magnetic interaction between particles exists and this changes with the particle size. ► For all the particle sizes the reentrant spin- glass and the superparamagnetic-like phases exist. ► RSG and SP critical temperatures increase with increasing the dipolar magnetic interaction (the mean particle size).

  2. Mesoporous Niobium Oxide Spheres as an Effective Catalyst for the Transamidation of Primary Amides with Amines

    KAUST Repository

    Ghosh, Subhash Chandra; Li, Cheng Chao; Zeng, Hua Chun; Ngiam, Joyce S Y; Seayad, Abdul M.; Chen, Anqi

    2014-01-01

    Mesoporous niobium oxide spheres (MNOS), conveniently prepared by a novel antisolvent precipitation approach, have been shown to be an effective catalyst for the transamidation of primary amides with amines. This novel transamidation can be efficiently carried out under solvent-free conditions and is applicable to a wide range of primary amides and amines to provide N-alkyl amides in good to excellent yields. The catalyst is highly stable and reusable. The application of this transamidation reaction has been demonstrated in the synthesis of antidepressant drug moclobemide and other druglike compounds. © 2014 Wiley-VCH Verlag GmbH&Co. KGaA, Weinheim.

  3. Detection of amide I signals of interfacial proteins in situ using SFG.

    Science.gov (United States)

    Wang, Jie; Even, Mark A; Chen, Xiaoyun; Schmaier, Alvin H; Waite, J Herbert; Chen, Zhan

    2003-08-20

    In this Communication, we demonstrate the novel observation that it is feasible to collect amide signals from polymer/protein solution interfaces in situ using sum frequency generation (SFG) vibrational spectroscopy. Such SFG amide signals allow for acquisition of more detailed molecular level information of entire interfacial protein structures. Proteins investigated include bovine serum albumin, mussel protein mefp-2, factor XIIa, and ubiquitin. Our studies indicate that different proteins generate different SFG amide signals at the polystyrene/protein solution interface, showing that they have different interfacial coverage, secondary structure, or orientation.

  4. Amide Synthesis from Alcohols and Amines by the Extrusion of Dihydrogen

    DEFF Research Database (Denmark)

    Nordstrøm, Lars Ulrik Rubæk; Vogt, Henning; Madsen, R.

    2008-01-01

    An environmentally friendly method for synthesis of amides is presented where a simple ruthenium catalyst mediates the direct coupling between an alcohol and an amine with the liberation of two molecules of dihydrogen. The active catalyst is generated in situ from an easily available ruthenium...... complex, an N-heterocyclic carbene and a phosphine. The reaction allows primary alcohols to be coupled with primary alkyamines to afford the corresponding secondary amides in good yields. The amide formation presumably proceeds through a catalytic cycle where the intermediate aldehyde and hemiaminal...

  5. Stereoelectronic model to explain the resolution of enantiomeric ibuprofen amides on the Pirkle chiral stationary phase.

    Science.gov (United States)

    Nicoll-Griffith, D A

    1987-07-31

    A chiral recognition model is proposed which incorporates the electronic and steric interactions between amide derivatives of ibuprofen and the (R)-N-(3,5-dinitrobenzoyl)phenylglycine-derived Pirkle chiral stationary phase during high-performance liquid chromatography. Based on this rationale, amide derivatives of ibuprofen were prepared using 4-chloroaniline, 4-bromoaniline, aniline, 4-methoxyaniline and 1-aminonaphthylene to improve the enantiomer separation over previously reported results with this column. The amides prepared gave separation values of 1.16, 1.16, 1.19, 1.21 and 1.23, respectively. These high separation values are consistent with the proposed model.

  6. Mesoporous Niobium Oxide Spheres as an Effective Catalyst for the Transamidation of Primary Amides with Amines

    KAUST Repository

    Ghosh, Subhash Chandra

    2014-02-06

    Mesoporous niobium oxide spheres (MNOS), conveniently prepared by a novel antisolvent precipitation approach, have been shown to be an effective catalyst for the transamidation of primary amides with amines. This novel transamidation can be efficiently carried out under solvent-free conditions and is applicable to a wide range of primary amides and amines to provide N-alkyl amides in good to excellent yields. The catalyst is highly stable and reusable. The application of this transamidation reaction has been demonstrated in the synthesis of antidepressant drug moclobemide and other druglike compounds. © 2014 Wiley-VCH Verlag GmbH&Co. KGaA, Weinheim.

  7. A Convenient One-Pot Method for the Synthesis of N-Methoxy-N-methyl Amides from Carboxylic Acids

    International Nuclear Information System (INIS)

    Kim, Joong Gon; Jang, Doo Ok

    2010-01-01

    We have developed a mild and convenient method for one-pot synthesis of Weinreb amides from carboxylic acids. The process is general for the preparation of Weinreb amides from a variety of carboxylic acids. The reaction was also applicable to the preparation of α-amino Weinreb amides and proceeded without deprotection of the N-Fmoc protecting group or racemization of the stereogenic centers. N-Methoxy-N-methyl amides, or Weinreb amides, have been widely used as versatile synthetic intermediates in organic syntheses. These amides serve as excellent acylating agents for organolithium or organomagnesium reagents and as robust aldehyde group equivalents. The utility of Weinreb amides has been extended to the preparation of N-protected amino aldehydes, useful intermediates for many chemoselective transformations in peptide chemistry

  8. Palladium-catalyzed Suzuki-Miyaura coupling of amides by carbon-nitrogen cleavage: general strategy for amide N-C bond activation.

    Science.gov (United States)

    Meng, Guangrong; Szostak, Michal

    2016-06-15

    The first palladium-catalyzed Suzuki-Miyaura cross-coupling of amides with boronic acids for the synthesis of ketones by sterically-controlled N-C bond activation is reported. The transformation is characterized by operational simplicity using bench-stable, commercial reagents and catalysts, and a broad substrate scope, including substrates with electron-donating and withdrawing groups on both coupling partners, steric-hindrance, heterocycles, halides, esters and ketones. The scope and limitations are presented in the synthesis of >60 functionalized ketones. Mechanistic studies provide insight into the catalytic cycle of the cross-coupling, including the first experimental evidence for Pd insertion into the amide N-C bond. The synthetic utility is showcased by a gram-scale cross-coupling and cross-coupling at room temperature. Most importantly, this process provides a blueprint for the development of a plethora of metal catalyzed reactions of typically inert amide bonds via acyl-metal intermediates. A unified strategy for amide bond activation to enable metal insertion into N-C amide bond is outlined ().

  9. Decreasing Distortion Energies without Strain: Diazo-Selective 1,3-Dipolar Cycloadditions.

    Science.gov (United States)

    Gold, Brian; Aronoff, Matthew R; Raines, Ronald T

    2016-07-15

    The diazo group has attributes that complement those of the azido group for applications in chemical biology. Here, we use computational analyses to provide insights into the chemoselectivity of the diazo group in 1,3-dipolar cycloadditions. Dipole distortion energies are responsible for ∼80% of the overall energetic barrier for these reactions. Here, we show that diazo compounds, unlike azides, provide an opportunity to decrease that barrier substantially without introducing strain into the dipolarophile. The ensuing rate enhancement is due to the greater nucleophilic character of a diazo group compared to that of an azido group, which can accommodate decreased distortion energies without predistortion. The tuning of distortion energies with substituents in a diazo compound or dipolarophile can enhance reactivity and selectivity in a predictable manner. Notably, these advantages of diazo groups are amplified in water. Our findings provide a theoretical framework that can guide the design and application of both diazo compounds and azides in "orthogonal" contexts, especially for biological investigations.

  10. Differential Membrane Dipolar Orientation Induced by Acute and Chronic Cholesterol Depletion.

    Science.gov (United States)

    Sarkar, Parijat; Chakraborty, Hirak; Chattopadhyay, Amitabha

    2017-06-30

    Cholesterol plays a crucial role in cell membrane organization, dynamics and function. Depletion of cholesterol represents a popular approach to explore cholesterol-sensitivity of membrane proteins. An emerging body of literature shows that the consequence of membrane cholesterol depletion often depends on the actual process (acute or chronic), although the molecular mechanism underlying the difference is not clear. Acute depletion, using cyclodextrin-type carriers, is faster relative to chronic depletion, in which inhibitors of cholesterol biosynthesis are used. With the overall goal of addressing molecular differences underlying these processes, we monitored membrane dipole potential under conditions of acute and chronic cholesterol depletion in CHO-K1 cells, using a voltage-sensitive fluorescent dye in dual wavelength ratiometric mode. Our results show that the observed membrane dipole potential exhibits difference under acute and chronic cholesterol depletion conditions, even when cholesterol content was identical. To the best of our knowledge, these results provide, for the first time, molecular insight highlighting differences in dipolar reorganization in these processes. A comprehensive understanding of processes in which membrane cholesterol gets modulated would provide novel insight in its interaction with membrane proteins and receptors, thereby allowing us to understand the role of cholesterol in cellular physiology associated with health and disease.

  11. Determination of structural fluctuations of proteins from structure-based calculations of residual dipolar couplings

    International Nuclear Information System (INIS)

    Montalvao, Rinaldo W.; De Simone, Alfonso; Vendruscolo, Michele

    2012-01-01

    Residual dipolar couplings (RDCs) have the potential of providing detailed information about the conformational fluctuations of proteins. It is very challenging, however, to extract such information because of the complex relationship between RDCs and protein structures. A promising approach to decode this relationship involves structure-based calculations of the alignment tensors of protein conformations. By implementing this strategy to generate structural restraints in molecular dynamics simulations we show that it is possible to extract effectively the information provided by RDCs about the conformational fluctuations in the native states of proteins. The approach that we present can be used in a wide range of alignment media, including Pf1, charged bicelles and gels. The accuracy of the method is demonstrated by the analysis of the Q factors for RDCs not used as restraints in the calculations, which are significantly lower than those corresponding to existing high-resolution structures and structural ensembles, hence showing that we capture effectively the contributions to RDCs from conformational fluctuations.

  12. Independent alignment of RNA for dynamic studies using residual dipolar couplings

    Energy Technology Data Exchange (ETDEWEB)

    Bardaro, Michael F.; Varani, Gabriele, E-mail: varani@chem.washington.edu [University of Washington, Department of Chemistry (United States)

    2012-09-15

    Molecular motion and dynamics play an essential role in the biological function of many RNAs. An important source of information on biomolecular motion can be found in residual dipolar couplings which contain dynamics information over the entire ms-ps timescale. However, these methods are not fully applicable to RNA because nucleic acid molecules tend to align in a highly collinear manner in different alignment media. As a consequence, information on dynamics that can be obtained with this method is limited. In order to overcome this limitation, we have generated a chimeric RNA containing both the wild type TAR RNA, the target of our investigation of dynamics, as well as the binding site for U1A protein. When U1A protein was bound to the portion of the chimeric RNA containing its binding site, we obtained independent alignment of TAR by exploiting the physical chemical characteristics of this protein. This technique can allow the extraction of new information on RNA dynamics, which is particularly important for time scales not covered by relaxation methods where important RNA motions occur.

  13. Determination of ground and excited state dipole moments of dipolar laser dyes by solvatochromic shift method.

    Science.gov (United States)

    Patil, S K; Wari, M N; Panicker, C Yohannan; Inamdar, S R

    2014-04-05

    The absorption and fluorescence spectra of three medium sized dipolar laser dyes: coumarin 478 (C478), coumarin 519 (C519) and coumarin 523 (C523) have been recorded and studied comprehensively in various solvents at room temperature. The absorption and fluorescence spectra of C478, C519 and C523 show a bathochromic and hypsochromic shifts with increasing solvent polarity indicate that the transitions involved are π→π(∗) and n→π(∗). Onsager radii determined from ab initio calculations were used in the determination of dipole moments. The ground and excited state dipole moments were evaluated by using solvatochromic correlations. It is observed that the dipole moment values of excited states (μe) are higher than corresponding ground state values (μg) for the solvents studied. The ground and excited state dipole moments of these probes computed from ab initio calculations and those determined experimentally are compared and the results are discussed. Copyright © 2013 Elsevier B.V. All rights reserved.

  14. A new dipolar potential for numerical simulations of polar fluids on the 4D hypersphere

    International Nuclear Information System (INIS)

    Caillol, Jean-Michel; Trulsson, Martin

    2014-01-01

    We present a new method for Monte Carlo or Molecular Dynamics numerical simulations of three-dimensional polar fluids. The simulation cell is defined to be the surface of the northern hemisphere of a four-dimensional (hyper)sphere. The point dipoles are constrained to remain tangent to the sphere and their interactions are derived from the basic laws of electrostatics in this geometry. The dipole-dipole potential has two singularities which correspond to the following boundary conditions: when a dipole leaves the northern hemisphere at some point of the equator, it reappears at the antipodal point bearing the same dipole moment. We derive all the formal expressions needed to obtain the thermodynamic and structural properties of a polar liquid at thermal equilibrium in actual numerical simulation. We notably establish the expression of the static dielectric constant of the fluid as well as the behavior of the pair correlation at large distances. We report and discuss the results of extensive numerical Monte Carlo simulations for two reference states of a fluid of dipolar hard spheres and compare these results with previous methods with a special emphasis on finite size effects

  15. A practical strategy for the accurate measurement of residual dipolar couplings in strongly aligned small molecules

    Science.gov (United States)

    Liu, Yizhou; Cohen, Ryan D.; Martin, Gary E.; Williamson, R. Thomas

    2018-06-01

    Accurate measurement of residual dipolar couplings (RDCs) requires an appropriate degree of alignment in order to optimize data quality. An overly weak alignment yields very small anisotropic data that are susceptible to measurement errors, whereas an overly strong alignment introduces extensive anisotropic effects that severely degrade spectral quality. The ideal alignment amplitude also depends on the specific pulse sequence used for the coupling measurement. In this work, we introduce a practical strategy for the accurate measurement of one-bond 13C-1H RDCs up to a range of ca. -300 to +300 Hz, corresponding to an alignment that is an order of magnitude stronger than typically employed for small molecule structural elucidation. This strong alignment was generated in the mesophase of the commercially available poly-γ-(benzyl-L-glutamate) polymer. The total coupling was measured by the simple and well-studied heteronuclear two-dimensional J-resolved experiment, which performs well in the presence of strong anisotropic effects. In order to unequivocally determine the sign of the total coupling and resolve ambiguities in assigning total couplings in the CH2 group, coupling measurements were conducted at an isotropic condition plus two anisotropic conditions of different alignment amplitudes. Most RDCs could be readily extracted from these measurements whereas more complicated spectral effects resulting from strong homonuclear coupling could be interpreted either theoretically or by simulation. Importantly, measurement of these very large RDCs actually offers significantly improved data quality and utility for the structure determination of small organic molecules.

  16. Cluster-cluster aggregation of Ising dipolar particles under thermal noise

    KAUST Repository

    Suzuki, Masaru

    2009-08-14

    The cluster-cluster aggregation processes of Ising dipolar particles under thermal noise are investigated in the dilute condition. As the temperature increases, changes in the typical structures of clusters are observed from chainlike (D1) to crystalline (D2) through fractal structures (D1.45), where D is the fractal dimension. By calculating the bending energy of the chainlike structure, it is found that the transition temperature is associated with the energy gap between the chainlike and crystalline configurations. The aggregation dynamics changes from being dominated by attraction to diffusion involving changes in the dynamic exponent z=0.2 to 0.5. In the region of temperature where the fractal clusters grow, different growth rates are observed between charged and neutral clusters. Using the Smoluchowski equation with a twofold kernel, this hetero-aggregation process is found to result from two types of dynamics: the diffusive motion of neutral clusters and the weak attractive motion between charged clusters. The fact that changes in structures and dynamics take place at the same time suggests that transitions in the structure of clusters involve marked changes in the dynamics of the aggregation processes. © 2009 The American Physical Society.

  17. Manipulation and control of the interfacial polarization in organic light-emitting diodes by dipolar doping

    Directory of Open Access Journals (Sweden)

    Lars Jäger

    2016-09-01

    Full Text Available Most of the commonly used electron transporting materials in organic light-emitting diodes exhibit interfacial polarization resulting from partially aligned permanent dipole moments of the molecules. This property modifies the internal electric field distribution of the device and therefore enables an earlier flat band condition for the hole transporting side, leading to improved charge carrier injection. Recently, this phenomenon was studied with regard to different materials and degradation effects, however, so far the influence of dilution has not been investigated. In this paper we focus on dipolar doping of the hole transporting material 4,4-bis[N-(1-naphthyl-N-phenylamino]-biphenyl (NPB with the polar electron transporting material tris-(8-hydroxyquinolate aluminum (Alq3. Impedance spectroscopy reveals that changes of the hole injection voltage do not scale in a simple linear fashion with the effective thickness of the doped layer. In fact, the measured interfacial polarization reaches a maximum value for a 1:1 blend. Taking the permanent dipole moment of Alq3 into account, an increasing degree of dipole alignment is found for decreasing Alq3 concentration. This observation can be explained by the competition between dipole-dipole interactions leading to dimerization and the driving force for vertical orientation of Alq3 dipoles at the surface of the NPB layer.

  18. Manipulation and control of the interfacial polarization in organic light-emitting diodes by dipolar doping

    Science.gov (United States)

    Jäger, Lars; Schmidt, Tobias D.; Brütting, Wolfgang

    2016-09-01

    Most of the commonly used electron transporting materials in organic light-emitting diodes exhibit interfacial polarization resulting from partially aligned permanent dipole moments of the molecules. This property modifies the internal electric field distribution of the device and therefore enables an earlier flat band condition for the hole transporting side, leading to improved charge carrier injection. Recently, this phenomenon was studied with regard to different materials and degradation effects, however, so far the influence of dilution has not been investigated. In this paper we focus on dipolar doping of the hole transporting material 4,4-bis[N-(1-naphthyl)-N-phenylamino]-biphenyl (NPB) with the polar electron transporting material tris-(8-hydroxyquinolate) aluminum (Alq3). Impedance spectroscopy reveals that changes of the hole injection voltage do not scale in a simple linear fashion with the effective thickness of the doped layer. In fact, the measured interfacial polarization reaches a maximum value for a 1:1 blend. Taking the permanent dipole moment of Alq3 into account, an increasing degree of dipole alignment is found for decreasing Alq3 concentration. This observation can be explained by the competition between dipole-dipole interactions leading to dimerization and the driving force for vertical orientation of Alq3 dipoles at the surface of the NPB layer.

  19. Dipolar-Biased Tunneling of Magnetization in Crystals of Single Molecule Magnets

    Science.gov (United States)

    Awaga, Kunio

    2007-03-01

    The molecular cluster Mn12 has attracted much interest as a single-molecule magnet (SMM) and as a multi-redox system. It has a high-spin ground state of S=10 and a strong uniaxial magnetic anisotropy, and the combination of the two natures makes an effective potential barrier between the up and down spin states. At low temperatures, the magnetization curve exhibited a hysteresis loop and the quantum tunneling of magnetization (QTM). In the present work, we studied the structure and magnetic properties of the mixed-metal SMM, Mn11Cr, through the analysis of Mn11Cr/Mn12 mixed crystal. High-frequency EPR spectra were well explained by assuming that Mn11Cr was in a ground spin-state of S=19/2 with nearly the same EPR parameter set as for Mn12. QTM in Mn11Cr was observed with the same field interval as for Mn12. The magnetization of Mn11Cr and Mn12 in the mixed crystal can be independently manipulated by utilizing the difference between their coercive fields. The resonance fields of QTM in Mn11Cr are significantly affected by the magnetization direction of Mn12, suggesting the effect of dipolar-biased tunneling. Besides SMM, we would also like to report the unusual magnetic properties of spherical hollow nanomagnets, the electrical properties of heterocyclic thiazyl radicals, and their possible applications in spintronics and organic electronics.

  20. Structural and dipolar properties of the voltage-dependent pore former alamethicin in octanol/dioxane.

    Science.gov (United States)

    Schwarz, G; Savko, P

    1982-01-01

    Dielectric constant and loss of the membrane-active peptide alamethicin in octanol/dioxane mixtures have been measured at frequencies between 5 kHz and 50 MHz. On the basis of a rotational mechanism of dipolar orientation, the observed dispersion provides information regarding size, shape, and dipole moment of the structural entities which the solute may assume in media of diverse lipophilicity. Particularly detailed results are obtained in a pure octanol solvent where an apparent molecular weight of alamethicin could be determined. It turns out that in this quite lipophilic medium most of the peptide material exists as a monomer particle that has approximate length and diameter of 35 and 13 A, respectively. It carries a dipole moment of approximately 75 Debye units (directed nearly parallel to the long axis). At our concentrations of a few milligrams per milliliters, appreciable formation of dimers by head-to-tail linkage is indicated. When the octanol content is reduced by adding greater amounts of dioxane, larger particles are encountered. This is accompanied by a decrease of the effective polarity. The inherent increase of hydrophilicity in the dioxane-enriched solvent apparently favors another monomer conformation that has a low dipole moment and easily aggregates to some kind of micelle. PMID:7115881

  1. Nanoscale smoothing and the analysis of interfacial charge and dipolar densities

    International Nuclear Information System (INIS)

    Junquera, Javier; Cohen, Morrel H; Rabe, Karin M

    2007-01-01

    The interface properties of interest in multilayers include interfacial charge densities, dipole densities, band offsets, and screening lengths, among others. Most such properties are inaccessible to direct measurements, but are key to understanding the physics of the multilayers. They are contained within first-principles electronic structure computations but are buried within the vast amount of quantitative information those computations generate. Thus far, they have been extracted from the numerical data by heuristic nanosmoothing procedures which do not necessarily provide results independent of the smoothing process. In the present paper we develop the theory of nanosmoothing, establishing procedures for both unpolarized and polarized systems which yield interfacial charge and dipole densities and band offsets invariant to the details of the smoothing procedures when the criteria we have established are met. We show also that dipolar charge densities, i.e. the densities of charge transferred across the interface, and screening lengths are not invariant. We illustrate our procedure with a toy model in which real, transversely averaged charge densities are replaced by sums of Gaussians. (topical review)

  2. Role of lower hybrid waves in ion heating at dipolarization fronts

    Science.gov (United States)

    Greco, A.; Artemyev, A.; Zimbardo, G.; Angelopoulos, V.; Runov, A.

    2017-05-01

    One of the important sources of hot ions in the magnetotail is the bursty bulk flows propagating away from the reconnection region and heating the ambient plasma. Charged particles interact with nonlinear magnetic field pulses (dipolarization fronts, DFs) embedded into these flows. The convection electric fields associated with DF propagation are known to reflect and accelerate ambient ions. Moreover, a wide range of waves is observed within/near these fronts, the electric field fluctuations being dominated by the lower hybrid drift (LHD) instability. Here we investigate the potential role of these waves in the further acceleration of ambient ions. We use a LHD wave emission profile superimposed on the leading edge of a two-dimensional model profile of a DF and a test particle approach. We show that LHD waves with realistic amplitudes can significantly increase the upper limit of energies gained by ions. Wave-particle interaction near the front is more effective in producing superthermal ions than in increasing the flux of thermal ions. Comparison of test particle simulations and Time History of Events and Macroscale Interactions during Substorms observations show that ion acceleration by LHD waves is more important for slower DFs.

  3. Formation of classical crystals of dipolar particles in a helical geometry

    International Nuclear Information System (INIS)

    Pedersen, J K; Fedorov, D V; Jensen, A S; Zinner, N T

    2014-01-01

    We consider crystal formation of particles with dipole–dipole interactions that are confined to move in a one-dimensional helical geometry with their dipole moments oriented along the symmetry axis of the confining helix. The stable classical lowest-energy configurations are found to be chain structures for a large range of pitch-to-radius ratios for a relatively low density of dipoles and a moderate total number of particles. The classical normal mode spectra support the chain interpretation through both structure and distinct degeneracies, depending discretely on the number of dipoles per revolution. A larger total number of dipoles leads to a clusterization where the dipolar chains move closer to each other. This implies a change in the local density and the emergence of two length scales, one for the cluster size and one for the inter-cluster distance along the helix. Starting from three dipoles per revolution, this implies a breaking of the initial periodicity to form a cluster of two chains close together and a third chain removed from the cluster. This is driven by the competition between in-chain and out-of-chain interactions, or alternatively by the side-by-side repulsion and the head-to-tail attraction in the system. The speed of sound propagates along the chains. It is independent of the number of chains, although it does depend on the geometry. (paper)

  4. On the Acceleration and Anisotropy of Ions Within Magnetotail Dipolarizing Flux Bundles

    Science.gov (United States)

    Zhou, Xu-Zhi; Runov, Andrei; Angelopoulos, Vassilis; Artemyev, Anton V.; Birn, Joachim

    2018-01-01

    Dipolarizing flux bundles (DFBs), earthward propagating structures with enhanced northward magnetic field Bz, are usually believed to carry a distinctly different plasma population from that in the ambient magnetotail plasma sheet. The ion distribution functions within the DFB, however, have been recently found to be largely controlled by the ion adiabaticity parameter κ in the ambient plasma sheet outside the DFB. According to these observations, the ambient κ values of 2-3 usually correspond to a strong perpendicular anisotropy of suprathermal ions within the DFB, whereas for lower κ values the DFB ions become more isotropic. Here we utilize a simple, test particle model to explore the nature of the anisotropy and its dependence on the ambient κ values. We find that the anisotropy originates from successive ion reflections and reentries to the DFB, during which the ions are consecutively accelerated in the perpendicular direction by the DFB-associated electric field. This consecutive acceleration may be interrupted, however, when magnetic field lines are highly curved in the ambient plasma sheet. In this case, the ion trajectories become stochastic outside the DFB, which makes the reflected ions less likely to return to the DFB for another cycle of acceleration; as a consequence, the perpendicular ion anisotropy does not appear. Given that the DFB ions are a free energy source for instabilities when they are injected toward Earth, our simple model (that reproduces most observational features on the anisotropic DFB ion distributions) may shed new lights on the coupling process between magnetotail and inner magnetosphere.

  5. Measurement of imino {sup 1}H-{sup 1}H residual dipolar couplings in RNA

    Energy Technology Data Exchange (ETDEWEB)

    Latham, Michael P. [University of Toronto, Department of Molecular Genetics (Canada); Pardi, Arthur [University of Colorado, Department of Chemistry and Biochemistry, 215 UCB (United States)], E-mail: arthur.pardi@colorado.edu

    2009-02-15

    Imino {sup 1}H-{sup 15}N residual dipolar couplings (RDCs) provide additional structural information that complements standard {sup 1}H-{sup 1}H NOEs leading to improvements in both the local and global structure of RNAs. Here, we report measurement of imino {sup 1}H-{sup 1}H RDCs for the Iron Responsive Element (IRE) RNA and native E. coli tRNA{sup Val} using a BEST-Jcomp-HMQC2 experiment. {sup 1}H-{sup 1}H RDCs are observed between the imino protons in G-U wobble base pairs and between imino protons on neighboring base pairs in both RNAs. These imino {sup 1}H-{sup 1}H RDCs complement standard {sup 1}H-{sup 15}N RDCs because the {sup 1}H-{sup 1}H vectors generally point along the helical axis, roughly perpendicular to {sup 1}H-{sup 15}N RDCs. The use of longitudinal relaxation enhancement increased the signal-to-noise of the spectra by {approx}3.5-fold over the standard experiment. The ability to measure imino {sup 1}H-{sup 1}H RDCs offers a new restraint, which can be used in NMR domain orientation and structural studies of RNAs.

  6. Dipolar interaction induced band gaps and flat modes in surface-modulated magnonic crystals

    Science.gov (United States)

    Gallardo, R. A.; Schneider, T.; Roldán-Molina, A.; Langer, M.; Fassbender, J.; Lenz, K.; Lindner, J.; Landeros, P.

    2018-04-01

    Theoretical results for the magnetization dynamics of a magnonic crystal formed by grooves on the surface of a ferromagnetic film, called a surface-modulated magnonic crystal, are presented. For such a system, the role of the periodic dipolar field induced by the geometrical modulation is addressed by using the plane-wave method. The results reveal that, under the increasing of the depth of the grooves, zones with magnetizing and demagnetizing fields act on the system in such a way that magnonic band gaps are observed in both Damon-Eshbach and backward volume geometries. Particularly, in the backward volume configuration, high-frequency band gaps and low-frequency flat modes are obtained. By taking into account the properties of the internal field induced by the grooves, the flattening of the modes and their shift towards low frequencies are discussed and explained. To test the validity of the model, the theoretical results of this work are confirmed by micromagnetic simulations, and good agreement between both methods is achieved. The theoretical model allows for a detailed understanding of the physics underlying these kinds of systems, thereby providing an outlook for potential applications on magnonic devices.

  7. Magnetic history dependence of metastable states in thin films with dipolar interactions

    International Nuclear Information System (INIS)

    Iglesias, Oscar; Labarta, Amilcar

    2000-01-01

    We present the results of a Monte Carlo simulation of the ground state and magnetic relaxation of a model of a thin film consisting of a two-dimensional square lattice of Heisenberg spins with perpendicular anisotropy K, exchange J and long-range dipolar interactions g. We have studied the ground state configurations of this system for a wide range of the interaction parameters J/g, K/g by means of the simulated annealing procedure, showing that the model is able to reproduce the different magnetic configurations found in real samples. We have found the existence of a certain range of K/g, J/g values for which in-plane and out-of-plane configurations are quasi-degenerated in energy. We show that when a system in this region of parameters is perturbed by an external force that is subsequently removed, different kinds of ordering may be induced depending on the followed procedure. In particular, simulations of relaxations from saturation under an AC demagnetizing field or in zero field are in qualitative agreement with recent experiments on epitaxial and granular alloy thin films, which show a wide variety of magnetic patterns depending on their magnetic history

  8. Understanding the Origins of Dipolar Couplings and Correlated Motion in the Vibrational Spectrum of Water.

    Science.gov (United States)

    Heyden, Matthias; Sun, Jian; Forbert, Harald; Mathias, Gerald; Havenith, Martina; Marx, Dominik

    2012-08-16

    The combination of vibrational spectroscopy and molecular dynamics simulations provides a powerful tool to obtain insights into the molecular details of water structure and dynamics in the bulk and in aqueous solutions. Applying newly developed approaches to analyze correlations of charge currents, molecular dipole fluctuations, and vibrational motion in real and k-space, we compare results from nonpolarizable water models, widely used in biomolecular modeling, to ab initio molecular dynamics. For the first time, we unfold the infrared response of bulk water into contributions from correlated fluctuations in the three-dimensional, anisotropic environment of an average water molecule, from the OH-stretching region down to the THz regime. Our findings show that the absence of electronic polarizability in the force field model not only results in differences in dipolar couplings and infrared absorption but also induces artifacts into the correlated vibrational motion between hydrogen-bonded water molecules, specifically at the intramolecular bending frequency. Consequently, vibrational motion is partially ill-described with implications for the accuracy of non-self-consistent, a posteriori methods to add polarizability.

  9. Measurement of one-bond 15N-13C' dipolar couplings in medium sized proteins

    International Nuclear Information System (INIS)

    Chou, James J.; Delaglio, Frank; Bax, Ad

    2000-01-01

    A simple and accurate method is described for measurement of 1 J C'N splittings in isotopically enriched proteins. The method is of the quantitative J correlation type, and the 1 J C'N splitting is derived from the relative intensity in two 3D TROSY-HNCO spectra with 1 J C'N dephasing intervals of ∼1/(2 1 J C'N ) (reference intensity) and ∼1/ 1 J C'N (residual intensity). If the two spectra are recorded under identical conditions and with the same number of scans, the random error in the 1 J C'N value extracted in this manner is inversely related to the signal-to-noise (S/N) in the reference spectrum. A S/N of 30:1 in the reference spectrum yields random errors of less than 0.2 Hz in the extracted 1 J C'N value. Dipolar couplings obtained from the difference in 1 J C'N splitting in the isotropic and liquid crystalline phase for the C-terminal domain of calmodulin are in excellent agreement with its 1.68-A crystal structure, but agree considerably less with the 2.2-A structure

  10. GLP-1-(9-36) amide reduces blood glucose in anesthetized pigs by a mechanism that does not involve insulin secretion

    DEFF Research Database (Denmark)

    Deacon, Carolyn F; Plamboeck, Astrid; Møller, Søren

    2002-01-01

    impossible to assess its true efficacy in vivo. In chloralose-anesthetized pigs given valine-pyrrolidide (to block endogenous DPP IV activity), the independent effects of GLP-1-(7-36) amide on glucose and insulin responses to intravenous glucose were assessed, and the metabolite generated by DPP IV, GLP-1......-(9-36) amide, was investigated for any ability to influence these responses. GLP-1-(7-36) amide enhanced insulin secretion (P amide was without effect, either alone or when coinfused with GLP-1-(7-36) amide. In contrast, GLP-1-(9-36) amide did affect glucose responses (P...... amide (73 +/- 19 mmol x l(-1) x min; P amide (62 +/- 13 mmol x l(-1) x min; P amide + GLP-1-(9-36) amide (50 +/-13 mmol x l(-1) x min; P

  11. Binary and ternary cocrystals of sulfa drug acetazolamide with pyridine carboxamides and cyclic amides.

    Science.gov (United States)

    Bolla, Geetha; Nangia, Ashwini

    2016-03-01

    A novel design strategy for cocrystals of a sulfonamide drug with pyridine carboxamides and cyclic amides is developed based on synthon identification as well as size and shape match of coformers. Binary adducts of acetazolamide (ACZ) with lactams (valerolactam and caprolactam, VLM, CPR), cyclic amides (2-pyridone, labeled as 2HP and its derivatives MeHP, OMeHP) and pyridine amides (nicotinamide and picolinamide, NAM, PAM) were obtained by manual grinding, and their single crystals by solution crystallization. The heterosynthons in the binary cocrystals of ACZ with these coformers suggested a ternary combination for ACZ with pyridone and nicotinamide. Novel supramolecular synthons of ACZ with lactams and pyridine carboxamides are reported together with binary and ternary cocrystals for a sulfonamide drug. This crystal engineering study resulted in the first ternary cocrystal of acetazolamide with amide coformers, ACZ-NAM-2HP (1:1:1).

  12. Binary and ternary cocrystals of sulfa drug acetazolamide with pyridine carboxamides and cyclic amides

    Directory of Open Access Journals (Sweden)

    Geetha Bolla

    2016-03-01

    Full Text Available A novel design strategy for cocrystals of a sulfonamide drug with pyridine carboxamides and cyclic amides is developed based on synthon identification as well as size and shape match of coformers. Binary adducts of acetazolamide (ACZ with lactams (valerolactam and caprolactam, VLM, CPR, cyclic amides (2-pyridone, labeled as 2HP and its derivatives MeHP, OMeHP and pyridine amides (nicotinamide and picolinamide, NAM, PAM were obtained by manual grinding, and their single crystals by solution crystallization. The heterosynthons in the binary cocrystals of ACZ with these coformers suggested a ternary combination for ACZ with pyridone and nicotinamide. Novel supramolecular synthons of ACZ with lactams and pyridine carboxamides are reported together with binary and ternary cocrystals for a sulfonamide drug. This crystal engineering study resulted in the first ternary cocrystal of acetazolamide with amide coformers, ACZ–NAM–2HP (1:1:1.

  13. Dynamics of urokinase receptor interaction with Peptide antagonists studied by amide hydrogen exchange and mass spectrometry

    DEFF Research Database (Denmark)

    Jørgensen, Thomas J D; Gårdsvoll, Henrik; Danø, Keld

    2004-01-01

    Using amide hydrogen exchange combined with electrospray ionization mass spectrometry, we have in this study determined the number of amide hydrogens on several peptides that become solvent-inaccessible as a result of their high-affinity interaction with the urokinase-type plasminogen activator...... receptor (uPAR). These experiments reveal that at least six out of eight amide hydrogens in a synthetic nine-mer peptide antagonist (AE105) become sequestered upon engagement in uPAR binding. Various uPAR mutants with decreased affinity for this peptide antagonist gave similar results, thereby indicating...... that deletion of the favorable interactions involving the side chains of these residues in uPAR does not affect the number of hydrogen bonds established by the main chain of the peptide ligand. The isolated growth factor-like domain (GFD) of the cognate serine protease ligand for uPAR showed 11 protected amide...

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

    DEFF Research Database (Denmark)

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

    2014-01-01

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

  15. Crystal structure of beryllium amide, Be(NH2)2

    International Nuclear Information System (INIS)

    Jacobs, H.

    1976-01-01

    The x-ray investigation of single crystals of beryllium amide led to the following results. The compound crystallizes tetragonally a = 10.170 +- 0.005 A, c = 16.137 +- 0.008 A, and c/a = 1.587. The space group is I4 1 /acd. The lattice contains 32 formula units. The positions of all atoms including hydrogen were determined. The structure of Be(NH 2 ) 2 can be described by a strongly deformed cubic closepacking of anions. The cations occupy tetrahedral interstices so that 4 Be 2+ ions form a regular tetrahedron with the shortest Be-Be distances. This causes units, which can be described by Be 4 (NH 2 ) 6 (NH 2 ) 4 / 2 whereas the outer 4 amide ions serve as bridging anions to give a threedimensional arrangement. The orientation of the amide ions is given and compared with earlier results on similar metal amides. (author)

  16. Magnetic-superexchange interactions of uranium(IV) chloride-addition complexes with amides, 2

    International Nuclear Information System (INIS)

    Miyake, Chie; Hinatsu, Yukio; Imoto, Shosuke

    1983-01-01

    The magnetic susceptibilities of five cyclic amide (lactam)-addition complexes of uranium(IV) chloride were measured between room temperature and 2 K. Magnetic-exchange interaction was found only for N-methyl-substituted amide complexes, and a dimer structure was assumed for them on the basis of their chemical properties. Treating interdimer interaction with a molecular-field approximation, the magnetic susceptibilities were calculated to be in good agreement with the experimental results in the temperature region of the maxima in chi sub(A). The transmission of antiparallel spin coupling via the π orbitals of the bridging amide ligands is proposed to explain the strong intradimer superexchange interaction for the uranium(IV) chloride-amide complexes with the magnetic-susceptibility maximum. (author)

  17. Alpha-amidated peptides derived from pro-opiomelanocortin in normal human pituitary

    DEFF Research Database (Denmark)

    Fenger, M; Johnsen, A H

    1988-01-01

    Normal human pituitaries were extracted in boiling water and acetic acid, and the alpha-amidated peptide products of pro-opiomelanocortin (POMC), alpha-melanocyte-stimulating hormone (alpha MSH), gamma-melanocyte-stimulating hormone (gamma 1MSH), and amidated hinge peptide (HP-N), as well...... (ACTH)-(1-39), ACTH-(1-14) and alpha MSH immunoreactivity]. alpha MSH and ACTH-(1-14) were only present in non- or mono-acetylated forms. Only large forms of gamma 1MSH and gamma 2MSH were present in partly glycosylated states. The hinge peptides were amidated to an extent two to three orders...... amidated POMC-related peptides are present in normal human pituitary. It also shows that cleavage in vivo at all dibasic amino acids but one, takes place at the N-terminal POMC region; the exception is at the POMC-(49-50) N-terminal of the gamma MSH sequence. The pattern of peptides produced suggests...

  18. Mechanistic Studies on the Copper-Catalyzed N-Arylation of Amides

    Science.gov (United States)

    Strieter, Eric R.; Bhayana, Brijesh; Buchwald, Stephen L.

    2009-01-01

    The copper-catalyzed N-arylation of amides, i.e., the Goldberg reaction, is an efficient method for the construction of products relevant to both industry and academic settings. Herein, we present mechanistic details concerning the catalytic and stoichiometric N-arylation of amides. In the context of the catalytic reaction, our findings reveal the importance of chelating diamine ligands in controlling the concentration of the active catalytic species. The consistency between the catalytic and stoichiometric results suggest that the activation of aryl halides occurs through a 1,2-diamine-ligated copper(I) amidate complex. Kinetic studies on the stoichiometric N-arylation of aryl iodides using 1,2-diamine ligated Cu(I) amidates also provide insights into the mechanism of aryl halide activation. PMID:19072233

  19. First Novozym 435 lipase-catalyzed Morita-Baylis-Hillman reaction in the presence of amides.

    Science.gov (United States)

    Tian, Xuemei; Zhang, Suoqin; Zheng, Liangyu

    2016-03-01

    The first Novozym 435 lipase-catalyzed Morita-Baylis-Hillman (MBH) reaction with amides as co-catalyst was realized. Results showed that neither Novozym 435 nor amide can independently catalyze the reaction. This co-catalytic system that used a catalytic amount of Novozym 435 with a corresponding amount of amide was established and optimized. The MBH reaction strongly depended on the structure of aldehyde substrate, amide co-catalyst, and reaction additives. The optimized reaction yield (43.4%) was achieved in the Novozym 435-catalyzed MBH reaction of 2, 4-dinitrobenzaldehyde and cyclohexenone with isonicotinamide as co-catalyst and β-cyclodextrin as additive only in 2 days. Although enantioselectivity of Novozym 435 was not found, the results were still significant because an MBH reaction using lipase as biocatalyst was realized for the first time. Copyright © 2015 Elsevier Inc. All rights reserved.

  20. Direct Synthesis of Medium-Bridged Twisted Amides via a Transannular Cyclization Strategy

    Science.gov (United States)

    Szostak, Michal; Aubé, Jeffrey

    2009-01-01

    The sequential RCM to construct a challenging medium-sized ring followed by a transannular cyclization across a medium-sized ring delivers previously unattainable twisted amides from simple acyclic precursors. PMID:19708701