Sample records for synthesis solid-state nmr

  1. Synthesis, Isotopic Enrichment, and Solid-State NMR Characterization of Zeolites Derived from the Assembly, Disassembly, Organization, Reassembly Process. (United States)

    Bignami, Giulia P M; Dawson, Daniel M; Seymour, Valerie R; Wheatley, Paul S; Morris, Russell E; Ashbrook, Sharon E


    The great utility and importance of zeolites in fields as diverse as industrial catalysis and medicine has driven considerable interest in the ability to target new framework types with novel properties and applications. The recently introduced and unconventional assembly, disassembly, organization, reassembly (ADOR) method represents one exciting new approach to obtain solids with targeted structures by selectively disassembling preprepared hydrolytically unstable frameworks and then reassembling the resulting products to form materials with new topologies. However, the hydrolytic mechanisms underlying such a powerful synthetic method are not understood in detail, requiring further investigation of the kinetic behavior and the outcome of reactions under differing conditions. In this work, we report the optimized ADOR synthesis, and subsequent solid-state characterization, of (17)O- and doubly (17)O- and (29)Si-enriched UTL-derived zeolites, by synthesis of (29)Si-enriched starting Ge-UTL frameworks and incorporation of (17)O from (17)O-enriched water during hydrolysis. (17)O and (29)Si NMR experiments are able to demonstrate that the hydrolysis and rearrangement process occurs over a much longer time scale than seen by diffraction. The observation of unexpectedly high levels of (17)O in the bulk zeolitic layers, rather than being confined only to the interlayer spacing, reveals a much more extensive hydrolytic rearrangement than previously thought. This work sheds new light on the role played by water in the ADOR process and provides insight into the detailed mechanism of the structural changes involved.

  2. Scalar operators in solid-state NMR

    Energy Technology Data Exchange (ETDEWEB)

    Sun, Boqin [Univ. of California, Berkeley, CA (United States)


    Selectivity and resolution of solid-state NMR spectra are determined by dispersion of local magnetic fields originating from relaxation effects and orientation-dependent resonant frequencies of spin nuclei. Theoretically, the orientation-dependent resonant frequencies can be represented by a set of irreducible tensors. Among these tensors, only zero rank tensors (scalar operators) are capable of providing high resolution NMR spectra. This thesis presents a series of new developments in high resolution solid-state NMR concerning the reconstruction of various scalar operators motion in solid C60 is analyzed.

  3. Oriented solid-state NMR spectrosocpy

    DEFF Research Database (Denmark)

    Bertelsen, Kresten

    This thesis is concerned with driving forward oriented solid-state NMR spectroscopy as a viable technique for studying peptides in membrane bilayers. I will show that structural heterogeneity is an intrinsic part of the peptide/lipid system and that NMR can be used to characterize static...... and dynamic structural features of the peptides and its local surroundings. In fact one need to take into account the dynamical features of the system in order to correctly predict the structure from oriented solid-state NMR spectra.      ...

  4. Developments in Solid-State NMR

    Indian Academy of Sciences (India)

    Home; Journals; Resonance – Journal of Science Education; Volume 20; Issue 11. Developments in Solid-State NMR. K V Ramanathan. General Article Volume 20 Issue 11 November 2015 pp 1040-1052. Fulltext. Click here to view fulltext PDF. Permanent link: ...

  5. Solid-state NMR for bacterial biofilms (United States)

    Reichhardt, Courtney; Cegelski, Lynette


    Bacteria associate with surfaces and one another by elaborating an extracellular matrix to encapsulate cells, creating communities termed biofilms. Biofilms are beneficial in some ecological niches, but also contribute to the pathogenesis of serious and chronic infectious diseases. New approaches and quantitative measurements are needed to define the composition and architecture of bacterial biofilms to help drive the development of strategies to interfere with biofilm assembly. Solid-state nuclear magnetic resonance (NMR) is uniquely suited to the examination of insoluble and complex macromolecular and whole-cell systems. This article highlights three examples that implement solid-state NMR to deliver insights into bacterial biofilm composition and changes in cell-wall composition as cells transition to the biofilm lifestyle. Most recently, solid-state NMR measurements provided a total accounting of the protein and polysaccharide components in the extracellular matrix of an Escherichia coli biofilm and transformed our qualitative descriptions of matrix composition into chemical parameters that permit quantitative comparisons among samples. We present additional data for whole biofilm samples (cells plus the extracellular matrix) that complement matrix-only analyses. The study of bacterial biofilms by solid-state NMR is an exciting avenue ripe with many opportunities and we close the article by articulating some outstanding questions and future directions in this area.

  6. Synthesis and conformational study of silk model polypeptides [Ala-Gly] 12 by solid-state NMR (United States)

    Kishi, Satoshi; Santos, Andres; Ishii, Osamu; Ishikawa, Kazuo; Kunieda, Shingo; Kimura, Hideaki; Shoji, Akira


    A series of well-defined model polypeptides of Bombyx mori silk fibroin, [Ala-Gly] n ( n=12 and 5-9), [Ala d4Gly] 12 and [Gly d2Ala] 12, (where Ala, Gly, Ala d4 and Gly d2 denote L-alanine, glycine, 2,3,3,3-deuterated L-alanine and 2,2-deuterated glycine residues, respectively), were successfully synthesized by an automatic solid phase peptide synthesizer. Followed by treatment with 9 M lithium bromide (LiBr) solution to convert their conformation from the silk II to the silk I form. We determined the intrinsic 1H, 13C and 15N NMR chemical shifts of Ala and Gly residues, characteristic to the silk I and silk II forms in Bombyx mori, by high-resolution and solid-state 13C CP-MAS, 1H CRAMPS, 1H- 13C HETCOR and 15N CP-MAS NMR measurements. Next, we demonstrated that it is necessary at least 12 amino acid residues ( n=6) in the [Ala-Gly] n-I series for the formation of stable silk I form by 13C CP-MAS NMR. Finally, we found that the intrinsic 1H and 13C chemical shifts of the specific deuterium labeled polypeptides, [Ala d4-Gly] 12 and [Gly d2-Ala] 12, cause a meaningful chemical shift displacement, suggesting that the deuterium interacts with proton and/or carbon atoms in the solid state. Thus, the selective deuterium labeling has a potential to useful for the structural analysis by 1H NMR in the solid state.

  7. Solid state NMR of biopolymers and synthetic polymers

    Energy Technology Data Exchange (ETDEWEB)

    Jelinski, Lynn W. [Cornell Univ., Geneva, NY (United States)


    Solid state NMR has been invaluable in evaluating the structure, phase separation, and dynamics of polymers. Because polymers are generally used in the solid state, solid state NMR is especially powerful because it provides information about the materials in their native state. This review gives a general overview of solid state NMR, concentrating on solid state {sup 13} C and {sup 2} H NMR. It then focuses on two examples: the biopolymer spider silka and the engineering material polyurethane. It illustrates how solid state NMR can provide new information about synthetic and bio-polymers. (author) 11 refs., 5 figs., 3 tabs.

  8. Solid-state NMR basic principles and practice

    CERN Document Server

    Apperley, David C; Hodgkinson, Paul


    Nuclear Magnetic Resonance (NMR) has proved to be a uniquely powerful and versatile tool for analyzing and characterizing chemicals and materials of all kinds. This book focuses on the latest developments and applications for "solid-state" NMR, which has found new uses from archaeology to crystallography to biomaterials and pharmaceutical science research. The book will provide materials engineers, analytical chemists, and physicists, in and out of lab, a survey of the techniques and the essential tools of solid-state NMR, together with a practical guide on applications. In this concise introduction to the growing field of solid-state nuclear magnetic resonance spectroscopy The reader will find: * Basic NMR concepts for solids, including guidance on the spin-1/2 nuclei concept * Coverage of the quantum mechanics aspects of solid state NMR and an introduction to the concept of quadrupolar nuclei * An understanding relaxation, exchange and quantitation in NMR * An analysis and interpretation of NMR data, with e...

  9. Solid State NMR Investigations of Zeolite - Intercalate Structures

    Energy Technology Data Exchange (ETDEWEB)

    Fyfe, Colin A.; Diaz, Anix; Brouwer, Darren H.; Lee, Joseph; Schneider, Celine M.; Scheffler, Franziska A.; Darton, Richard J.


    We will describe two topics in which structural information on complexes of zeolites is obtained from solid state NMR. In the first, recent work on the determination of the complete three-dimensional structures of the complexes of zeolites with organic sorbates will be briefly reported. The method has been optimized and the presentation of the results systematized. In the second topic, we will describe how solid state NMR can be used in the reverse sense to probe for the existence and structures of “nanocrystals” whose dimensions are too small to give proper Bragg scattering and which have been proposed to be the synthesis route for the formation of zeolite ZSM-5. In this study, the spectral parameters of “probe” template molecules are used as being diagnostic of whether the local environment of the framework has been formed. These are independent of the “crystal” dimensions and this general approach may be applicable to other similar “nano” systems.

  10. Advanced solid-state NMR spectroscopy of natural organic matter. (United States)

    Mao, Jingdong; Cao, Xiaoyan; Olk, Dan C; Chu, Wenying; Schmidt-Rohr, Klaus


    Solid-state NMR is essential for the characterization of natural organic matter (NOM) and is gaining importance in geosciences and environmental sciences. This review is intended to highlight advanced solid-state NMR techniques, especially a systematic approach to NOM characterization, and their applications to the study of NOM. We discuss some basics of how to acquire high-quality and quantitative solid-state 13 C NMR spectra, and address some common technical mistakes that lead to unreliable spectra of NOM. The identification of specific functional groups in NOM, primarily based on 13 C spectral-editing techniques, is described and the theoretical background of some recently-developed spectral-editing techniques is provided. Applications of solid-state NMR to investigating nitrogen (N) in NOM are described, focusing on limitations of the widely used 15 N CP/MAS experiment and the potential of improved advanced NMR techniques for characterizing N forms in NOM. Then techniques used for identifying proximities, heterogeneities and domains are reviewed, and some examples provided. In addition, NMR techniques for studying segmental dynamics in NOM are reviewed. We also briefly discuss applications of solid-state NMR to NOM from various sources, including soil organic matter, aquatic organic matter, organic matter in atmospheric particulate matter, carbonaceous meteoritic organic matter, and fossil fuels. Finally, examples of NMR-based structural models and an outlook are provided. Copyright © 2016 Elsevier B.V. All rights reserved.

  11. The solid-state synthesis of tritium labelled heterocyclic bases

    Energy Technology Data Exchange (ETDEWEB)

    Sidorov, G.V.; Myasoedov, N.F. (AN SSSR, Moscow (Russian Federation). Inst. Molekulyarnoj Genetiki)


    The results of a study of the solid-state catalytic hydrogenation and the synthesis of tritium labelled native heterocyclic bases are presented. The effect of different palladium catalysts and reaction conditions on yield and molar radioactivity of final compounds was investigated. For some compounds, data on the intramolecular distribution of tritium were obtained by using the isotope exchange reaction and tritium NMR. Tritium labelled purine and pyrimidine bases (25-180 Ci/mmol.) were synthesized. (Author).

  12. Solid-State NMR Spectroscopy for the Physical Chemistry Laboratory (United States)

    Kinnun, Jacob J.; Leftin, Avigdor; Brown, Michael F.


    Solid-state nuclear magnetic resonance (NMR) spectroscopy finds growing application to inorganic and organic materials, biological samples, polymers, proteins, and cellular membranes. However, this technique is often neither included in laboratory curricula nor typically covered in undergraduate courses. On the other hand, spectroscopy and…

  13. Solid-State NMR and DFT Studies on the Formation of Well-Defined Silica-Supported Tantallaaziridines: From Synthesis to Catalytic Application

    KAUST Repository

    Hamzaoui, Bilel


    Single-site, well-defined, silica-supported tantallaaziridine intermediates [≡Si-O-Ta(η2-NRCH2)(NMe2)2] [R=Me (2), Ph (3)] were prepared from silica-supported tetrakis(dimethylamido)tantalum [≡Si-O-Ta(NMe2)4] (1) and fully characterized by FTIR spectroscopy, elemental analysis, and 1H,13C HETCOR and DQ TQ solid-state (SS) NMR spectroscopy. The formation mechanism, by β-H abstraction, was investigated by SS NMR spectroscopy and supported by DFT calculations. The C-H activation of the dimethylamide ligand is favored for R=Ph. The results from catalytic testing in the hydroaminoalkylation of alkenes were consistent with the N-alkyl aryl amine substrates being more efficient than N-dialkyl amines. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. DFT calculations of quadrupolar solid-state NMR properties: Some examples in solid-state inorganic chemistry. (United States)

    Cuny, Jerome; Messaoudi, Sabri; Alonzo, Veronique; Furet, Eric; Halet, Jean-François; Le Fur, Eric; Ashbrook, Sharon E; Pickard, Chris J; Gautier, Regis; Le Polles, Laurent


    This article presents results of first-principles calculations of quadrupolar parameters measured by solid-state nuclear magnetic measurement (NMR) spectroscopy. Different computational methods based on density functional theory were used to calculate the quadrupolar parameters. Through a series of illustrations from different areas of solid state inorganic chemistry, it is shown how quadrupolar solid-state NMR properties can be tackled by a theoretical approach and can yield structural information. (c) 2008 Wiley Periodicals, Inc.

  15. Phosphide oxides RE2AuP2O (RE = La, Ce, Pr, Nd): synthesis, structure, chemical bonding, magnetism, and 31P and 139La solid state NMR. (United States)

    Bartsch, Timo; Wiegand, Thomas; Ren, Jinjun; Eckert, Hellmut; Johrendt, Dirk; Niehaus, Oliver; Eul, Matthias; Pöttgen, Rainer


    Polycrystalline samples of the phosphide oxides RE(2)AuP(2)O (RE = La, Ce, Pr, Nd) were obtained from mixtures of the rare earth elements, binary rare earth oxides, gold powder, and red phosphorus in sealed silica tubes. Small single crystals were grown in NaCl/KCl fluxes. The samples were studied by powder X-ray diffraction, and the structures were refined from single crystal diffractometer data: La(2)AuP(2)O type, space group C2/m, a = 1515.2(4), b = 424.63(8), c = 999.2(2) pm, β = 130.90(2)°, wR2 = 0.0410, 1050 F(2) values for Ce(2)AuP(2)O, and a = 1503.6(4), b = 422.77(8), c = 993.0(2) pm, β = 130.88(2)°, wR2 = 0.0401, 1037 F(2) values for Pr(2)AuP(2)O, and a = 1501.87(5), b = 420.85(5), c = 990.3(3) pm, β = 131.12(1)°, wR2 = 0.0944, 1143 F(2) values for Nd(2)AuP(2)O with 38 variables per refinement. The structures are composed of [RE(2)O](4+) polycationic chains of cis-edge-sharing ORE(4/2) tetrahedra and polyanionic strands [AuP(2)](4-), which contain gold in almost trigonal-planar phosphorus coordination by P(3-) and P(2)(4-) entities. The isolated phosphorus atoms and the P(2) pairs in La(2)AuP(2)O could clearly be distinguished by (31)P solid state NMR spectroscopy and assigned on the basis of a double quantum NMR technique. Also, the two crystallographically inequivalent La sites could be distinguished by static (139)La NMR in conjunction with theoretical electric field gradient calculations. Temperature-dependent magnetic susceptibility measurements show diamagnetic behavior for La(2)AuP(2)O. Ce(2)AuP(2)O and Pr(2)AuP(2)O are Curie-Weiss paramagnets with experimental magnetic moments of 2.35 and 3.48 μ(B) per rare earth atom, respectively. Their solid state (31)P MAS NMR spectra are strongly influenced by paramagnetic interactions. Ce(2)AuP(2)O orders antiferromagnetically at 13.1(5) K and shows a metamagnetic transition at 11.5 kOe. Pr(2)AuP(2)O orders ferromagnetically at 7.0 K.

  16. RNA structure determination by solid-state NMR spectroscopy. (United States)

    Marchanka, Alexander; Simon, Bernd; Althoff-Ospelt, Gerhard; Carlomagno, Teresa


    Knowledge of the RNA three-dimensional structure, either in isolation or as part of RNP complexes, is fundamental to understand the mechanism of numerous cellular processes. Because of its flexibility, RNA represents a challenge for crystallization, while the large size of cellular complexes brings solution-state NMR to its limits. Here, we demonstrate an alternative approach on the basis of solid-state NMR spectroscopy. We develop a suite of experiments and RNA labeling schemes and demonstrate for the first time that ssNMR can yield a RNA structure at high-resolution. This methodology allows structural analysis of segmentally labelled RNA stretches in high-molecular weight cellular machines—independent of their ability to crystallize—and opens the way to mechanistic studies of currently difficult-to-access RNA-protein assemblies.

  17. Monitoring Cocrystal Formation via In Situ Solid-State NMR. (United States)

    Mandala, Venkata S; Loewus, Sarel J; Mehta, Manish A


    A detailed understanding of the mechanism of organic cocrystal formation remains elusive. Techniques that interrogate a reacting system in situ are preferred, though experimentally challenging. We report here the results of a solid-state in situ NMR study of the spontaneous formation of a cocrystal between a pharmaceutical mimic (caffeine) and a coformer (malonic acid). Using (13)C magic angle spinning NMR, we show that the formation of the cocrystal may be tracked in real time. We find no direct evidence for a short-lived, chemical shift-resolved amorphous solid intermediate. However, changes in the line width and line center of the malonic acid methylene resonance, in the course of the reaction, provide subtle clues to the mode of mass transfer that underlies cocrystal formation.

  18. Solid State NMR Characterization of Complex Metal Hydrides systems for Hydrogen Storage Applications

    Directory of Open Access Journals (Sweden)

    Son-Jong Hwang


    Full Text Available Solid state NMR is widely applied in studies of solid state chemistries for hydrogen storage reactions. Use of 11B MAS NMR in studies of metal borohydrides (BH4 is mainly focused, revisiting the issue of dodecaborane formation and observation of 11B{1H} Nuclear Overhauser Effect.

  19. Lithium substitution in strontium chlorapatite studied by solid state NMR spectroscopy (United States)

    Subramanian, S.; Maji, B. K.; Jena, H.; Sairam, T. N.; Amarendra, G.


    Strontium Chlorapatites with various amounts of Li substitution (Sr10-xLix(PO4)6Cl2-δ) were prepared by solid state reaction method and characterized by powder XRD and solid state NMR spectroscopy. XRD reveals shortening of lattice parameters upon Li incorporation. The linewidth of 31P solid state Magic Angle Spinning NMR spectra decreases with increase in Li content within the apatite phase. This study confirms Li uptake within the apatite phase.

  20. Recent developments in solid-state NMR spectroscopy of crystalline microporous materials. (United States)

    Ashbrook, Sharon E; Dawson, Daniel M; Seymour, Valerie R


    Microporous materials, having pores and channels on the same size scale as small to medium molecules, have found many important applications in current technologies, including catalysis, gas separation and drug storage and delivery. Many of their properties and functions are related to their detailed local structure, such as the type and distribution of active sites within the pores, and the specific structures of these active sites. Solid-state NMR spectroscopy has a strong track record of providing the requisite detailed atomic-level insight into the structures of microporous materials, in addition to being able to probe dynamic processes occurring on timescales spanning many orders of magnitude (i.e., from s to ps). In this Perspective, we provide a brief review of some of the basic experimental approaches used in solid-state NMR spectroscopy of microporous materials, and then discuss some more recent advances in this field, particularly those applied to the study of crystalline materials such as zeolites and metal-organic frameworks. These advances include improved software for aiding spectral interpretation, the development of the NMR-crystallography approach to structure determination, new routes for the synthesis of isotopically-labelled materials, methods for the characterisation of host-guest interactions, and methodologies suitable for observing NMR spectra of paramagnetic microporous materials. Finally, we discuss possible future directions, which we believe will have the greatest impact on the field over the coming years.

  1. integrating Solid State NMR and Computations in Membrane Protein Science (United States)

    Cross, Timothy


    Helical membrane protein structures are influenced by their native environment. Therefore the characterization of their structure in an environment that models as closely as possible their native environment is critical for achieving not only structural but functional understanding of these proteins. Solid state NMR spectroscopy in liquid crystalline lipid bilayers provides an excellent tool for such characterizations. Two classes of restraints can be obtained - absolute restraints that constrain the structure to a laboratory frame of reference when using uniformly oriented samples (approximately 1° of mosaic spread) and relative restraints that restrain one part of the structure with respect to another part such as torsional and distance restraints. Here, I will discuss unique restraints derived from uniformly oriented samples and the characterization of initial structures utilizing both restraint types, followed by restrained molecular dynamics refinement in the same lipid bilayer environment as that used for the experimental restraint collection. Protein examples will be taken from Influenza virus and Mycobacterium tuberculosis. When available comparisons of structures to those obtained using different membrane mimetic environments will be shown and the causes for structural distortions explained based on an understanding of membrane biophysics and its sophisticated influence on membrane proteins.

  2. Structure of Green River oil shale kerogen: determination using solid state /sup 13/C NMR spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Trewhella, M.J.; Poplett, I.J.F.; Grint, A.


    A sample of kerogen isolated from a Green River oil shale has been examined using high resolution solid state /sup 13/C NMR spectroscopy. The relative concentrations of carbon types have been determined using a novel peak-synthesis technique applied to the /sup 13/C spectra. This technique has been successfully applied in determining the amount and type of individual carbon atoms in a sample of Green River oil shale kerogen, with sufficient resolution to enable an average structure to be proposed. The kerogen is highly aliphatic and appears to contain substantial quantities of both saturated polycondensed ring structures, and long chain n-alkanes or n-alkyl substituents. 20 references.

  3. Solid-State NMR Study of New Copolymers as Solid Polymer Electrolytes

    Directory of Open Access Journals (Sweden)

    Jean-Christophe Daigle


    Full Text Available We report the analysis of comb-like polymers by solid-state NMR. The polymers were previously evaluated as solid-polymer-electrolytes (SPE for lithium-polymer-metal batteries that have suitable ionic conductivity at 60 °C. We propose to develop a correlation between 13C solid-state NMR measurements and phase segregation. 13C solid-state NMR is a perfect tool for differentiating polymer phases with fast or slow motions. 7Li was used to monitor the motion of lithium ions in the polymer, and activation energies were calculated.

  4. Hydrothermal synthesis, crystal structure, and solid-state NMR spectroscopy of a new indium silicate: K2In(OH)(Si4O10). (United States)

    Hung, Ling-I; Wang, Sue-Lein; Kao, Hsien-Ming; Lii, Kwang-Hwa


    A new indium(III) silicate, K(2)In(OH)(Si(4)O(10)), has been synthesized by a high-temperature, high-pressure hydrothermal method. It crystallizes in the monoclinic space group P2(1)/m (No. 11) with a = 11.410(1) A, b = 8.373(1) A, c = 11.611(1) A, beta = 112.201(2) degrees, and Z = 4. The structure, which is analogous to that of K(2)CuSi(4)O(10), consists of unbranched vierer 4-fold chains of corner-sharing SiO(4) tetrahedra running along the b axis linked together via corner sharing by chains of trans-corner-sharing InO(4)(OH)(2) octahedra to form a 3-D framework which delimits 8-ring and 6-ring channels to accommodate K(+) cations. The presence of hydroxyl groups is confirmed by IR spectroscopy. The (29)Si MAS NMR exhibits four resonances at -88.6, -90.1, -97.4, and -98.2 ppm corresponding to four distinct crystallographic Si sites. A (1)H --> (29)Si CP/MAS NMR experiment was performed to assign the four resonances.

  5. Ageing of starch based systems as observed with FT-IR and solid state NMR spectroscopy

    NARCIS (Netherlands)

    Vliegenthart, J.F.G.; Smits, A.L.M.; Ruhnau, F.C.; Soest, J.J.G. van


    The retrogradation and physical ageing of model starch systems with respect to their glass transition temperatures Tg have been investigated by Fourier transform infrared Spectroscopy and solid state NMR spectroscopy. Diffuse reflectance Fourier transform infrared (DRIFT) spectra demonstrate the

  6. Ageing of Starch Based Systems as observed with FT-IR and Solid State NMR Spectroscopy

    NARCIS (Netherlands)

    Smits, A.L.M.; Ruhnau, F.C.; Vliegenthart, J.F.G.; Soest, van J.J.G.


    The retrogradation and physical ageing of model starch systems with respect to their glass transition temperatures Tg have been investigated by Fourier transform infrared spectroscopy and solid state NMR spectroscopy. Diffuse reflectance Fourier transform infrared (DRIFT) spectra demonstrate the

  7. A Toolbox of Solid-State NMR Experiments for the Characterization of Soft Organic Nanomaterials

    KAUST Repository

    Straasø, Lasse Arnt


    Determining how organic molecules self-assemble into a solid material is a challenging and demanding task if a single crystal of the material cannot be produced. Solid-state NMR spectroscopy offers access to such molecular details via an appropriate selection of techniques. This report gives a selected overview of 1D and 2D solid-state NMR techniques for elucidating the structure of soft organic solids. We focus on how the solid-state NMR techniques are designed from the perspective of the different nuclear interactions, using average Hamiltonian theory and product operators. We also introduce recent methods for quantification and reduction of experimental artifacts. Finally, we highlight how the solid-state NMR techniques can be applied to soft organic materials by reviewing recent applications to semicrystalline polymers, π-conjugated polymers, natural silk, and graphene-related materials.

  8. Lithium substitution in strontium chlorapatite studied by solid state NMR spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Subramanian, S.; Sairam, T. N., E-mail:; Amarendra, G. [Materials Science Group, Indira Gandhi Centre for Atomic Research, Kalpakkam-603102 (India); Maji, B. K.; Jena, H. [Chemical Group, Indira Gandhi Centre for Atomic Research, Kalpakkam-603102 (India)


    Strontium Chlorapatites with various amounts of Li substitution (Sr{sub 10-x}Li{sub x}(PO{sub 4}){sub 6}Cl{sub 2-δ}) were prepared by solid state reaction method and characterized by powder XRD and solid state NMR spectroscopy. XRD reveals shortening of lattice parameters upon Li incorporation. The linewidth of {sup 31}P solid state Magic Angle Spinning NMR spectra decreases with increase in Li content within the apatite phase. This study confirms Li uptake within the apatite phase.

  9. Exploring the limits of (73)Ge solid-state NMR spectroscopy at ultrahigh magnetic field. (United States)

    Sutrisno, Andre; Hanson, Margaret A; Rupar, Paul A; Terskikh, Victor V; Baines, Kim M; Huang, Yining


    The ultrahigh field natural abundance (73)Ge solid-state wide-line NMR study of germanium dichloride complexed with 1,4-dioxane and tetraphenylgermane yields the largest (73)Ge quadrupolar coupling constant determined by NMR spectroscopy to date and the first direct observation of (73)Ge chemical shift anisotropy.

  10. Solid-state 29Si NMR and FTIR analyses of lignin-silica coprecipitates

    DEFF Research Database (Denmark)

    Cabrera Orozco, Yohanna; Cabrera, Andrés; Larsen, Flemming Hofmann


    investigated by characterizing lignin and silica coprecipitates by FTIR and solid state NMR. Silica particles were coprecipitated with three different lignins, three lignin model compounds, and two silanes representing silica-in-lignin model compounds. Comparison of 29Si SP/MAS NMR spectra revealed differences...

  11. Solid-state 73Ge NMR spectroscopy of simple organogermanes. (United States)

    Hanson, Margaret A; Sutrisno, Andre; Terskikh, Victor V; Baines, Kim M; Huang, Yining


    Germanium-73 is an extremely challenging nucleus to examine by NMR spectroscopy due to its unfavorable NMR properties. Through the use of an ultrahigh (21.1 T) magnetic field, a systematic study of a series of simple organogermanes was carried out. In those cases for which X-ray structural data were available, correlations were drawn between the NMR parameters and structural metrics. These data were combined with DFT calculations to obtain insight into the structures of several compounds with unknown crystal structures. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Oxide based functional materials through solid state and electrochemical synthesis


    Todorova, Vanya


    The presented dissertation combines synthesis and characterization techniques of solid state chemistry and electrochemistry. The work is organized into two main parts. The first part deals with the synthesis, structural characterization and investigation of the physical properties of new ternary and quaternary transition metal oxides with layered structures. Several compounds of delafossite structure ABO2 with silver on A position and different trivalent cation capable of adopting an octa...

  13. Atomic substitutions in synthetic apatite; Insights from solid-state NMR spectroscopy (United States)

    Vaughn, John S.

    Apatite, Ca5(PO4)3X (where X = F, Cl, or OH), is a unique mineral group capable of atomic substitutions for cations and anions of varied size and charge. Accommodation of differing substituents requires some kind of structural adaptation, e.g. new atomic positions, vacancies, or coupled substitutions. These structural adaptations often give rise to important physicochemical properties relevant to a range of scientific disciplines. Examples include volatile trapping during apatite crystallization, substitution for large radionuclides for long-term storage of nuclear fission waste, substitution for fluoride to improve acid resistivity in dental enamel composed dominantly of hydroxylapatite, and the development of novel biomaterials with enhanced biocompatibility. Despite the importance and ubiquity of atomic substitutions in apatite materials, many of the mechanisms by which these reactions occur are poorly understood. Presence of substituents at dilute concentration and occupancy of disordered atomic positions hinder detection by bulk characterization methods such as X-ray diffraction (XRD) and infrared (IR) spectroscopy. Solid-state nuclear magnetic resonance (NMR) spectroscopy is an isotope-specific structural characterization technique that does not require ordered atomic arrangements, and is therefore well suited to investigate atomic substitutions and structural adaptations in apatite. In the present work, solid-state NMR is utilized to investigate structural adaptations in three different types of apatite materials; a series of near-binary F, Cl apatite, carbonate-hydroxylapatite compositions prepared under various synthesis conditions, and a heat-treated hydroxylapatite enriched in 17O. The results indicate that hydroxyl groups in low-H, near binary F,Cl apatite facilitate solid-solution between F and Cl via column reversals, which result in average hexagonal symmetry despite very dilute OH concentration ( 2 mol percent). In addition, 19F NMR spectra indicate

  14. Solid state NMR method development and studies of biological and biomimetic nanocomposites

    Energy Technology Data Exchange (ETDEWEB)

    Hu, Yanyan [Iowa State Univ., Ames, IA (United States)


    This thesis describes application and development of advanced solid-state nuclear magnetic resonance techniques for complex materials, in particular organic-inorganic nanocomposites and thermoelectric tellurides. The apatite-collagen interface, essential for understanding the biomineralization process in bone and engineering the interface for controlled bio-mimetic synthesis and optimized mechanical properties, is buried within the nanocomposite of bone. We used multinuclear solid-state NMR to study the composition and structure of the interface. Citrate has been identified as the main organic molecule strongly bound to the apatite surface with a density of 1/(2 nm)2, covering 1/6 of the total surface area in bovine bone. Citrate provides more carboxylate groups, one of the key functional groups found to affect apatite nucleation and growth, than all the non-collagenous proteins all together in bone; thus we propose that citrate stabilizes apatite crystals at a very small thickness of ~3 nm (4 unit cells) to increase bone fracture tolerance. The hypothesis has been confirmed in vitro by adding citrate in the bio-mimetic synthesis of polymerhydroxyapatite nanocomposites. The results have shown that the size of hydroxyapatite nanocrystals decreases as increasing citrate concentration. With citrate concentrations comparable to that in body fluids, similar-sized nanocrystals as in bone have been produced. Besides the dimensions of the apatite crystals, the composition of bone also affects its biofunctional and macroscopic mechanical properties; therefore, our team also extended its effort to enhance the inorganic portion in our bio-mimetic synthesis from originally 15 wt% to current 50 wt% compared to 65 wt% in bovine bone, by using Lysine-Leucine hydroxyapatite nucleating diblock co-polypeptide, which forms a gel at very low concentration. In this thesis, various advanced solid state NMR techniques have been employed to characterize nanocomposites

  15. Optimized "detectors" for dynamics analysis in solid-state NMR (United States)

    Smith, Albert A.; Ernst, Matthias; Meier, Beat H.


    Relaxation in nuclear magnetic resonance (NMR) results from stochastic motions that modulate anisotropic NMR interactions. Therefore, measurement of relaxation-rate constants can be used to characterize molecular-dynamic processes. The motion is often characterized by Markov processes using an auto-correlation function, which is assumed to be a sum of multiple decaying exponentials. We have recently shown that such a model can lead to severe misrepresentation of the real motion, when the real correlation function is more complex than the model. Furthermore, multiple distributions of motion may yield the same set of dynamics data. Therefore, we introduce optimized dynamics "detectors" to characterize motions which are linear combinations of relaxation-rate constants. A detector estimates the average or total amplitude of motion for a range of motional correlation times. The information obtained through the detectors is less specific than information obtained using an explicit model, but this is necessary because the information contained in the relaxation data is ambiguous, if one does not know the correct motional model. On the other hand, if one has a molecular dynamics trajectory, one may calculate the corresponding detector responses, allowing direct comparison to experimental NMR dynamics analysis. We describe how to construct a set of optimized detectors for a given set of relaxation measurements. We then investigate the properties of detectors for a number of different data sets, thus gaining an insight into the actual information content of the NMR data. Finally, we show an example analysis of ubiquitin dynamics data using detectors, using the DIFRATE software.

  16. Solid state NMR studies of materials for energy technology (United States)

    Nambukara Kodiweera Arachchilage, Chandana K.

    Presented in this dissertation are NMR investigations of the dynamical and structural properties of materials for energy conversion and storage devices. 1H and 2H NMR was used to study water and methanol transportation in sulfonated poly(arylene ether ketone) based membranes for direct methanol fuel cells (DMFC). These results are presented in chapter 3. The amount of liquid in the membrane and ion exchange capacity (IEC) are two main factors that govern the dynamics in these membranes. Water and methanol diffusion coefficients also are comparable. Chapters 4 and 5 are concerned with 31P and 1H NMR in phosphoric acid doped PBI membranes (para-PBI and 2OH-PBI) as well as PBI membranes containing ionic liquids (H3PO4/PMIH2PO4/PBI). These membranes are designed for higher-temperature fuel cell operation. In general, stronger short and long range interactions were observed in the 2OH-PBI matrix, yielding reduced proton transport compared to that of para-PBI. In the case of H3PO4/PMIH2PO 4/PBI, both conductivity and diffusion are higher for the sample with molar ratio 2/4/1. Finally, chapter 6 is devoted to the 31P NMR MAS study of phosphorus-containing structural groups on the surfaces of micro/mesoporous activated carbons. Two spectral features were observed and the narrow feature identifies surface phosphates while the broad component identifies heterogeneous subsurface phosphorus environments including phosphate and more complex structure multiple P-C, P-N and P=N bonds.

  17. A solid state and solution NMR study of the tautomerism in hydroxyquinoline carboxylic acids. (United States)

    Gudat, Dietrich; Nycz, Jacek E; Polanski, Jaroslaw


    Some hydroxyquinoline carboxylic acids and their conjugate acids and bases were characterized by 13C and 15N NMR spectroscopy in solution and in the solid state. Differences in 13C and, in particular, 15N chemical shift patterns allow to distinguish between individual tautomers and confirm the presence of zwitterionic species in the solid state. Solution NMR spectra in dimethyl sulfoxide (DMSO) show effects resulting as a consequence of dynamic exchange and suggest the presence of an equilibrium mixture of hydroxyquinoline carboxylic acid and zwitterionic hydroxyquinolinium carboxylate tautomers.

  18. Solid-state NMR and ESR studies of activated carbons produced from pecan shells (United States)

    Activated carbon from pecan shells has shown promise as an adsorbent in water treatment and sugar refining. However, the chemistry of the material is complex and not fully understood. We report here the application of solid state NMR and ESR to study the chemical structure, mobility, and pore volu...

  19. Efficient 2D double-quantum solid-state NMR spectroscopy with large spectral widths. (United States)

    Märker, Katharina; Hediger, Sabine; De Paëpe, Gaël


    2D double-quantum single-quantum correlation spectra with arbitrary spectral widths can be recorded with SR26 and related supercycled recoupling sequences when applying Supercycle-Timing-Compensation (STiC) phase shifts. This concept widely extends the applicability of supercycled sequences, most importantly for obtaining long-range distance constraints for structure determination with solid-state NMR.

  20. High-Resolution Solid-State NMR Spectroscopy: Characterization of Polymorphism in Cimetidine, a Pharmaceutical Compound (United States)

    Pacilio, Julia E.; Tokarski, John T.; Quiñones, Rosalynn; Iuliucci, Robbie J.


    High-resolution solid-state NMR (SSNMR) spectroscopy has many advantages as a tool to characterize solid-phase material that finds applications in polymer chemistry, nanotechnology, materials science, biomolecular structure determination, and others, including the pharmaceutical industry. The technology associated with achieving high resolution…

  1. Structural rearrangements of membrane proteins probed by water-edited solid-state NMR spectroscopy

    NARCIS (Netherlands)

    Ader, C.; Schneider, R.; Seidel, K.; Etzkorn, M.; Becker, S.; Baldus, M.


    We show that water-edited solid-state NMR spectroscopy allows for probing global protein conformation and residue-specific solvent accessibility in a lipid bilayer environment. The transfer dynamics can be well described by a general time constant, irrespective of protein topology and lipid

  2. Identification of double four-ring units in germanosilicate ITQ-13 zeolite by solid-state NMR spectroscopy. (United States)

    Liu, Xiaolong; Chu, Yueying; Wang, Qiang; Wang, Weiyu; Wang, Chao; Xu, Jun; Deng, Feng


    Well-crystallized Ge-free and Ge-ITQ-13 were successfully obtained by solid state synthesis method. The Ge/Si ratio and the water content that are the two important factors in the synthesis of germanosilicate zeolites were explored for the formation of ITQ-13. The effect of the mineralizing agents (NH4F and NH4Cl) on the ITQ-13 synthesis was investigated as well. The obtained pure silica ITQ-13 and Ge-ITQ-13 were characterized by one- and two-dimensional solid- state NMR techniques. One-dimensional (1D) 19F MAS, 1H→29Si CP/MAS and 19F→29Si CP/MAS NMR spectroscopy evidenced the formation of pure Si-D4R (double four ring) and Ge-D4R units, with the latter being generated by substitution of Si atom from the former units. The detailed configurations of the Ge-D4R units in ITQ-13 was revealed by two-dimensional (2D) 29Si{19F} HETCOR NMR spectroscopy. With the help of theoretical calculations on the 19F and 29Si NMR chemical shifts, six types of D4R units were determined. The formation of the specific D4R unit confirms the structural directing roles of Ge atom and F ions in the formation of the D4R units in zeolite framework. The identification of the SiOSi bonds in the D4R units that connects the layers of ITQ-13 framework provided rationale for the high stability of the ITQ-13 in the degermanation treatment. Copyright © 2017 Elsevier Inc. All rights reserved.

  3. Automated solid-state NMR resonance assignment of protein microcrystals and amyloids

    Energy Technology Data Exchange (ETDEWEB)

    Schmidt, Elena [Goethe University Frankfurt am Main, Center for Biomolecular Magnetic Resonance, Institute of Biophysical Chemistry (Germany); Gath, Julia [ETH Zurich, Physical Chemistry (Switzerland); Habenstein, Birgit [UMR 5086 CNRS/Universite de Lyon 1, Institut de Biologie et Chimie des Proteines (France); Ravotti, Francesco; Szekely, Kathrin; Huber, Matthias [ETH Zurich, Physical Chemistry (Switzerland); Buchner, Lena [Goethe University Frankfurt am Main, Center for Biomolecular Magnetic Resonance, Institute of Biophysical Chemistry (Germany); Boeckmann, Anja, E-mail: [UMR 5086 CNRS/Universite de Lyon 1, Institut de Biologie et Chimie des Proteines (France); Meier, Beat H., E-mail: [ETH Zurich, Physical Chemistry (Switzerland); Guentert, Peter, E-mail: [Goethe University Frankfurt am Main, Center for Biomolecular Magnetic Resonance, Institute of Biophysical Chemistry (Germany)


    Solid-state NMR is an emerging structure determination technique for crystalline and non-crystalline protein assemblies, e.g., amyloids. Resonance assignment constitutes the first and often very time-consuming step to a structure. We present ssFLYA, a generally applicable algorithm for automatic assignment of protein solid-state NMR spectra. Application to microcrystals of ubiquitin and the Ure2 prion C-terminal domain, as well as amyloids of HET-s(218-289) and {alpha}-synuclein yielded 88-97 % correctness for the backbone and side-chain assignments that are classified as self-consistent by the algorithm, and 77-90 % correctness if also assignments classified as tentative by the algorithm are included.

  4. Solid-state NMR, electrophysiology and molecular dynamics characterization of human VDAC2

    Energy Technology Data Exchange (ETDEWEB)

    Gattin, Zrinka; Schneider, Robert; Laukat, Yvonne; Giller, Karin [Max Planck Institute for Biophysical Chemistry (Germany); Maier, Elke [Theodor-Boveri-Institut (Biozentrum) der Universität Würzburg, Lehrstuhl für Biotechnologie (Germany); Zweckstetter, Markus; Griesinger, Christian [Max Planck Institute for Biophysical Chemistry (Germany); Benz, Roland [Theodor-Boveri-Institut (Biozentrum) der Universität Würzburg, Lehrstuhl für Biotechnologie (Germany); Becker, Stefan; Lange, Adam, E-mail: [Max Planck Institute for Biophysical Chemistry (Germany)


    The voltage-dependent anion channel (VDAC) is the most abundant protein of the outer mitochondrial membrane and constitutes the major pathway for the transport of ADP, ATP, and other metabolites. In this multidisciplinary study we combined solid-state NMR, electrophysiology, and molecular dynamics simulations, to study the structure of the human VDAC isoform 2 in a lipid bilayer environment. We find that the structure of hVDAC2 is similar to the structure of hVDAC1, in line with recent investigations on zfVDAC2. However, hVDAC2 appears to exhibit an increased conformational heterogeneity compared to hVDAC1 which is reflected in broader solid-state NMR spectra and less defined electrophysiological profiles.

  5. Solid-state NMR: a powerful tool for characterization of metal-organic frameworks. (United States)

    Sutrisno, Andre; Huang, Yining


    Metal-organic frameworks (MOFs) are a new type of porous materials with numerous current and potential applications in many areas including ion-exchange, catalysis, sensing, separation, molecular recognition, drug delivery and, in particular, gas storage. Solid-state NMR (SSNMR) has played a pivotal role in structural characterization and understanding of host-guest interactions in MOFs. This article provides an overview on application of SSNMR to MOF systems. Copyright © 2012 Elsevier Inc. All rights reserved.


    Energy Technology Data Exchange (ETDEWEB)

    Gao, A.; Heck, R.W.


    This paper details a way to produce azurin with an effi ciency over 10 times greater than previously described and demonstrates the fi rst solid state nuclear magnetic resonance spectrum of 65Cu(I) in a metalloprotein. A synthetic gene for azurin based upon the DNA sequence from Pseudomonas aeruginosa including the periplasmic targeting sequence was subcloned into a T7 overexpression vector to create the plasmid pGS-azurin, which was transformed into BL21 (DE3) competent cells. The leader sequence on the expressed protein causes it to be exported to the periplasmic space of Escherichia coli. Bacteria grown in a fermentation unit were induced to overexpress the azurin, which was subsequently purifi ed through an endosmotic shock procedure followed by high performance liquid chromatography (HPLC). 1,500 mg of azurin were purifi ed per liter of culture. 65Cu(II) was added to apo-azurin and then reduced. The 65Cu metal cofactor in azurin was observed with solid state nuclear magnetic resonance (NMR) to determine any structural variations that accompanied copper reduction. This is the fi rst solid state NMR spectra of a copper(I) metalloprotein. Analysis of the NMR spectra is being used to complement hypotheses set forth by x-ray diffraction and computational calculations of electron transfer mechanisms in azurin.

  7. Solid-State NMR Spectroscopy of Metal–Organic Framework Compounds (MOFs

    Directory of Open Access Journals (Sweden)

    Stefan Kaskel


    Full Text Available Nuclear Magnetic Resonance (NMR spectroscopy is a well-established method for the investigation of various types of porous materials. During the past decade, metal–organic frameworks have attracted increasing research interest. Solid-state NMR spectroscopy has rapidly evolved into an important tool for the study of the structure, dynamics and flexibility of these materials, as well as for the characterization of host–guest interactions with adsorbed species such as xenon, carbon dioxide, water, and many others. The present review introduces and highlights recent developments in this rapidly growing field.

  8. Prospects for207Pb solid-state NMR studies of lead tetrel bonds. (United States)

    Southern, Scott A; Errulat, Dylan; Frost, Jamie M; Gabidullin, Bulat; Bryce, David L


    The feasibility and value of 207 Pb solid-state NMR experiments on compounds featuring lead tetrel bonds is explored. Although the definition remains to be formalized, lead tetrel bonds may be qualitatively described as existing when there is evidence of a net attractive interaction between an electrophilic region associated with lead in a molecular entity and a nucleophilic region in another, or the same, molecular entity. Unambiguous identification of lead tetrel bonds can be challenging due to the hypervalent tendency of lead. We report here a series of 207 Pb solid-state NMR experiments on five metal-organic frameworks featuring lead coordinated to hydrazone-based ligands. Such frameworks may be held together in part by lead tetrel bonds. The acquisition of 207 Pb solid-state NMR spectra for such materials is feasible and is readily accomplished using a combination of magic-angle spinning and Carr-Purcell-Meiboom-Gill methods in moderate to low applied magnetic fields. The lead centres are characterized by 207 Pb isotropic chemical shifts ranging from -426 to -2591 ppm and chemical shift tensor spans ranging from 910 to 2681 ppm. Careful inspection of the structures of the compounds and the literature 207 Pb NMR data may suggest that a tetrel bond to lead results in chemical shift parameters which are intermediate between those which are characteristic of holodirected and hemidirected lead coordination geometries. Challenges associated with DFT computations of the 207 Pb NMR parameters are discussed. In summary, the 207 Pb data for the compounds studied herein show a marked response to the presence of non-coordinating electron-rich moieties in close contact with the electrophilic surface of formally hemidirectionally coordinated lead compounds.

  9. Structure determination of helical filaments by solid-state NMR spectroscopy (United States)

    Ahmed, Mumdooh; Spehr, Johannes; König, Renate; Lünsdorf, Heinrich; Rand, Ulfert; Lührs, Thorsten; Ritter, Christiane


    The controlled formation of filamentous protein complexes plays a crucial role in many biological systems and represents an emerging paradigm in signal transduction. The mitochondrial antiviral signaling protein (MAVS) is a central signal transduction hub in innate immunity that is activated by a receptor-induced conversion into helical superstructures (filaments) assembled from its globular caspase activation and recruitment domain. Solid-state NMR (ssNMR) spectroscopy has become one of the most powerful techniques for atomic resolution structures of protein fibrils. However, for helical filaments, the determination of the correct symmetry parameters has remained a significant hurdle for any structural technique and could thus far not be precisely derived from ssNMR data. Here, we solved the atomic resolution structure of helical MAVSCARD filaments exclusively from ssNMR data. We present a generally applicable approach that systematically explores the helical symmetry space by efficient modeling of the helical structure restrained by interprotomer ssNMR distance restraints. Together with classical automated NMR structure calculation, this allowed us to faithfully determine the symmetry that defines the entire assembly. To validate our structure, we probed the protomer arrangement by solvent paramagnetic resonance enhancement, analysis of chemical shift differences relative to the solution NMR structure of the monomer, and mutagenesis. We provide detailed information on the atomic contacts that determine filament stability and describe mechanistic details on the formation of signaling-competent MAVS filaments from inactive monomers. PMID:26733681

  10. Solid-state NMR studies of theophylline co-crystals with dicarboxylic acids. (United States)

    Pindelska, Edyta; Sokal, Agnieszka; Szeleszczuk, Lukasz; Pisklak, Dariusz Maciej; Kolodziejski, Waclaw


    In this work, three polycrystalline materials containing co-crystals of theophylline with malonic, maleic, and glutaric acids were studied using (13)C, (15)N and (1)H solid-state NMR and FT-IR spectroscopy. The NMR assignments were supported by gauge including projector augmented waves (GIPAW) calculations of chemical shielding, performed using X-ray determined geometry. The experimental (13)C cross polarization/magic angle spinning (CP/MAS) NMR results and the calculated isotropic chemical shifts were in excellent agreement. A rapid and convenient method for theophylline co-crystals crystal structure analysis has been proposed for co-crystals, which are potentially new APIs. Copyright © 2014 Elsevier B.V. All rights reserved.

  11. Freezing point depression of water in phospholipid membranes: a solid-state NMR study. (United States)

    Lee, Dong-Kuk; Kwon, Byung Soo; Ramamoorthy, Ayyalusamy


    Lipid-water interaction plays an important role in the properties of lipid bilayers, cryoprotectants, and membrane-associated peptides and proteins. The temperature at which water bound to lipid bilayers freezes is lower than that of free water. Here, we report a solid-state NMR investigation on the freezing point depression of water in phospholipid bilayers in the presence and absence of cholesterol. Deuterium NMR spectra at different temperatures ranging from -75 to + 10 degrees C were obtained from fully (2)H2O-hydrated POPC (1-palmitoyl-2-oleoylphosphatidylcholine) multilamellar vesicles (MLVs), prepared with and without cholesterol, to determine the freezing temperature of water and the effect of cholesterol on the freezing temperature of water in POPC bilayers. Our 2H NMR experiments reveal the motional behavior of unfrozen water molecules in POPC bilayers even at temperatures significantly below 0 degrees C and show that the presence of cholesterol further lowered the freezing temperature of water in POPC bilayers. These results suggest that in the presence of cholesterol the fluidity and dynamics of lipid bilayers can be retained even at very low temperatures as exist in the liquid crystalline phase of the lipid. Therefore, bilayer samples prepared with a cryoprotectant like cholesterol should enable the performance of multidimensional solid-state NMR experiments to investigate the structure, dynamics, and topology of membrane proteins at a very low temperature with enhanced sample stability and possibly a better sensitivity. Phosphorus-31 NMR data suggest that lipid bilayers can be aligned at low temperatures, while 15N NMR experiments demonstrate that such aligned samples can be used to enhance the signal-to-noise ratio of is 15N chemical shift spectra of a 37-residue human antimicrobial peptide, LL-37.

  12. Spatially resolved solid-state 1H NMR for evaluation of gradient-composition polymeric libraries. (United States)

    Leisen, Johannes; Gomez, Ismael J; Roper, John A; Meredith, J Carson; Beckham, Haskell W


    Polyurethane libraries consisting of films with composition gradients of aliphatic polyisocyanate and hydroxy-terminated polyacrylate resin were characterized using methods of (1)H NMR microimaging (i.e., magnetic resonance imaging, (MRI)) and solid-state NMR. Molecular mobilities and underlying structural information were extracted as a function of the relative content of each of the two components. Routine NMR microimaging using the spin-echo sequence only allows investigations of transverse relaxation of magnetization at echo times >2 ms. A single-exponential decay was found, which is likely due to free, noncross-linked polymer chains. The mobility of these chains decreases with increasing content of the aliphatic polyisocyanate. The concept of a 1D NMR profiler is introduced as a novel modality for library screening, which allows the convenient measurement of static solid-state NMR spectra as a function of spatial location along a library sample that is repositioned in the rf coil between experiments. With this setup the complete transverse relaxation function was measured using Bloch decays and spin echoes. For all positions within the gradient-composition film, relaxation data consisted of at least three components that were attributed to a rigid highly cross-linked resin, an intermediate cross-linked but mobile constituent, and the highly mobile free polymer chains (the latter is also detectable by MRI). Analysis of this overall relaxation function measured via Bloch decays and spin echoes revealed only minor changes in the mobilities of the individual fractions. Findings with respect to the most mobile components are consistent with the results obtained by NMR microimaging. The major effect is the significant increase in the rigid-component fraction with the addition of the hydroxy-terminated polyacrylate resin.

  13. Solid-state NMR paramagnetic relaxation enhancement immersion depth studies in phospholipid bilayers

    KAUST Repository

    Chu, Shidong


    A new approach for determining the membrane immersion depth of a spin-labeled probe has been developed using paramagnetic relaxation enhancement (PRE) in solid-state NMR spectroscopy. A DOXYL spin label was placed at different sites of 1-palmitoyl-2-stearoyl-sn-glycero-3-phosphocholine (PSPC) phospholipid bilayers as paramagnetic moieties and the resulting enhancements of the longitudinal relaxation (T1) times of 31P nuclei on the surface of the bilayers were measured by a standard inversion recovery pulse sequence. The 31P NMR spin-lattice relaxation times decrease steadily as the DOXYL spin label moves closer to the surface as well as the concentration of the spin-labeled lipids increase. The enhanced relaxation vs. the position and concentration of spin-labels indicate that PRE induced by the DOXYL spin label are significant to determine longer distances over the whole range of the membrane depths. When these data were combined with estimated correlation times τc, the r-6-weighted, time-averaged distances between the spin-labels and the 31P nuclei on the membrane surface were estimated. The application of using this solid-state NMR PRE approach coupled with site-directed spin labeling (SDSL) may be a powerful method for measuring membrane protein immersion depth. © 2010 Elsevier Inc. All rights reserved.

  14. Sensitivity and resolution enhancement in solid-state NMR spectroscopy of bicelles (United States)

    Dvinskikh, Sergey V.; Yamamoto, Kazutoshi; Dürr, Ulrich H. N.; Ramamoorthy, Ayyalusamy


    Magnetically aligned bicelles are becoming attractive model membranes to investigate the structure, dynamics, geometry, and interaction of membrane-associated peptides and proteins using solution- and solid-state NMR experiments. Recent studies have shown that bicelles are more suitable than mechanically aligned bilayers for multidimensional solid-state NMR experiments. In this work, we describe experimental aspects of the natural abundance 13C and 14N NMR spectroscopy of DMPC/DHPC bicelles. In particular, approaches to enhance the sensitivity and resolution and to quantify radio-frequency heating effects are presented. Sensitivity of 13C detection using single pulse excitation, conventional cross-polarization (CP), ramp-CP, and NOE techniques are compared. Our results suggest that the proton decoupling efficiency of the FLOPSY pulse sequence is better than that of continuous wave decoupling, TPPM, SPINAL, and WALTZ sequences. A simple method of monitoring the water proton chemical shift is demonstrated for the measurement of sample temperature and calibration of the radio-frequency-induced heating in the sample. The possibility of using 14N experiments on bicelles is also discussed.

  15. Solid-state NMR of the Yersinia pestis outer membrane protein Ail in lipid bilayer nanodiscs sedimented by ultracentrifugation

    Energy Technology Data Exchange (ETDEWEB)

    Ding, Yi; Fujimoto, L. Miya; Yao, Yong; Marassi, Francesca M., E-mail: [Sanford-Burnham Medical Research Institute (United States)


    Solid-state NMR studies of sedimented soluble proteins has been developed recently as an attractive approach for overcoming the size limitations of solution NMR spectroscopy while bypassing the need for sample crystallization or precipitation (Bertini et al. Proc Natl Acad Sci USA 108(26):10396–10399, 2011). Inspired by the potential benefits of this method, we have investigated the ability to sediment lipid bilayer nanodiscs reconstituted with a membrane protein. In this study, we show that nanodiscs containing the outer membrane protein Ail from Yersinia pestis can be sedimented for solid-state NMR structural studies, without the need for precipitation or lyophilization. Optimized preparations of Ail in phospholipid nanodiscs support both the structure and the fibronectin binding activity of the protein. The same sample can be used for solution NMR, solid-state NMR and activity assays, facilitating structure–activity correlation experiments across a wide range of timescales.

  16. Crystallographic and dynamic aspects of solid-state NMR calibration compounds: towards ab initio NMR crystallography

    DEFF Research Database (Denmark)

    Li, Xiaozhou; Tapmeyer, Lukas; Bolte, Michael


    The excellent results of dispersion-corrected density functional theory (DFT-D) calculations for static systems have been well established over the past decade. The introduction of dynamics into DFT-D calculations is a target, especially for the field of molecular NMR crystallography. Four 13C ss-NMR...

  17. Solid-state NMR spectroscopic study of phosphate sorption mechanisms on aluminum (Hydr)oxides. (United States)

    Li, Wei; Feng, Xionghan; Yan, Yupeng; Sparks, Donald L; Phillips, Brian L


    Sorption reactions occurring at mineral/water interfaces are of fundamental importance in controlling the sequestration and bioavailability of nutrients and pollutants in aqueous environments. To advance the understanding of sorption reactions, development of new methodology is required. In this study, we applied novel (31)P solid-state nuclear magnetic resonance (NMR) spectroscopy to investigate the mechanism of phosphate sorption on aluminum hydroxides under different environmental conditions, including pH (4-10), concentration (0.1-10 mM), ionic strength (0.001-0.5 M), and reaction time (15 min-22 days). Under these conditions, the NMR results suggest formation of bidentate binuclear inner-sphere surface complexes was the dominant mechanism. However, it was found that surface wetting caused a small difference. A small amount (phosphate sorption not only on the macroscopic sorption capacity but also on their (31)P NMR spectra. Very similar NMR peaks were observed for phosphate sorbed to gibbsite and bayerite, whereas the spectra for phosphate adsorbed to boehmite, corundum, and γ-alumina were significantly different. All of these measurements reveal that NMR spectroscopy is a useful analytical tool for studying phosphorus chemistry at environmental interfaces.

  18. Dynamics and interactions of ibuprofen in cyclodextrin nanosponges by solid-state NMR spectroscopy

    Directory of Open Access Journals (Sweden)

    Monica Ferro


    Full Text Available Two different formulations of cyclodextrin nanosponges (CDNS, obtained by polycondensation of β-cyclodextrin with ethylenediaminetetraacetic acid dianhydride (EDTAn, were treated with aqueous solutions of ibuprofen sodium salt (IbuNa affording hydrogels that, after lyophilisation, gave two solid CDNS-drug formulations. 1H fast MAS NMR and 13C CP-MAS NMR spectra showed that IbuNa was converted in situ into its acidic and dimeric form (IbuH after freeze-drying. 13C CP-MAS NMR spectra also indicated that the structure of the nanosponge did not undergo changes upon drug loading compared to the unloaded system. However, the 13C NMR spectra collected under variable contact time cross-polarization (VCT-CP conditions showed that the polymeric scaffold CDNS changed significantly its dynamic regime on passing from the empty CDNS to the drug-loaded CDNS, thus showing that the drug encapsulation can be seen as the formation of a real supramolecular aggregate rather than a conglomerate of two solid components. Finally, the structural features obtained from the different solid-state NMR approaches reported matched the information from powder X-ray diffraction profiles.

  19. A Solid-State NMR Study of Selenium Substitution into Nanocrystalline Hydroxyapatite (United States)

    Kolmas, Joanna; Kuras, Marzena; Oledzka, Ewa; Sobczak, Marcin


    The substitution of selenium oxyanions in the hydroxyapatite structure was examined using multinuclear solid-state resonance spectroscopy (ssNMR). The study was supported by powder X-ray diffractometry (PXRD) and wavelength dispersion X-ray fluorescence (WD-XRF). Samples of pure hydroxyapatite (HA300) and selenate (HA300-1.2SeO4) or selenite (HA300-1.2SeO3) substituted hydroxyapatites were synthesized using the standard wet method and heated at 300 °C to remove loosely bonded water. PXRD data showed that all samples are single-phase, nanocrystalline hydroxyapatite. The incorporation of selenite and selenate ions affected the lattice constants. In selenium-containing samples the concentration of Se was very similar and amounted to 9.55% and 9.64%, for HA300-1.2SeO4 and HA300-1.2SeO3, respectively. PXRD and ssNMR data showed that the selenite doping significantly decreases the crystallite size and crystallinity degree. 31P and 1H NMR experiments demonstrated the developed surface hydrated layer in all samples, especially in HA300-1.2SeO3. 1H NMR studies showed the dehydroxylation of HA during the selenium oxyanions substitution and the existence of hydrogen bonding in structural hydroxyl group channels. 1H→77Se cross polarization NMR experiments indicated that selenites and selenates are located in the crystal lattice and on the crystal surface. PMID:25997001

  20. A Solid-State NMR Study of Selenium Substitution into Nanocrystalline Hydroxyapatite

    Directory of Open Access Journals (Sweden)

    Joanna Kolmas


    Full Text Available The substitution of selenium oxyanions in the hydroxyapatite structure was examined using multinuclear solid-state resonance spectroscopy (ssNMR. The study was supported by powder X-ray diffractometry (PXRD and wavelength dispersion X-ray fluorescence (WD-XRF. Samples of pure hydroxyapatite (HA300 and selenate (HA300-1.2SeO4 or selenite (HA300-1.2SeO3 substituted hydroxyapatites were synthesized using the standard wet method and heated at 300 °C to remove loosely bonded water. PXRD data showed that all samples are single-phase, nanocrystalline hydroxyapatite. The incorporation of selenite and selenate ions affected the lattice constants. In selenium-containing samples the concentration of Se was very similar and amounted to 9.55% and 9.64%, for HA300-1.2SeO4 and HA300-1.2SeO3, respectively. PXRD and ssNMR data showed that the selenite doping significantly decreases the crystallite size and crystallinity degree. 31P and 1H NMR experiments demonstrated the developed surface hydrated layer in all samples, especially in HA300-1.2SeO3. 1H NMR studies showed the dehydroxylation of HA during the selenium oxyanions substitution and the existence of hydrogen bonding in structural hydroxyl group channels. 1H→77Se cross polarization NMR experiments indicated that selenites and selenates are located in the crystal lattice and on the crystal surface.

  1. A solid-state NMR study of selenium substitution into nanocrystalline hydroxyapatite. (United States)

    Kolmas, Joanna; Kuras, Marzena; Oledzka, Ewa; Sobczak, Marcin


    The substitution of selenium oxyanions in the hydroxyapatite structure was examined using multinuclear solid-state resonance spectroscopy (ssNMR). The study was supported by powder X-ray diffractometry (PXRD) and wavelength dispersion X-ray fluorescence (WD-XRF). Samples of pure hydroxyapatite (HA300) and selenate (HA300-1.2SeO4) or selenite (HA300-1.2SeO3) substituted hydroxyapatites were synthesized using the standard wet method and heated at 300 °C to remove loosely bonded water. PXRD data showed that all samples are single-phase, nanocrystalline hydroxyapatite. The incorporation of selenite and selenate ions affected the lattice constants. In selenium-containing samples the concentration of Se was very similar and amounted to 9.55% and 9.64%, for HA300-1.2SeO4 and HA300-1.2SeO3, respectively. PXRD and ssNMR data showed that the selenite doping significantly decreases the crystallite size and crystallinity degree. 31P and 1H NMR experiments demonstrated the developed surface hydrated layer in all samples, especially in HA300-1.2SeO3. 1H NMR studies showed the dehydroxylation of HA during the selenium oxyanions substitution and the existence of hydrogen bonding in structural hydroxyl group channels. 1H→77Se cross polarization NMR experiments indicated that selenites and selenates are located in the crystal lattice and on the crystal surface.

  2. A 1H/19F minicoil NMR probe for solid-state NMR: application to 5-fluoroindoles. (United States)

    Graether, Steffen P; DeVries, Jeffrey S; McDonald, Robert; Rakovszky, Melissa L; Sykes, Brian D


    We show that it is feasible to use a minicoil for solid-state 19F 1H NMR experiments that has short pulse widths, good RF homogeneity, and excellent signal-to-noise for small samples while using low power amplifiers typical to liquid-state NMR. The closely spaced resonant frequencies of 1H and 19F and the ubiquitous use of fluorine in modern plastics and electronic components present two major challenges in the design of a high-sensitivity, high-field 1H/19F probe. Through the selection of specific components, circuit design, and pulse sequence, we were able to build a probe that has low 19F background and excellent separation of 1H and 19F signals. We determine the principle components of the chemical shift anisotropy tensor of 5-fluoroindole-3-acetic acid (5FIAA) and 5-fluorotryptophan. We also solve the crystal structure of 5FIAA, determine the orientation dependence of the chemical shift of a single crystal of 5FIAA, and predict the 19F chemical shift based on the orientation of the fluorine in the crystal. The results show that this 1H/19F probe is suitable for solid-state NMR experiments with low amounts of biological molecules that have been labeled with 19F.

  3. Visualising crystal packing interactions in solid-state NMR: Concepts and applications (United States)

    Zilka, Miri; Sturniolo, Simone; Brown, Steven P.; Yates, Jonathan R.


    In this article, we introduce and apply a methodology, based on density functional theory and the gauge-including projector augmented wave approach, to explore the effects of packing interactions on solid-state nuclear magnetic resonance (NMR) parameters. A visual map derived from a so-termed "magnetic shielding contribution field" can be made of the contributions to the magnetic shielding of a specific site—partitioning the chemical shift to specific interactions. The relation to the established approaches of examining the molecule to crystal change in the chemical shift and the nuclear independent chemical shift is established. The results are applied to a large sample of 71 molecular crystals and three further specific examples from supermolecular chemistry and pharmaceuticals. This approach extends the NMR crystallography toolkit and provides insight into the development of both cluster based approaches to the predictions of chemical shifts and for empirical predictions of chemical shifts in solids.

  4. High resolution solid state 2D NMR analysis of biomass and biochar. (United States)

    Le Brech, Yann; Delmotte, Luc; Raya, Jesus; Brosse, Nicolas; Gadiou, Roger; Dufour, Anthony


    Solid state NMR methods are required to analyze biomass as a function of its chemical or biological treatment for biofuels, chemicals, or biochar production. The native polymers network in lignocellulosic biomass and other solid materials, such as coal, coke, or biochar, can hardly be analyzed by liquid state NMR due to their poor swelling ability without chemical modification. A (1)H-(13)C two-dimensional heteronuclear correlation (HETCOR) experiment with frequency-switched Lee-Goldburg (FSLG) irradiation is performed on a high field spectrometer (750 MHz). This method leads to previously unattained resolution for biomass and biochar and offers a unique ability to reveal their chemical composition. The formation of aromatic moieties from carbohydrates and lignin thermal conversion is clearly distinguished. This method can be applied to all other carbonaceous materials.

  5. Solid state NMR studies for a new carbonization process with high temperature preheating (United States)

    Saito, Koji; Hatakeyama, Moriaki; Komaki, Ikuo; Katoh, Kenji


    A new carbonization process with rapid preheating and coke discharging at medium temperature has been developed in Japan. The result of this process shows that even when no or slightly coking coal is by 50 wt% the coking property is improved and a coking coke with cold strength usable at blast furnace can be manufactured with the new carbonization process. The mechanism of the coking property improvement was examined by coal properties using mainly solid state NMR ( 1H CRAMPS and 13C SPE/MAS, CP/MAS) and NMR imaging (single point imaging, in-situ imaging). It has been clarified that the molecular structure of coal is relaxed by the rapid heating treatment and, in addition, there is a close relation between hydrogen bonding and relaxation of the molecular structure of coal.

  6. Solid-state NMR and EPR Spectroscopy of Mn2+ -Substituted ATP-Fueled Protein Engines. (United States)

    Wiegand, Thomas; Lacabanne, Denis; Keller, Katharina; Cadalbert, Riccardo; Lecoq, Lauriane; Yulikov, Maxim; Terradot, Laurent; Jeschke, Gunnar; Meier, Beat H; Böckmann, Anja


    Paramagnetic metal ions deliver structural information both in EPR and solid-state NMR experiments, offering a profitable synergetic approach to study bio-macromolecules. We demonstrate the spectral consequences of Mg2+ / Mn2+ substitution and the resulting information contents for two different ATP:Mg2+ -fueled protein engines, a DnaB helicase from Helicobacter pylori active in the bacterial replisome, and the ABC transporter BmrA, a bacterial efflux pump. We show that, while EPR spectra report on metal binding and provide information on the geometry of the metal centers in the proteins, paramagnetic relaxation enhancements identified in the NMR spectra can be used to localize residues at the binding site. Protein engines are ubiquitous and the methods described herein should be applicable in a broad context. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. A High Resolution Solid State NMR Approach for the Structural Studies of Bicelles (United States)

    Dvinskikh, Sergey; Dürr, Ulrich; Yamamoto, Kazutoshi; Ramamoorthy, Ayyalusamy


    Bicelles are increasingly being used as membrane mimicking systems in NMR experiments to investigate the structure of membrane proteins. In this study, we demonstrate the effectiveness of a 2D solid-state NMR approach that can be used to measure the structural constraints such as heteronuclear dipolar couplings between 1H, 13C and 31P nuclei in bicelles without the need for isotopic enrichment. This method does not require a high radio frequency power unlike the presently used rotating-frame separated-local-field (SLF) techniques like PISEMA. In addition, multiple dipolar couplings can be measured accurately and the presence of a strong dipolar coupling does not suppress the weak couplings. High resolution spectra obtained from magnetically aligned DMPC:DHPC bicelles even in the presence of peptides suggest that this approach will be useful in understanding lipid-protein interactions that play a vital role in shaping up the function of membrane proteins. PMID:16683791

  8. A high-resolution solid-state NMR approach for the structural studies of bicelles. (United States)

    Dvinskikh, Sergey; Dürr, Ulrich; Yamamoto, Kazutoshi; Ramamoorthy, Ayyalusamy


    Bicelles are increasingly being used as membrane mimicking systems in NMR experiments to investigate the structure of membrane proteins. In this study, we demonstrate the effectiveness of a 2D solid-state NMR approach that can be used to measure the structural constraints, such as heteronuclear dipolar couplings between 1H, 13C, and 31P nuclei, in bicelles without the need for isotopic enrichment. This method does not require a high radio frequency power unlike the presently used rotating-frame separated-local-field (SLF) techniques, such as PISEMA. In addition, multiple dipolar couplings can be measured accurately, and the presence of a strong dipolar coupling does not suppress the weak couplings. High-resolution spectra obtained from magnetically aligned DMPC:DHPC bicelles even in the presence of peptides suggest that this approach will be useful in understanding lipid-protein interactions that play a vital role in shaping up the function of membrane proteins.

  9. Peptidoglycan architecture of Gram-positive bacteria by solid-state NMR. (United States)

    Kim, Sung Joon; Chang, James; Singh, Manmilan


    Peptidoglycan is an essential component of cell wall in Gram-positive bacteria with unknown architecture. In this review, we summarize solid-state NMR approaches to address some of the unknowns in the Gram-positive bacteria peptidoglycan architecture: 1) peptidoglycan backbone conformation, 2) PG-lattice structure, 3) variations in the peptidoglycan architecture and composition, 4) the effects of peptidoglycan bridge-length on the peptidoglycan architecture in Fem mutants, 5) the orientation of glycan strands with respect to the membrane, and 6) the relationship between the peptidoglycan structure and the glycopeptide antibiotic mode of action. Solid-state NMR analyses of Staphylococcus aureus cell wall show that peptidoglycan chains are surprisingly ordered and densely packed. The peptidoglycan disaccharide backbone adopts 4-fold screw helical symmetry with the disaccharide unit periodicity of 40Å. Peptidoglycan lattice in the S. aureus cell wall is formed by cross-linked PG stems that have parallel orientations. The structural characterization of Fem-mutants of S. aureus with varying lengths of bridge structures suggests that the PG-bridge length is an important determining factor for the PG architecture. Copyright © 2014 Elsevier B.V. All rights reserved.

  10. β-Helical architecture of cytoskeletal bactofilin filaments revealed by solid-state NMR (United States)

    Vasa, Suresh; Lin, Lin; Shi, Chaowei; Habenstein, Birgit; Riedel, Dietmar; Kühn, Juliane; Thanbichler, Martin; Lange, Adam


    Bactofilins are a widespread class of bacterial filament-forming proteins, which serve as cytoskeletal scaffolds in various cellular pathways. They are characterized by a conserved architecture, featuring a central conserved domain (DUF583) that is flanked by variable terminal regions. Here, we present a detailed investigation of bactofilin filaments from Caulobacter crescentus by high-resolution solid-state NMR spectroscopy. De novo sequential resonance assignments were obtained for residues Ala39 to Phe137, spanning the conserved DUF583 domain. Analysis of the secondary chemical shifts shows that this core region adopts predominantly β-sheet secondary structure. Mutational studies of conserved hydrophobic residues located in the identified β-strand segments suggest that bactofilin folding and polymerization is mediated by an extensive and redundant network of hydrophobic interactions, consistent with the high intrinsic stability of bactofilin polymers. Transmission electron microscopy revealed a propensity of bactofilin to form filament bundles as well as sheet-like, 2D crystalline assemblies, which may represent the supramolecular arrangement of bactofilin in the native context. Based on the diffraction pattern of these 2D crystalline assemblies, scanning transmission electron microscopy measurements of the mass per length of BacA filaments, and the distribution of β-strand segments identified by solid-state NMR, we propose that the DUF583 domain adopts a β-helical architecture, in which 18 β-strand segments are arranged in six consecutive windings of a β-helix. PMID:25550503

  11. Peptidoglycan Architecture of Gram-positive Bacteria by Solid-State NMR (United States)

    Kim, Sung Joon; Chang, James; Singh, Manmilan


    Peptidoglycan is an essential component of cell wall in Gram-positive bacteria with unknown architecture. In this review, we summarize solid-state NMR approaches to address some of the unknowns in the Gram-positive bacteria peptidoglycan architecture: 1) peptidoglycan backbone conformation, 2) PG-lattice structure, 3) variations in the peptidoglycan architecture and composition, 4) the effects of peptidoglycan bridge-length on the peptidoglycan architecture in Fem mutants, 5) the orientation of glycan strands respect to the membrane, and 6) the relationship between the peptidoglycan structure and the glycopeptide antibiotic mode of action. Solid-state NMR analyses of S. aureus cell wall show that peptidoglycan chains are surprisingly ordered and densely packed. The peptidoglycan disaccharide backbone adopts 4-fold screw helical symmetry with the disaccharide unit periodicity of 40 Å. Peptidoglycan lattice in S. aureus cell wall is formed by cross-linked PG stems that have parallel orientations. The structural characterization of Fem-mutants of S. aureus with varying lengths of bridge structures suggests that the PG-bridge length is an important determining factor for the PG architecture. PMID:24915020

  12. Solid-state NMR studies of the prion protein H1 fragment. (United States)

    Heller, J.; Kolbert, A. C.; Larsen, R.; Ernst, M.; Bekker, T.; Baldwin, M.; Prusiner, S. B.; Pines, A.; Wemmer, D. E.


    Conformational changes in the prion protein (PrP) seem to be responsible for prion diseases. We have used conformation-dependent chemical-shift measurements and rotational-resonance distance measurements to analyze the conformation of solid-state peptides lacking long-range order, corresponding to a region of PrP designated H1. This region is predicted to undergo a transformation of secondary structure in generating the infectious form of the protein. Solid-state NMR spectra of specifically 13C-enriched samples of H1, residues 109-122 (MKHMAGAAAAGAVV) of Syrian hamster PrP, have been acquired under cross-polarization and magic-angle spinning conditions. Samples lyophilized from 50% acetonitrile/50% water show chemical shifts characteristic of a beta-sheet conformation in the region corresponding to residues 112-121, whereas samples lyophilized from hexafluoroisopropanol display shifts indicative of alpha-helical secondary structure in the region corresponding to residues 113-117. Complete conversion to the helical conformation was not observed and conversion from alpha-helix back to beta-sheet, as inferred from the solid-state NMR spectra, occurred when samples were exposed to water. Rotational-resonance experiments were performed on seven doubly 13C-labeled H1 samples dried from water. Measured distances suggest that the peptide is in an extended, possibly beta-strand, conformation. These results are consistent with the experimental observation that PrP can exist in different conformational states and with structural predictions based on biological data and theoretical modeling that suggest that H1 may play a key role in the conformational transition involved in the development of prion diseases. PMID:8844854

  13. A combination of novel solid-state NMR methods and related software to study molecular assemblies and biomolecules

    NARCIS (Netherlands)

    Gradmann, S.H.E.


    Solid-state Nuclear Magnetic Resonance (ssNMR) is a versatile spectroscopic method that can be applied to various samples relevant in life and material science and provides atomic insight into molecular structure, dynamics and assembly. The present thesis describes the diversity and utility of ssNMR

  14. Solid-state and unilateral NMR study of deterioration of a Dead Sea Scroll fragment. (United States)

    Masic, A; Chierotti, M R; Gobetto, R; Martra, G; Rabin, I; Coluccia, S


    Unilateral and solid-state nuclear magnetic resonance (NMR) analyses were performed on a parchment fragment of the Dead Sea Scroll (DSS). The analyzed sample belongs to the collection of non-inscribed and nontreated fragments of known archaeological provenance from the John Rylands University Library in Manchester. Therefore, it can be considered as original DSS material free from any contamination related to the post-discovery period. Considering the paramount significance of the DSS, noninvasive approaches and portable in situ nondestructive methods are of fundamental importance for the determination of composition, structure, and chemical-physical properties of the materials under study. NMR studies reveal low amounts of water content associated with very short proton relaxation times, T(1), indicating a high level of deterioration of collagen molecules within scroll fragments. In addition, (13)C cross-polarization magic-angle-spinning (CPMAS) NMR spectroscopy shows characteristic peaks of lipids whose presence we attribute to the production technology that did not involve liming. Extraction with chloroform led to the reduction of both lipid and protein signals in the (13)C CPMAS spectrum indicating probable involvement of lipids in parchment degradation processes. NMR absorption and relaxation measurements provide nondestructive, discriminative, and sensitive tools for studying the deterioration effects on the organization and properties of water and collagen within ancient manuscripts.

  15. Solid state synthesis of water-dispersible silicon nanoparticles from silica nanoparticles (United States)

    Kravitz, Keren; Kamyshny, Alexander; Gedanken, Aharon; Magdassi, Shlomo


    A solid state synthesis for obtaining nanocrystalline silicon was performed by high temperature reduction of commercial amorphous nanosilica with magnesium powder. The obtained silicon powder contains crystalline silicon phase with lattice spacings characteristic of diamond cubic structure (according to high resolution TEM), and an amorphous phase. In 29Si CP MAS NMR a broad multicomponent peak corresponding to silicon is located at -61.28 to -69.45 ppm, i.e. between the peaks characteristic of amorphous and crystalline Si. The powder has displayed red luminescence while excited under UV illumination, due to quantum confinement within the nanocrystals. The silicon nanopowder was successfully dispersed in water containing poly(vinyl alcohol) as a stabilizing agent. The obtained dispersion was also characterized by red photoluminescence with a band maximum at 710 nm, thus enabling future functional coating applications.

  16. Action of the multifunctional peptide BP100 on native biomembranes examined by solid-state NMR

    Energy Technology Data Exchange (ETDEWEB)

    Misiewicz, Julia [Karlsruhe Institute of Technology (KIT), Institute of Organic Chemistry (Germany); Afonin, Sergii; Grage, Stephan L.; Berg, Jonas van den; Strandberg, Erik; Wadhwani, Parvesh [Karlsruhe Institute of Technology (KIT), Institute of Biological Interfaces (IBG-2) (Germany); Ulrich, Anne S., E-mail: [Karlsruhe Institute of Technology (KIT), Institute of Organic Chemistry (Germany)


    Membrane composition is a key factor that regulates the destructive activity of antimicrobial peptides and the non-leaky permeation of cell penetrating peptides in vivo. Hence, the choice of model membrane is a crucial aspect in NMR studies and should reflect the biological situation as closely as possible. Here, we explore the structure and dynamics of the short multifunctional peptide BP100 using a multinuclear solid-state NMR approach. The membrane alignment and mobility of this 11 amino acid peptide was studied in various synthetic lipid bilayers with different net charge, fluidity, and thickness, as well as in native biomembranes harvested from prokaryotic and eukaryotic cells. {sup 19}F-NMR provided the high sensitivity and lack of natural abundance background that are necessary to observe a labelled peptide even in protoplast membranes from Micrococcus luteus and in erythrocyte ghosts. Six selectively {sup 19}F-labeled BP100 analogues gave remarkably similar spectra in all of the macroscopically oriented membrane systems, which were studied under quasi-native conditions of ambient temperature and full hydration. This similarity suggests that BP100 has the same surface-bound helical structure and high mobility in the different biomembranes and model membranes alike, independent of charge, thickness or cholesterol content of the system. {sup 31}P-NMR spectra of the phospholipid components did not indicate any bilayer perturbation, so the formation of toroidal wormholes or micellarization can be excluded as a mechanism of its antimicrobial or cell penetrating action. However, {sup 2}H-NMR analysis of the acyl chain order parameter profiles showed that BP100 leads to considerable membrane thinning and thereby local destabilization.

  17. A solid-state NMR method for solution of zeolite crystal structures. (United States)

    Brouwer, Darren H; Darton, Richard J; Morris, Russell E; Levitt, Malcolm H


    Since zeolites are notoriously difficult to prepare as large single crystals, structure determination usually relies on powder X-ray diffraction (XRD). However, structure solution (i.e., deriving an initial structural model) directly from powder XRD data is often very difficult due to the diffraction phase problem and the high degree of overlap between the individual reflections, particularly for materials with the structural complexity of most zeolites. Here, we report a method for structure determination of zeolite crystal structures that combines powder XRD and nuclear magnetic resonance (NMR) spectroscopy in which the crucial step of structure solution is achieved using solid-state (29)Si double-quantum dipolar recoupling NMR, which probes the distance-dependent dipolar interactions between naturally abundant (29)Si nuclei in the zeolite framework. For two purely siliceous zeolite blind test samples, we demonstrate that the NMR data can be combined with the unit cell parameters and space group to solve structural models that refine successfully against the powder XRD data.

  18. Structure and orientation of dynorphin bound to lipid bilayers by 13C solid-state NMR (United States)

    Uezono, Takiko; Toraya, Shuichi; Obata, Maki; Nishimura, Katsuyuki; Tuzi, Satoru; Saitô, Hazime; Naito, Akira


    Secondary structure and orientation of dynorphin bound to dimyristoylphosphatidylcholine (DMPC) bilayer were investigated by solid-state 13C NMR spectroscopy. For this purpose, 13C NMR spectra of the site-specifically 13C-labeled dynorphin were measured in the membrane-bound state under static, magic angle spinning (MAS), and slow MAS conditions. In the static experiment, magnetically oriented vesicle system (MOVS) induced by dynorphin was successfully used to investigate the orientation of dynorphin bound to the lipid bilayers. It was found that dynorphin adopts an α-helical structure in the N-terminus from Gly 2 to Leu 5 by analyses of the isotropic chemical shifts obtained from the MAS experiments. In contrast, it adopts disordered conformations from the center to the C-terminus and is located on the membrane surface. The static 13C NMR spectra indicated that MOVS-bound dynorphin was oriented to the magnetic field and rotated rapidly about the bilayer normal. Subsequently, we analyzed the 13C chemical shift tensors of carbonyl carbons in the peptide backbone by considering the rotational motion of the N-terminal α-helix. It was revealed that the N-terminal α-helix is inserted into the membrane with the tilt angle of 21° to the bilayer normal. This structure suggests a possibility that dynorphin interacts with the extracellular loop II of the κ-receptor through a helix-helix interaction.

  19. Solid state NMR investigation of a novel Li ion ceramic electrolyte. Li doped BPO sub 4

    CERN Document Server

    Dodd, A J


    Over the last decade lithium ion conducting batteries have emerged as the leading technology in battery materials. Their performance, however, is limited to applications below around 50 deg C by the liquid nature of the electrolytes used. In the quest for a solid state electrolyte for use in high temperature applications the nano-crystalline ceramic lithium doped boron phosphate material was developed. Solid state nuclear magnetic resonance (NMR) has been employed to investigate some of the fundamental properties of this material including ionic mobility, defect structure, sample purity and ionic distribution. The findings of this work show that when synthesised at a reaction temperature above 600 deg C the loss of boron from the structure results in the incorporation of vacancy sites about which the Li ions gather in small clusters. Multiple-pulse multiple-quantum spin counting techniques are employed in an effort to count the number of quadrupolar sup 7 Li nuclei interacting in a cluster though it is ultima...

  20. Polymorphs of Theophylline Characterized by DNP Enhanced Solid-State NMR. (United States)

    Pinon, Arthur C; Rossini, Aaron J; Widdifield, Cory M; Gajan, David; Emsley, Lyndon


    We show how dynamic nuclear polarization (DNP) enhanced solid-state NMR spectroscopy can be used to characterize polymorphs and solvates of organic solids. We applied DNP to three polymorphs and one hydrated form of the asthma drug molecule theophylline. For some forms of theophylline, sample grinding and impregnation with the radical-containing solution, which are necessary to prepare the samples for DNP, were found to induce polymorphic transitions or desolvation between some forms. We present protocols for sample preparation for solid-state magic-angle spinning (MAS) DNP experiments that avoid the polymorphic phase transitions in theophylline. These protocols include cryogrinding, grinding under inert atmosphere, and the appropriate choice of the impregnating liquid. By applying these procedures, we subsequently demonstrate that two-dimensional correlation experiments, such as (1)H-(13)C and (1)H-(15)N HETCOR or (13)C-(13)C INADEQUATE, can be obtained at natural isotopic abundance in reasonable times, thus enabling more advanced structural characterization of polymorphs.

  1. A solid state NMR investigation of char forming processes in polymer degradation

    CERN Document Server

    Dick, C M


    A detailed knowledge of the condensed phase chemistry occurring in polymers exposed to elevated temperatures is crucial to understanding the behaviour of polymers exposed to fire. This is particularly true when trying to reduce polymer flammability by means of promoting char-forming reactions. Until recently, however, structural information on highly crosslinked chars and their precursors has been difficult to obtain, and as a consequence many degradation workers have merely labelled degradation residues as 'intractable'. However, the application of solid state NMR techniques developed in our laboratories for the structural characterisation of coals has provided a considerable insight into the structure and chemistry of polymer chars formed under both oxidative and non-oxidative conditions. A series of polymers including poly(vinyl chloride), poly(vinyl acetate), polyurethanes, polychloropene, cis and trans polyisoprene have been studied. These polymers have been used to describe the application of quantitati...

  2. Solid-State NMR Comparison of Various Spiders’ Dragline Silk Fiber (United States)

    Creager, Melinda S.; Jenkins, Janelle E; Thagard-Yeaman, Leigh A.; Brooks, Amanda E.; Jones, Justin A.; Lewis, Randolph V.; Holland, Gregory P.; Yarger, Jeffery L.


    Major ampullate (dragline) spider silk is a coveted biopolymer due to its combination of strength and extensibility. The dragline silk of different spiders have distinct mechanical properties that can be qualitatively correlated to the protein sequence. This study uses amino acid analysis and carbon-13 solid-state NMR to compare the molecular composition, structure and dynamics of major ampullate dragline silk of four orb-web spider species (Nephila clavipes, Araneus gemmoides, Argiope aurantia and Argiope argentata) and one cobweb species (Latrodectus hesperus). The mobility of the protein backbone and amino acid side chains in water exposed silk fibers is shown to correlate to the proline content. This implies that regions of major ampullate spidroin 2 protein, which is the only dragline silk protein with any significant proline content, become significantly hydrated in dragline spider silk. PMID:20593757

  3. Folding of xylan onto cellulose fibrils in plant cell walls revealed by solid-state NMR (United States)

    Simmons, Thomas J.; Mortimer, Jenny C.; Bernardinelli, Oigres D.; Pöppler, Ann-Christin; Brown, Steven P.; Deazevedo, Eduardo R.; Dupree, Ray; Dupree, Paul


    Exploitation of plant lignocellulosic biomass is hampered by our ignorance of the molecular basis for its properties such as strength and digestibility. Xylan, the most prevalent non-cellulosic polysaccharide, binds to cellulose microfibrils. The nature of this interaction remains unclear, despite its importance. Here we show that the majority of xylan, which forms a threefold helical screw in solution, flattens into a twofold helical screw ribbon to bind intimately to cellulose microfibrils in the cell wall. 13C solid-state magic-angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy, supported by in silico predictions of chemical shifts, shows both two- and threefold screw xylan conformations are present in fresh Arabidopsis stems. The twofold screw xylan is spatially close to cellulose, and has similar rigidity to the cellulose microfibrils, but reverts to the threefold screw conformation in the cellulose-deficient irx3 mutant. The discovery that induced polysaccharide conformation underlies cell wall assembly provides new principles to understand biomass properties.

  4. Solid-state NMR study of ultrastable zeolite Y modified with orthophosphoric acid. (United States)

    Kolodziejski, W; Fornés, V; Corma, A


    29Si, 27Al and 31P solid-state NMR under magic-angle spinning was used for the study of ultrastable zeolite Y modified with H3PO4. The material is a potential candidate for a new generation of oil-cracking catalysts. Bloch decay and cross-polarization spectra were compared. It was found that amorphous aluminium phosphate is formed during the P-impregnation and the following activation, and that it occupies the zeolite surface and internal voids. For a high P-content under steaming conditions, aluminium phosphate is converted into a crystalline form. No evidence has been found for incorporation of P atoms into the zeolite framework.

  5. Characterization of the Vibrio cholerae extracellular matrix: a top-down solid-state NMR approach. (United States)

    Reichhardt, Courtney; Fong, Jiunn C N; Yildiz, Fitnat; Cegelski, Lynette


    Bacterial biofilms are communities of bacterial cells surrounded by a self-secreted extracellular matrix. Biofilm formation by Vibrio cholerae, the human pathogen responsible for cholera, contributes to its environmental survival and infectivity. Important genetic and molecular requirements have been identified for V. cholerae biofilm formation, yet a compositional accounting of these parts in the intact biofilm or extracellular matrix has not been described. As insoluble and non-crystalline assemblies, determinations of biofilm composition pose a challenge to conventional biochemical and biophysical analyses. The V. cholerae extracellular matrix composition is particularly complex with several proteins, complex polysaccharides, and other biomolecules having been identified as matrix parts. We developed a new top-down solid-state NMR approach to spectroscopically assign and quantify the carbon pools of the intact V. cholerae extracellular matrix using ¹³C CPMAS and ¹³C{(¹⁵N}, ¹⁵N{³¹P}, and ¹³C{³¹P}REDOR. General sugar, lipid, and amino acid pools were first profiled and then further annotated and quantified as specific carbon types, including carbonyls, amides, glycyl carbons, and anomerics. In addition, ¹⁵N profiling revealed a large amine pool relative to amide contributions, reflecting the prevalence of molecular modifications with free amine groups. Our top-down approach could be implemented immediately to examine the extracellular matrix from mutant strains that might alter polysaccharide production or lipid release beyond the cell surface; or to monitor changes that may accompany environmental variations and stressors such as altered nutrient composition, oxidative stress or antibiotics. More generally, our analysis has demonstrated that solid-state NMR is a valuable tool to characterize complex biofilm systems. Copyright © 2014. Published by Elsevier B.V.

  6. In situ solid-state NMR spectroscopy of electrochemical cells: batteries, supercapacitors, and fuel cells. (United States)

    Blanc, Frédéric; Leskes, Michal; Grey, Clare P


    Electrochemical cells, in the form of batteries (or supercapacitors) and fuel cells, are efficient devices for energy storage and conversion. These devices show considerable promise for use in portable and static devices to power electronics and various modes of transport and to produce and store electricity both locally and on the grid. For example, high power and energy density lithium-ion batteries are being developed for use in hybrid electric vehicles where they improve the efficiency of fuel use and help to reduce greenhouse gas emissions. To gain insight into the chemical reactions involving the multiple components (electrodes, electrolytes, interfaces) in the electrochemical cells and to determine how cells operate and how they fail, researchers ideally should employ techniques that allow real-time characterization of the behavior of the cells under operating conditions. This Account reviews the recent use of in situ solid-state NMR spectroscopy, a technique that probes local structure and dynamics, to study these devices. In situ NMR studies of lithium-ion batteries are performed on the entire battery, by using a coin cell design, a flat sealed plastic bag, or a cylindrical cell. The battery is placed inside the NMR coil, leads are connected to a potentiostat, and the NMR spectra are recorded as a function of state of charge. (7)Li is used for many of these experiments because of its high sensitivity, straightforward spectral interpretation, and relevance to these devices. For example, (7)Li spectroscopy was used to detect intermediates formed during electrochemical cycling such as LixC and LiySiz species in batteries with carbon and silicon anodes, respectively. It was also used to observe and quantify the formation and growth of metallic lithium microstructures, which can cause short circuits and battery failure. This approach can be utilized to identify conditions that promote dendrite formation and whether different electrolytes and additives can help

  7. SIMPSON: A general simulation program for solid-state NMR spectroscopy (United States)

    Bak, Mads; Rasmussen, Jimmy T.; Nielsen, Niels Chr.


    A computer program for fast and accurate numerical simulation of solid-state NMR experiments is described. The program is designed to emulate a NMR spectrometer by letting the user specify high-level NMR concepts such as spin systems, nuclear spin interactions, RF irradiation, free precession, phase cycling, coherence-order filtering, and implicit/explicit acquisition. These elements are implemented using the Tel scripting language to ensure a minimum of programming overhead and direct interpretation without the need for compilation, while maintaining the flexibility of a full-featured programming language. Basicly, there are no intrinsic limitations to the number of spins, types of interactions, sample conditions (static or spinning, powders, uniaxially oriented molecules, single crystals, or solutions), and the complexity or number of spectral dimensions for the pulse sequence. The applicability ranges from simple ID experiments to advanced multiple-pulse and multiple-dimensional experiments, series of simulations, parameter scans, complex data manipulation/visualization, and iterative fitting of simulated to experimental spectra. A major effort has been devoted to optimizing the computation speed using state-of-the-art algorithms for the time-consuming parts of the calculations implemented in the core of the program using the C programming language. Modification and maintenance of the program are facilitated by releasing the program as open source software (General Public License) currently at The general features of the program are demonstrated by numerical simulations of various aspects for REDOR, rotational resonance, DRAMA, DRAWS, HORROR, C7, TEDOR, POST-C7, CW decoupling, TPPM, F-SLG, SLF, SEMA-CP, PISEMA, RFDR, QCPMG-MAS, and MQ-MAS experiments.

  8. Characterization of Silicon Nanocrystal Surfaces by Multidimensional Solid-State NMR Spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Hanrahan, Michael P. [Department; US DOE Ames Laboratory, Ames, Iowa 50011, United States; Fought, Ellie L. [Department; Windus, Theresa L. [Department; Wheeler, Lance M. [Chemistry; Anderson, Nicholas C. [Chemistry; Neale, Nathan R. [Chemistry; Rossini, Aaron J. [Department; US DOE Ames Laboratory, Ames, Iowa 50011, United States


    The chemical and photophysical properties of silicon nanocrystals (Si NCs) are strongly dependent on the chemical composition and structure of their surfaces. Here we use fast magic angle spinning (MAS) and proton detection to enable the rapid acquisition of dipolar and scalar 2D 1H-29Si heteronuclear correlation (HETCOR) solid-state NMR spectra and reveal a molecular picture of hydride-terminated and alkyl-functionalized surfaces of Si NCs produced in a nonthermal plasma. 2D 1H-29Si HETCOR and dipolar 2D 1H-1H multiple-quantum correlation spectra illustrate that resonances from surface mono-, di-, and trihydride groups cannot be resolved, contrary to previous literature assignments. Instead the 2D NMR spectra illustrate that there is large distribution of 1H and 29Si chemical shifts for the surface hydride species in both the as-synthesized and functionalized Si NCs. However, proton-detected 1H-29Si refocused INEPT experiments can be used to unambiguously differentiate NMR signals from the different surface hydrides. Varying the 29Si evolution time in refocused INEPT experiments and fitting the oscillation of the NMR signals allows for the relative populations of the different surface hydrides to be estimated. This analysis confirms that monohydride species are the predominant surface species on the as-synthesized Si NCs. A reduction in the populations of the di- and trihydrides is observed upon functionalization with alkyl groups, consistent with our previous hypothesis that the trihydride, or silyl (*SiH3), group is primarily responsible for initiating surface functionalization reactions. Density functional theory (DFT) calculations were used to obtain quantum chemical structural models of the Si NC surface and reproduce the observed 1H and 29Si chemical shifts. The approaches outlined here will be useful to obtain a more detailed picture of surface structures for Si NCs and other hydride-passivated nanomaterials.

  9. 59 Solid State Synthesis, Characterisation and Biological Activity of ...

    African Journals Online (AJOL)



    Nov 21, 2014 ... synthesized complexes are non-electrolytes. Keywords: Hydrogen bond network, Mechanochemistry, Coordination ploymers. INTRODUCTION. Solid-state reactivity of molecular crystals has an old history but it was initially restricted to photochemical reactions and acid–base reactions. (Kaupp, 1996).

  10. Solid-state 17O NMR study of benzoic acid adsorption on metal oxide surfaces. (United States)

    Hagaman, Edward W; Chen, Banghao; Jiao, Jian; Parsons, William


    Solid-state (17)O NMR spectra of (17)O-labeled benzoic and anisic acids are reported and benzoic acid is used to probe the surface of metal oxides. Complexes formed when benzoic acid is dry mixed with mesoporous silica, and nonporous titania and alumina are characterized. Chemical reactions with silica are not observed. The nature of benzoic acid on silica is a function of the water content of the oxide. The acid disperses in the pores of the silica if the silica is in equilibrium with ambient laboratory humidity. The acid displays high mobility as evidenced by a liquid-like, Lorentzian resonance. Excess benzoic acid remains as the crystalline hydrogen-bonded dimer. Benzoic acid reacts with titania and alumina surfaces in equilibrium with laboratory air to form the corresponding titanium and aluminum benzoates. In both materials the oxygen of the (17)O-labeled acid is bound to the metal, showing the reaction proceeds by bond formation between oxygen deficient metal sites and the oxygen of the carboxylic acid. (27)Al MAS NMR confirms this mechanism for the reaction on alumina. Dry mixing of benzoic acid with alumina rapidly quenches pentacoordinate aluminum sites, excellent evidence that these sites are confined to the surface of the alumina particles. Copyright © 2011 Elsevier Inc. All rights reserved.

  11. Dynamic membrane interactions of antibacterial and antifungal biomolecules, and amyloid peptides, revealed by solid-state NMR spectroscopy. (United States)

    Naito, Akira; Matsumori, Nobuaki; Ramamoorthy, Ayyalusamy


    A variety of biomolecules acting on the cell membrane folds into a biologically active structure in the membrane environment. It is, therefore, important to determine the structures and dynamics of such biomolecules in a membrane environment. While several biophysical techniques are used to obtain low-resolution information, solid-state NMR spectroscopy is one of the most powerful means for determining the structure and dynamics of membrane bound biomolecules such as antibacterial biomolecules and amyloidogenic proteins; unlike X-ray crystallography and solution NMR spectroscopy, applications of solid-state NMR spectroscopy are not limited by non-crystalline, non-soluble nature or molecular size of membrane-associated biomolecules. This review article focuses on the applications of solid-state NMR techniques to study a few selected antibacterial and amyloid peptides. Solid-state NMR studies revealing the membrane inserted bent α-helical structure associated with the hemolytic activity of bee venom melittin and the chemical shift oscillation analysis used to determine the transmembrane structure (with α-helix and 310-helix in the N- and C-termini, respectively) of antibiotic peptide alamethicin are discussed in detail. Oligomerization of an amyloidogenic islet amyloid polypeptide (IAPP, or also known as amylin) resulting from its aggregation in a membrane environment, molecular interactions of the antifungal natural product amphotericin B with ergosterol in lipid bilayers, and the mechanism of lipid raft formation by sphingomyelin studied using solid state NMR methods are also discussed in this review article. This article is part of a Special Issue entitled "Biophysical Exploration of Dynamical Ordering of Biomolecular Systems" edited by Dr. Koichi Kato. Copyright © 2017 Elsevier B.V. All rights reserved.

  12. Perspectives for sensitivity enhancement in proton-detected solid-state NMR of highly deuterated proteins by preserving water magnetization

    Energy Technology Data Exchange (ETDEWEB)

    Chevelkov, Veniamin, E-mail:; Xiang, ShengQi; Giller, Karin; Becker, Stefan; Lange, Adam [Max-Planck-Institut für biophysikalische Chemie (MPI-bpc) (Germany); Reif, Bernd [Technische Universität München (TUM), Munich Center for Integrated Protein Science (CIPS-M), Department Chemie (Germany)


    In this work, we show how the water flip-back approach that is widely employed in solution-state NMR can be adapted to proton-detected MAS solid-state NMR of highly deuterated proteins. The scheme allows to enhance the sensitivity of the experiment by decreasing the recovery time of the proton longitudinal magnetization. The method relies on polarization transfer from non-saturated water to the protein during the inter-scan delay.

  13. Applications of solid-state Nuclear Magnetic Resonance (NMR) in studies of Portland cements-based materials

    DEFF Research Database (Denmark)

    Skibsted, Jørgen; Andersen, Morten Daugaard; Jakobsen, Hans Jørgen


    Solid-state NMR spectroscopy represents an important research tool in the characterization of a range of structural properties for cement-based materials. Different approaches of the technique can be used to obtain information on hydration kinetics, mobile and bound water, porosity, and local...

  14. Solid-state NMR spectroscopy of the quadrupolar halogens: chlorine-35/37, bromine-79/81, and iodine-127. (United States)

    Bryce, David L; Sward, Gregory D


    A thorough review of 35/37Cl, 79/81Br, and 127I solid-state nuclear magnetic resonance (SSNMR) data is presented. Isotropic chemical shifts (CS), quadrupolar coupling constants, and other available information on the magnitude and orientation of the CS and electric field gradient (EFG) tensors for chlorine, bromine, and iodine in diverse chemical compounds is tabulated on the basis of over 200 references. Our coverage is through July 2005. Special emphasis is placed on the information available from the study of powdered diamagnetic solids in high magnetic fields. Our survey indicates a recent notable increase in the number of applications of solid-state quadrupolar halogen NMR, particularly 35Cl NMR, as high magnetic fields have become more widely available to solid-state NMR spectroscopists. We conclude with an assessment of possible future directions for research involving 35/37Cl, 79/81Br, and 127I solid-state NMR spectroscopy. 2006 John Wiley & Sons, Ltd.

  15. Interaction between dry starch and plasticisers glycerol or ethylene glycol, measured by differential scanning calorimetry and solid state NMR spectroscopy

    NARCIS (Netherlands)

    Smits, A.L.M.; Kruiskamp, P.H.; Soest, van J.J.G.; Vliegenthart, J.F.G.


    The interaction of crystalline amylose and of crystalline and amorphous amylopectin with the plasticisers glycerol or ethylene glycol in the absence of water was studied, by using differential scanning calorimetry (DSC) and solid state nuclear magnetic resonance (NMR) spectroscopy. Upon heating

  16. Epoxy networks reinforced with polyhedral oligomeric silsesquioxanes: structure and segmental dynamics as studied by solid-state NMR

    Czech Academy of Sciences Publication Activity Database

    Brus, Jiří; Urbanová, Martina; Strachota, Adam


    Roč. 41, č. 2 (2008), s. 372-386 ISSN 0024-9297 R&D Projects: GA AV ČR IAA400500602 Institutional research plan: CEZ:AV0Z40500505 Keywords : solid-state NMR * polymer networks * polysilsequioxanes Subject RIV: CD - Macromolecular Chemistry Impact factor: 4.407, year: 2008

  17. Crystal structure and tautomerism of Pigment Yellow 138 determined by X-ray powder diffraction and solid-state NMR

    DEFF Research Database (Denmark)

    Gumbert, Silke D.; Körbitzer, Meike; Alig, Edith


    The crystal structure of C.I. Pigment Yellow 138 was determined from X-ray powder diffraction data using real-space methods with subsequent Rietveld refinements. The tautomeric state was investigated by solid-state 1D and 2D multinuclear NMR experiments. In the crystals, the compound exhibits...... is not a packing effect, but caused by intramolecular steric hindrance....

  18. Interaction of epothilone B (patupilone) with microtubules as detected by two-dimensional solid-state NMR spectroscopy

    NARCIS (Netherlands)

    Kumar, A.; Heise, H.; Blommers, M. J. J.; Krastel, P.; Schmitt, E.; Petersen, F.; Jeganathan, S.; Mandelkow, E. -M; Carlomagno, T.; Griesinger, C.; Baldus, M.


    Solid evidence: Induction of the polymerization of β-tubulin dimers into microtubules by epothilones, such as patupilone, by an as yet unknown mechanism leads to the apoptosis of cancer cells. Solid-state NMR spectroscopy of patupilone bound to microtubules has now enabled the identification of

  19. Application of solid state NMR for the study of surface bound species and fossil fuels (United States)

    Althaus, Stacey

    Recent advances in solid state NMR have been utilized to study a variety of systems. These advancements have allowed for the acquisition of sequences previously only available for solution state detection. The protocol for the measurement of coals and other carbonaceous materials was updated to incorporate the recent advancements in fast magic angle spinning (MAS) and high magnetic fields. Argonne Premium Coals were used to test the sensitivity and resolution of the experiments preformed at high field and fast MAS. The higher field spectra were shown to be slightly less sensitive than the traditional lower field spectra, however, the new high field fast MAS spectra had better resolution. This increased resolution allowed for the separation of a variety of different functional groups, thereby allowing the composition of the coal to be determined. The use of 1 H detection allowed for 2D spectra of coals for the first time. These spectra could be filtered to examine either through-space or through-bond correlations. Indirect detection via 1 H was also pivotal in the detection of natural abundance 15 N spectra. Through-space and through-bond 2D spectra of natural abundance bulk species are shown with a sensitivity increase of 15 fold over traditional detection. This sensitivity enhancement allowed for the detection of natural abundance 15 N surface bound species in 2D, something that could not be acquired via traditional methods. The increased efficiency of the through-space magnetization transfer, Cross polarization, at fast MAS compared to the slower MAS rates is shown. The through-bond magnetization transfer via INEPT was examined and the effect of J-coupling is confirmed. Solid State NMR can be utilized to help improve catalytic interactions. Solid state NMR was used to examine the aldol condensation between p-nitrobenzaldehyde and acetone. The formation of a stable intermediate with p-nitrobenzaldehyde was found on the primary functionalized amine mesoporous

  20. Synthesis of Pyridine– and Pyrazine–BF 3 Complexes and Their Characterization in Solution and Solid State

    Energy Technology Data Exchange (ETDEWEB)

    Chénard, Etienne; Sutrisno, Andre; Zhu, Lingyang; Assary, Rajeev S.; Kowalski, Jeffrey A.; Barton, John L.; Bertke, Jeffery A.; Gray, Danielle L.; Brushett, Fikile R.; Curtiss, Larry A.; Moore, Jeffrey S.


    Following the discovery of the redox-active 1,4- bis-BF3-quinoxaline complex, we undertook a structure- activity study with the objective to understand the active nature of the quinoxaline complex. Through systematic synthesis and characterization, we have compared complexes prepared from pyridine and pyrazine derivatives, as heterocyclic core analogues. This paper reports the structural requirements that give rise to the electrochemical features of the 1,4-bis-BF3-quinoxaline adduct. Using solution and solidstate NMR spectroscopy, the role of aromatic ring fusion and nitrogen incorporation in bonding and electronics was elucidated. We establish the boron atom location and its interaction with its environment from 1D and 2D solution NMR, X-ray diffraction analysis, and 11B solid-state NMR experiments. Crystallographic analysis of single crystals helped to correlate the boron geometry with 11B quadrupolar coupling constant (CQ) and asymmetry parameter (ηQ), extracted from 11B solid-state NMR spectra. Additionally, computations based on density functional theory were performed to predict electrochemical behavior of the BF3-heteroaromatic complexes. We then experimentally measured electrochemical potential using cyclic voltammetry and found that the redox potentials and CQ values are similarly affected by electronic changes in the complexes.

  1. An explanation for the high stability of polycarboxythiophenes in photovoltaic devices—A solid-state NMR dipolar recoupling study

    DEFF Research Database (Denmark)

    Bierring, M.; Nielsen, J.S.; Siu, Ana


    acid carbon atoms were measured by C-13 solid-state magic-angle-spinning (MAS) NMR using symmetry-based double-quantum (2Q) dipolar recoupling. This revealed the presence of C-13-C-13 distances of 3.85 angstrom, which correspond to the C-C distance in hydrogen-bonded carboxylic acid dimers. In spite...... of the presence of carboxylic groups in the polymer as demonstrated by C-13 CP/MAS NMR and IR spectroscopy, the absence of carboxylic protons in solid state H-1 NMR spectra indicate that they are mobile. We link the extraordinary stability of this system to the rigid nature, cross-linking through a hydrogen...

  2. Molecular simulations and solid-state NMR investigate dynamical structure in rhodopsin activation. (United States)

    Mertz, Blake; Struts, Andrey V; Feller, Scott E; Brown, Michael F


    Rhodopsin has served as the primary model for studying G protein-coupled receptors (GPCRs)-the largest group in the human genome, and consequently a primary target for pharmaceutical development. Understanding the functions and activation mechanisms of GPCRs has proven to be extraordinarily difficult, as they are part of a complex signaling cascade and reside within the cell membrane. Although X-ray crystallography has recently solved several GPCR structures that may resemble the activated conformation, the dynamics and mechanism of rhodopsin activation continue to remain elusive. Notably solid-state ((2))H NMR spectroscopy provides key information pertinent to how local dynamics of the retinal ligand change during rhodopsin activation. When combined with molecular mechanics simulations of proteolipid membranes, a new paradigm for the rhodopsin activation process emerges. Experiment and simulation both suggest that retinal isomerization initiates the rhodopsin photocascade to yield not a single activated structure, but rather an ensemble of activated conformational states. This article is part of a Special Issue entitled: Membrane protein structure and function. Copyright © 2011. Published by Elsevier B.V.

  3. Transient NOE enhancement in solid-state MAS NMR of mobile systems. (United States)

    Cui, Jiangyu; Li, Jun; Peng, Xinhua; Fu, Riqiang


    It has been known that the heteronuclear cross-relaxation affects the dilute S spin magnetization along the longitudinal direction, causing an overshoot phenomenon for those mobile systems in spin-lattice relaxation rate measurements. Here, we analyze the Solomon equations for an I-S system and derive the transient cross relaxation effect as to when an overshoot phenomenon would take place and what the maximum enhancement could be at the time of the overshoot. In order to utilize such a transient nuclear Overhauser effect (NOE), we first time apply it to dynamic solid samples by inverting the (1)H magnetization prior to the excitation of the S spin. It is found that the overshoot depends on the ratio of the I and S spin-lattice relaxation rates, i.e. RSS/RII. When RSS/RII≫1, the maximum enhancement factor for transient NOE could be larger than that obtained in steady-state NOE experiments. Furthermore, transient NOE appears to be more efficient in terms of sensitivity enhancement of dilute spins in solid-state NMR of mobile systems than the traditional cross polarization scheme whose efficiency is greatly compromised by molecular mobility. A sample of natural abundance l-isoleucine amino acid, in which the spin-lattice relaxation rates for the four methyl carbons are different, has been used to demonstrate sensitivity enhancement factors under various experimental schemes. Copyright © 2017 Elsevier Inc. All rights reserved.

  4. Detection of hydroxyl ions in bone mineral by solid-state NMR spectroscopy. (United States)

    Cho, Gyunggoo; Wu, Yaotang; Ackerman, Jerome L


    Previous measurements of the hydroxyl (OH-) ion content of the calcium phosphate crystals of bone mineral have indicated a substantial depletion or near-absence of OH-, despite its presumed status as a constituent of the hydroxyapatite lattice. Analytical methods for determining bone crystal OH- content have depended on procedures or assumptions that may have biased the results, such as chemical pretreatment to eliminate interference from the organic matrix. We demonstrate a two-dimensional solid-state nuclear magnetic resonance (NMR) spectroscopy technique that detects the proton spectrum of bone crystals while suppressing the interfering matrix signals, eliminating the need for specimen pretreatment other than cryogenic grinding. Results on fresh-frozen and ground whole bone of several mammalian species show that the bone crystal OH- is readily detectable; a rough estimate yields an OH- content of human cortical bone of about 20% of the amount expected in stoichiometric hydroxyapatite. This finding sheds light on the biochemical processes underlying normal and abnormal bone mineral metabolism.

  5. Studying assembly of the BAM complex in native membranes by cellular solid-state NMR spectroscopy. (United States)

    Pinto, Cecilia; Mance, Deni; Julien, Manon; Daniels, Mark; Weingarth, Markus; Baldus, Marc


    Significant progress has been made in obtaining structural insight into the assembly of the β-barrel assembly machinery complex (BAM). These crystallography and electron microscopy studies used detergent as a membrane mimetic and revealed structural variations in the central domain, BamA, as well as in the lipoprotein BamC. We have used cellular solid-state NMR spectroscopy to examine the entire BamABCDE complex in native outer membranes and obtained data on the BamCDE subcomplex in outer membranes, in addition to synthetic bilayers. To reduce spectral crowding, we utilized proton-detected experiments and employed amino-acid specific isotope-labelling in (13C, 13C) correlation experiments. Taken together, the results provide insight into the overall fold and assembly of the BAM complex in native membranes, in particular regarding the structural flexibility of BamC in the absence of the core unit BamA. Copyright © 2017 Elsevier Inc. All rights reserved.

  6. Solid state synthesis and structural characterization of zinc titanates

    Energy Technology Data Exchange (ETDEWEB)

    Ayed, Sarra, E-mail: [Laboratory of Composite Ceramic and Polymer Materials, Scientific Faculty of Sfax (Tunisia); Abdelkefi, Helmi; Khemakhem, Hamadi [Laboratory of Ferroelectric Materials, Scientific Faculty of Sfax (Tunisia); Matoussi, Adel [Laboratory of Composite Ceramic and Polymer Materials, Scientific Faculty of Sfax (Tunisia)


    Zinc titanate composite materials were synthesized via solid state sintering process using high-purity metal oxide powders (purity ∼99.99%). The titanium incorporation into ZnO matrix was investigated by X-ray diffraction which revealed the coexistence of spinel Zn{sub 2}TiO{sub 4} and hexagonal ZnTiO{sub 3} with the ZnO wurtzite structures. No reflection peaks of rutile TiO{sub 2} phase were detected. The IR spectroscopy and Raman scattering spectroscopy were used to characterize the structural and chemical properties of the ZnO/TiO{sub 2} composites. The IR bands and vibrational modes of all crystalline phases were detected. The effect of TiO{sub 2} doping rates (x = 3, 5 and 7 wt%) on bands shifting, Raman intensity and structural quality was discussed. - Highlights: • Zinc titanates materials were synthesized via solid state sintering process. • XRD measurements reveal the formation of Zn{sub 2}TiO{sub 4}, hexagonal ZnTiO{sub 3} and ZnO phases. • IR analysis provokes the presence of Ti−O stretching vibration bands. • Raman study provokes the appearance of new zinc titanates vibrational peaks. • The TiO{sub 2} effect into ZnO is sensed by the shift and intensity changes of peaks.

  7. Solid-state NMR enhanced by dynamic nuclear polarization as a novel tool for ribosome structural biology

    Energy Technology Data Exchange (ETDEWEB)

    Gelis, Ioannis [University of South Florida, Department of Chemistry (United States); Vitzthum, Veronika [Ecole Polytechnique Federale de Lausanne, Institut des Sciences et Ingenierie Chimiques (Switzerland); Dhimole, Neha [Goethe University Frankfurt, Buchmann Institute for Molecular Life Sciences, Institute of Organic Chemistry and Chemical Biology (Germany); Caporini, Marc A. [Ecole Polytechnique Federale de Lausanne, Institut des Sciences et Ingenierie Chimiques (Switzerland); Schedlbauer, Andreas [Goethe University Frankfurt, Buchmann Institute for Molecular Life Sciences, Institute of Organic Chemistry and Chemical Biology (Germany); Carnevale, Diego [Ecole Polytechnique Federale de Lausanne, Institut des Sciences et Ingenierie Chimiques (Switzerland); Connell, Sean R.; Fucini, Paola, E-mail: [Goethe University Frankfurt, Buchmann Institute for Molecular Life Sciences, Institute of Organic Chemistry and Chemical Biology (Germany); Bodenhausen, Geoffrey, E-mail: [Ecole Polytechnique Federale de Lausanne, Institut des Sciences et Ingenierie Chimiques (Switzerland)


    The impact of Nuclear Magnetic Resonance (NMR) on studies of large macromolecular complexes hinges on improvements in sensitivity and resolution. Dynamic nuclear polarization (DNP) in the solid state can offer improved sensitivity, provided sample preparation is optimized to preserve spectral resolution. For a few nanomoles of intact ribosomes and an 800 kDa ribosomal complex we demonstrate that the combination of DNP and magic-angle spinning NMR (MAS-NMR) allows one to overcome current sensitivity limitations so that homo- and heteronuclear {sup 13}C and {sup 15}N NMR correlation spectra can be recorded. Ribosome particles, directly pelleted and frozen into an NMR rotor, yield DNP signal enhancements on the order of {approx}25-fold and spectra that exhibit narrow linewidths, suitable for obtaining site-specific information. We anticipate that the same approach is applicable to other high molecular weight complexes.

  8. Melem (2,5,8-triamino-tri-s-triazine), an important intermediate during condensation of melamine rings to graphitic carbon nitride: synthesis, structure determination by X-ray powder diffractometry, solid-state NMR, and theoretical studies. (United States)

    Jürgens, Barbara; Irran, Elisabeth; Senker, Jürgen; Kroll, Peter; Müller, Helen; Schnick, Wolfgang


    Single-phase melem (2,5,8-triamino-tri-s-triazine) C(6)N(7)(NH(2))(3) was obtained as a crystalline powder by thermal treatment of different less condensed C-N-H compounds (e.g., melamine C(3)N(3)(NH(2))(3), dicyandiamide H(4)C(2)N(4), ammonium dicyanamide NH(4)[N(CN)(2)], or cyanamide H(2)CN(2), respectively) at temperatures up to 450 degrees C in sealed glass ampules. The crystal structure was determined ab initio by X-ray powder diffractometry (Cu K alpha(1): P2(1)/c (No. 14), a = 739.92(1) pm, b = 865.28(3) pm, c = 1338.16(4) pm, beta = 99.912(2) degrees, and Z = 4). In the solid, melem consists of nearly planar C(6)N(7)(NH(2))(3) molecules which are arranged into parallel layers with an interplanar distance of 327 pm. Detailed (13)C and (15)N MAS NMR investigations were performed. The presence of the triamino form instead of other possible tautomers was confirmed by a CPPI (cross-polarization combined with polarization inversion) experiment. Furthermore, the compound was characterized using mass spectrometry, vibrational (IR, Raman), and photoluminescence spectroscopy. The structural and vibrational properties of molecular melem were theoretically studied on both the B3LYP and the MP2 level. A structural optimization in the extended state was performed employing density functional methods utilizing LDA and GGA. A good agreement was found between the observed and calculated structural parameters and also for the vibrational frequencies of melem. According to temperature-dependent X-ray powder diffractometry investigations above 560 degrees C, melem transforms into a graphite-like C-N material.

  9. 13C solid-state NMR chemical shift anisotropy analysis of the anomeric carbon in carbohydrates. (United States)

    Chen, Ying-Ying; Luo, Shun-Yuan; Hung, Shang-Cheng; Chan, Sunney I; Tzou, Der-Lii M


    (13)C NMR solid-state structural analysis of the anomeric center in carbohydrates was performed on six monosaccharides: glucose (Glc), mannose (Man), galactose (Gal), galactosamine hydrochloride (GalN), glucosamine hydrochloride (GlcN), and N-acetyl-glucosamine (GlcNAc). In the 1D (13)C cross-polarization/magic-angle spinning (CP/MAS) spectrum, the anomeric center C-1 of these carbohydrates revealed two well resolved resonances shifted by 3-5ppm, which were readily assigned to the anomeric alpha and beta forms. From this experiment, we also extracted the (13)C chemical shift anisotropy (CSA) tensor elements of the two forms from their spinning sideband intensities, respectively. It was found out that the chemical shift tensor for the alpha anomer was more axially symmetrical than that of the beta form. A strong linear correlation was obtained when the ratio of the axial asymmetry of the (13)C chemical shift tensors of the two anomeric forms was plotted in a semilogarithmic plot against the relative population of the two anomers. Finally, we applied REDOR spectroscopy to discern whether or not there were any differences in the sugar ring conformation between the anomers. Identical two-bond distances of 2.57A (2.48A) were deduced for both the alpha and beta forms in GlcNAc (GlcN), suggesting that the two anomers have essentially identical sugar ring scaffolds in these sugars. In light of these REDOR distance measurements and the strong correlation observed between the ratio of the axial asymmetry parameters of the (13)C chemical shift tensors and the relative population between the two anomeric forms, we concluded that the anomeric effect arises principally from interaction of the electron charge clouds between the C-1-O-5 and the C-1-O-1 bonds in these monosaccharides.

  10. A DNP-supported solid-state NMR study of carbon species in fluid catalytic cracking catalysts. (United States)

    Mance, Deni; van der Zwan, Johan; Velthoen, Marjolein E Z; Meirer, Florian; Weckhuysen, Bert M; Baldus, Marc; Vogt, Eelco T C


    A combination of solid-state NMR techniques supported by EPR and SEM-EDX experiments was used to localize different carbon species (coke) in commercial fluid catalytic cracking catalysts. Aliphatic coke species formed during the catalytic process and aromatic coke species deposited directly from the feedstock respond differently to dynamic nuclear polarization signal enhancement in integral and crushed FCC particles, indicating that aromatic species are mostly concentrated on the outside of the catalyst particles, whereas aliphatic species are also located on the inside of the FCC particles. The comparison of solid-state NMR data with and without the DNP radical at low and ambient temperature suggests the proximity between aromatic carbon deposits and metals (mostly iron) on the catalyst surface. These findings potentially indicate that coke and iron deposit together, or that iron has a role in the formation of aromatic coke.

  11. Highly efficient F-19 heteronuclear decoupling in solid-state NMR spectroscopy using supercycled refocused-CW irradiation

    DEFF Research Database (Denmark)

    Equbal, Asif; Basse, Kristoffer; Nielsen, Niels Christian


    We present heteronuclear F-19 refocused CW (rCW) decoupling pulse sequences for solid-state magic-angle- spinning NMR applications. The decoupling sequences have been designed specifically to ensure suppression of the pertinent C-13-F-19 dipolar coupling interactions while simultaneously suppress......We present heteronuclear F-19 refocused CW (rCW) decoupling pulse sequences for solid-state magic-angle- spinning NMR applications. The decoupling sequences have been designed specifically to ensure suppression of the pertinent C-13-F-19 dipolar coupling interactions while simultaneously...... of which clearly render the new rCW schemes the methods of choice for 19F decoupling in rigid, fluorinated compounds - which is further supported by a Floquet-based theoretical analysis....

  12. Preparation of Uniformly 13C,15N-Labeled Recombinant Human Amylin for Solid-State NMR Investigation

    DEFF Research Database (Denmark)

    Kosicka, Iga; Kristensen, Torsten; Bjerring, Morten


    A number of diseases are caused by the formation of amyloid fibrils. Detailed understanding of structural features of amyloid fibers is of great importance for our understanding of disease progression and design of agents for diagnostics or potential prevention of protein aggregation. In lack of ...... and electron microscopy, show toxicity towards human cells, and demonstrate that produced material may form the basis for structure determination using solid-state NMR.......A number of diseases are caused by the formation of amyloid fibrils. Detailed understanding of structural features of amyloid fibers is of great importance for our understanding of disease progression and design of agents for diagnostics or potential prevention of protein aggregation. In lack of 3D...... crystal ordering, solid-state NMR forms the most suited method to determine the structures of the fibrils with atomic resolution. To exploit this potential, large amounts of isotopic-labeled protein need to be obtained through recombinant protein expression. However, expression and purification...

  13. The Surface of Nanoparticle Silicon as Studied by Solid-State NMR

    Directory of Open Access Journals (Sweden)

    Gary E. Maciel


    Full Text Available The surface structure and adjacent interior of commercially available silicon nanopowder (np-Si was studied using multinuclear, solid-state NMR spectroscopy. The results are consistent with an overall picture in which the bulk of the np-Si interior consists of highly ordered (“crystalline” silicon atoms, each bound tetrahedrally to four other silicon atoms. From a combination of 1H, 29Si and 2H magic-angle-spinning (MAS NMR results and quantum mechanical 29Si chemical shift calculations, silicon atoms on the surface of “as-received” np-Si were found to exist in a variety of chemical structures, with apparent populations in the order (a (Si–O–3Si–H > (b (Si–O–3SiOH > (c (HO–nSi(Sim(–OSi4−m−n ≈ (d (Si–O–2Si(HOH > (e (Si–O–2Si(–OH2 > (f (Si–O–4Si, where Si stands for a surface silicon atom and Si represents another silicon atom that is attached to Si by either a Si–Si bond or a Si–O–Si linkage. The relative populations of each of these structures can be modified by chemical treatment, including with O2 gas at elevated temperature. A deliberately oxidized sample displays an increased population of (Si–O–3Si–H, as well as (Si–O–3SiOH sites. Considerable heterogeneity of some surface structures was observed. A combination of 1H and 2H MAS experiments provide evidence for a substantial population of silanol (Si–OH moieties, some of which are not readily H-exchangeable, along with the dominant Si–H sites, on the surface of “as-received” np-Si; the silanol moieties are enhanced by deliberate oxidation. An extension of the DEPTH background suppression method is also demonstrated that permits measurement of the T2 relaxation parameter simultaneously with background suppression.

  14. Structure and membrane interactions of the antibiotic peptide dermadistinctin K by multidimensional solution and oriented 15N and 31P solid-state NMR spectroscopy. (United States)

    Verly, Rodrigo M; de Moraes, Cléria Mendonça; Resende, Jarbas M; Aisenbrey, Christopher; Bemquerer, Marcelo Porto; Piló-Veloso, Dorila; Valente, Ana Paula; Almeida, Fábio C L; Bechinger, Burkhard


    DD K, a peptide first isolated from the skin secretion of the Phyllomedusa distincta frog, has been prepared by solid-phase chemical peptide synthesis and its conformation was studied in trifluoroethanol/water as well as in the presence of sodium dodecyl sulfate and dodecylphosphocholine micelles or small unilamellar vesicles. Multidimensional solution NMR spectroscopy indicates an alpha-helical conformation in membrane environments starting at residue 7 and extending to the C-terminal carboxyamide. Furthermore, DD K has been labeled with (15)N at a single alanine position that is located within the helical core region of the sequence. When reconstituted into oriented phosphatidylcholine membranes the resulting (15)N solid-state NMR spectrum shows a well-defined helix alignment parallel to the membrane surface in excellent agreement with the amphipathic character of DD K. Proton-decoupled (31)P solid-state NMR spectroscopy indicates that the peptide creates a high level of disorder at the level of the phospholipid headgroup suggesting that DD K partitions into the bilayer where it severely disrupts membrane packing.

  15. Synthesis, structure, and physical properties of hybrid nanocomposites for solid-state dye lasers. (United States)

    García-Moreno, I; Costela, A; Cuesta, A; García, O; del Agua, D; Sastre, R


    We report on the synthesis, structural characterization, physical properties, and lasing action of two organic dyes, Rhodamine 6G (Rh6G) and Pyrromethene 597 (PM597), incorporated into new hybrid organic-inorganic materials, where the organic component was either poly(2-hydroxyethyl-methacrylate) (PHEMA) or copolymers of HEMA with methyl methacrylate (MMA), and the inorganic counterpart consisted of silica derived from hydrolysis-condensation of methyltriethoxysilane (TRIEOS) in weight proportion of up to 30%. Lasing efficiencies of up 23% and high photostabilities, with no sign of degradation in the initial laser output after 100 000 pump pulses at 10 Hz, were demonstrated when pumping the samples transversely at 534 nm with 5.5 mJ/pulse. A direct relationship could be established between the structure of the hybrid materials, analyzed by solid-state NMR, and their laser behavior. An inorganic network dominated by di-/tri- substituted silicates in a proportion approximately 35:65, corresponding to samples of HEMA with 15 and 20 wt % proportion of TRIEOS, optimizes the lasing photostability. The thermal properties of these materials, together with the high homogeneity revealed by atomic force microscopy (AFM) images, even in compounds with high silica content, indicate their microstructure to be a continuous phase, corresponding to the polymer matrix, which "traps" the silica components at molecular level via covalent bonding, with few or no silica islands.

  16. A natural abundance 33S solid-state NMR study of layered transition metal disulfides at ultrahigh magnetic field. (United States)

    Sutrisno, Andre; Terskikh, Victor V; Huang, Yining


    Using a series of layered transition metal disulfides we demonstrate that the wide-line natural abundance solid-state NMR spectra of 33S in a less symmetric environment can readily be obtained at ultrahigh magnetic field of 21.1 T and that surprisingly these closely related materials display a wide range of 33S quadrupole coupling constant and chemical shift anisotropy values.

  17. Natural rubber/Zr O{sub 2} blends studied by {sup 1} H solid-state NMR

    Energy Technology Data Exchange (ETDEWEB)

    Ricardo, Nagila M.P.; Cordeiro, Alexandra C.; Feitosa, Francisco Celio [Ceara Univ., Fortaleza, CE (Brazil). Dept. de Quimica Organica e Inorganica; Heatley, Frank [Manchester Univ. (United Kingdom). Dept. of Chemistry


    Natural rubber latex, particularly Manihot glaziovii was used in this work. Zirconium (in the form of ammonium zirconium carbonate)/(AZC) was added to the natural rubber latex after prior deproteinization without disturbing the colloidal stability of the system. This involved mixing AZC containing controlled amounts of ammonium carbonate with latex. Solid-state NMR was used to determine the extend of blending and interaction of the natural components via {sup 1}H broad line relaxation measurements. (author)

  18. Structural Investigations of Portland Cement Components, Hydration, and Effects of Admixtures by Solid-State NMR Spectroscopy

    DEFF Research Database (Denmark)

    Skibsted, Jørgen Bengaard; Andersen, Morten D.; Jakobsen, Hans Jørgen


    - and second-coordination spheres of the spin nucleus under investigation while it is less sensitive to long-range order. Thus, crystalline as well as amorphous phases can be detected in a quantitative manner by solid-state NMR. In particular the structure of the calcium-silicate-hydrate (C-S-H) phase have...... for the C-S-H phase formed during hydration. It will be demonstrated that Al3+ and flouride guest-ions in the anhydrous and hydrated calcium silicates can be studied in detail by 27Al and 19F MAS NMR, thereby providing information on the local structure and the mechanisms for incorporation of these ions...

  19. Solid-state ²H NMR shows equivalence of dehydration and osmotic pressures in lipid membrane deformation. (United States)

    Mallikarjunaiah, K J; Leftin, Avigdor; Kinnun, Jacob J; Justice, Matthew J; Rogozea, Adriana L; Petrache, Horia I; Brown, Michael F


    Lipid bilayers represent a fascinating class of biomaterials whose properties are altered by changes in pressure or temperature. Functions of cellular membranes can be affected by nonspecific lipid-protein interactions that depend on bilayer material properties. Here we address the changes in lipid bilayer structure induced by external pressure. Solid-state ²H NMR spectroscopy of phospholipid bilayers under osmotic stress allows structural fluctuations and deformation of membranes to be investigated. We highlight the results from NMR experiments utilizing pressure-based force techniques that control membrane structure and tension. Our ²H NMR results using both dehydration pressure (low water activity) and osmotic pressure (poly(ethylene glycol) as osmolyte) show that the segmental order parameters (S(CD)) of DMPC approach very large values of ≈ 0.35 in the liquid-crystalline state. The two stresses are thermodynamically equivalent, because the change in chemical potential when transferring water from the interlamellar space to the bulk water phase corresponds to the induced pressure. This theoretical equivalence is experimentally revealed by considering the solid-state ²H NMR spectrometer as a virtual osmometer. Moreover, we extend this approach to include the correspondence between osmotic pressure and hydrostatic pressure. Our results establish the magnitude of the pressures that lead to significant bilayer deformation including changes in area per lipid and volumetric bilayer thickness. We find that appreciable bilayer structural changes occur with osmotic pressures in the range of 10-100 atm or lower. This research demonstrates the applicability of solid-state ²H NMR spectroscopy together with bilayer stress techniques for investigating the mechanism of pressure sensitivity of membrane proteins. Copyright © 2011 Biophysical Society. Published by Elsevier Inc. All rights reserved.

  20. Tannin Fingerprinting in Vegetable Tanned Leather by Solid State NMR Spectroscopy and Comparison with Leathers Tanned by Other Processes

    Directory of Open Access Journals (Sweden)

    Jan H. van der Westhuizen


    Full Text Available Solid state 13C-NMR spectra of pure tannin powders from four different sources – mimosa, quebracho, chestnut and tara – are readily distinguishable from each other, both in pure commercial powder form, and in leather which they have been used to tan.  Groups of signals indicative of the source, and type (condensed vs. hydrolyzable of tannin used in the manufacture are well resolved in the spectra of the finished leathers.  These fingerprints are compared with those arising from leathers tanned with other common tanning agents.  Paramagnetic chromium (III tanning causes widespread but selective disappearance of signals from the spectrum of leather collagen, including resonances from acidic aspartyl and glutamyl residues, likely bound to Cr (III structures. Aluminium (III and glutaraldehyde tanning both cause considerable leather collagen signal sharpening suggesting some increase in molecular structural ordering. The 27Al-NMR signal from the former material is consistent with an octahedral coordination by oxygen ligands. Solid state NMR thus provides easily recognisable reagent specific spectral fingerprints of the products of vegetable and some other common tanning processes. Because spectra are related to molecular properties, NMR is potentially a powerful tool in leather process enhancement and quality or provenance assurance.

  1. Solid state synthesis of starch-capped silver nanoparticles. (United States)

    Hebeish, A; Shaheen, Th I; El-Naggar, Mehrez E


    The present research addresses the establishment of a technique which is solely devoted to environmentally friendly one-pot green synthesis of dry highly stable powdered silver nanoparticles (AgNPs) using starch as both reductant and stabilizing agent in the presence of sodium hydroxide. It is believed that the sodium hydroxide can improve the reduction potential of starch. Thus when the alkali treated starch is submitted to addition of silver nitrate (AgNO3), the alkali treated starch induces the well-established dual role of starch; reduction of silver ions (Ag(+)) to AgNPs and capping the as-formed AgNPs to prevent them from further growth and agglomeration. Beside assessment of AgNPs formation, structural and morphological characteristics of AgNPs are investigated by making use of UV-vis spectroscopy, transmission electron microscopy (TEM), dynamic light scattering (DLS), zeta potential, FT-IR and X-ray diffraction (XRD) analysis. Research outputs signify (a) the absorbance around 410-420nm in the UV-vis spectra of AgNPs appears most, probably owing to the presence of nanosized silver particles and the intensity of this peak increases by increasing AgNO3 concentration; (b) that highly stable AgNPs with well-dispersed particle are successfully prepared using the present research-based innovation; (c) that the size of AgNPs does not exceed 30nm with sphere-like morphology even at the highest Ag(+) concentration employed during synthesis operation; (d) that the XRD and FT-IR confirm the successful preparation of pure AgNPs without noticeable impurities; (d) and that the one-pot synthesis of powdered AgNPs in large scale is clean and easily operated and easily transportation which may be applied as per demands of industries such as textile and painting industry. Copyright © 2016. Published by Elsevier B.V.

  2. Ligand orientation in a membrane-embedded receptor site revealed by solid-state NMR with paramagnetic relaxation enhancement. (United States)

    Whittaker, Christopher A P; Patching, Simon G; Esmann, Mikael; Middleton, David A


    NMR relaxation enhancement by paramagnetic metals provides powerful restraints on the three-dimensional structures of proteins in solution, and this approach has recently been utilized in several NMR structural investigations of proteins in the solid-state. Here we utilize paramagnetic relaxation enhancement (PRE) by Mn(2+) with cross-polarization magic-angle spinning (CP-MAS) solid-state NMR to investigate the interaction of a membrane-embedded protein the Na,K-ATPase (NKA) with a cardiotonic steroid inhibitor. The inhibitor, a diacetonide derivate of the cardiac glycoside ouabain, with (13)C labelled acetonide groups in the rhamnose sugar and steroid moieties ([(13)C2]ODA), is 1000-fold less potent than the parent compound. It is shown that the (13)C CP-MAS solid-state NMR spectra of the NKA-[(13)C2]ODA complex exhibit distinct signals for the two (13)C labels of the inhibitor when bound to the ouabain site of membrane-embedded NKA. Recent crystal structures of NKA indicate that the catalytic α-subunit binds a single Mn(2+) in a transmembrane site close to the high-affinity ouabain site. Here, complexation of NKA with Mn(2+) broadens the resonance line from the rhamnose group substantially more than the steroid peak, indicating that the rhamnose group is closer to the Mn(2+) site than is the steroid group. These observations agree with computational molecular docking simulations and are consistent with ODA adopting an inverted orientation compared to ouabain in the cardiac glycoside site, with the modified rhamnose group drawn toward the transmembrane centre of the protein. This work demonstrates that PRE can provide unique information on the positions and orientations of ligands within their binding pockets of transmembrane proteins.

  3. Heating and temperature gradients of lipid bilayer samples induced by RF irradiation in MAS solid-state NMR experiments. (United States)

    Wang, Jing; Zhang, Zhengfeng; Zhao, Weijing; Wang, Liying; Yang, Jun


    The MAS solid-state NMR has been a powerful technique for studying membrane proteins within the native-like lipid bilayer environment. In general, RF irradiation in MAS NMR experiments can heat and potentially destroy expensive membrane protein samples. However, under practical MAS NMR experimental conditions, detailed characterization of RF heating effect of lipid bilayer samples is still lacking. Herein, using (1) H chemical shift of water for temperature calibration, we systematically study the dependence of RF heating on hydration levels and salt concentrations of three lipids in MAS NMR experiments. Under practical (1) H decoupling conditions used in biological MAS NMR experiments, three lipids show different dependence of RF heating on hydration levels as well as salt concentrations, which are closely associated with the properties of lipids. The maximum temperature elevation of about 10 °C is similar for the three lipids containing 200% hydration, which is much lower than that in static solid-state NMR experiments. The RF heating due to salt is observed to be less than that due to hydration, with a maximum temperature elevation of less than 4 °C in the hydrated samples containing 120 mmol l(-1) of salt. Upon RF irradiation, the temperature gradient across the sample is observed to be greatly increased up to 20 °C, as demonstrated by the remarkable broadening of (1) H signal of water. Based on detailed characterization of RF heating effect, we demonstrate that RF heating and temperature gradient can be significantly reduced by decreasing the hydration levels of lipid bilayer samples from 200% to 30%. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

  4. Crystal structure, magnetism, {sup 89}Y solid state NMR, and {sup 121}Sb Moessbauer spectroscopic investigations of YIrSb

    Energy Technology Data Exchange (ETDEWEB)

    Benndorf, Christopher [Institut fuer Physikalische Chemie, Universitaet Muenster (Germany); Institut fuer Anorganische und Analytische Chemie, Universitaet Muenster (Germany); Heletta, Lukas; Block, Theresa; Poettgen, Rainer [Institut fuer Anorganische und Analytische Chemie, Universitaet Muenster (Germany); Eckert, Hellmut [Institut fuer Physikalische Chemie, Universitaet Muenster (Germany); Institute of Physics in Sao Carlos, University of Sao Paulo, Sao Carlos (Brazil)


    The ternary antimonide YIrSb was synthesized from the binary precursor YIr and elemental antimony by a diffusion controlled solid-state reaction. Single crystals were obtained by a flux technique with elemental bismuth as an inert solvent. The YIrSb structure (TiNiSi type, space group Pnma) was refined from single-crystal X-ray diffractometer data: a = 711.06(9), b = 447.74(5), c = 784.20(8) pm, wR{sub 2} = 0.0455, 535 F{sup 2} values, 20 variables. {sup 89}Y solid state MAS NMR and {sup 121}Sb Moessbauer spectra show single resonance lines in agreement with single-crystal X-ray data. YIrSb is a Pauli paramagnet. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  5. Synergic Investigation Of The Self-Assembly Structure And Mechanism Of Retroviral Capsid Proteins By Solid State NMR, Transmission Electron Microscopy And Multiscale simulation (United States)


    AFRL-AFOSR-VA-TR-2017-0074 Synergic investigation of the self-assembly structure and mechanism of retroviral capsid proteins by solid state NMR...assembly structure and mechanism of retroviral capsid proteins by solid state NMR, transmission electron microscopy and multiscale simulation 5a.  CONTRACT...capsid protein (CA). In vitro, tubular assembly can be obtained with the CA with similar underlying structural properties as the authentic RSV capsid

  6. Solid-state reaction synthesis of boron carbonitride nanotubes (United States)

    Mo, Libin; Chen, Yongjun; Luo, Lijie


    In this study, a simple route for synthesis of ternary boron carbonitride (B-C-N) nanotubes was demonstrated, by heating ball-milled mixture powders of amorphous boron and activated charcoal with a small amount of iron oxide (Fe2O3) at 1000-1200°C under a mixture gas flow of nitrogen (N2) and hydrogen (H2). The reduction of Fe2O3 by H2 at 650°C produced Fe nanoparticles, playing the role of a catalyst during the nanotube growth. The nanotubes synthesized at 1100°C exhibit two morphologies. One is a bamboo-like structure with thick compartments. The other is a quasi-cylindrical structure with thin or disappearing compartments. The average diameter of the nanotubes is about 80 nm. It is found that the reaction temperature has a great influence on the morphology, diameter and yield of the B-C-N nanotubes. Higher temperature (1200°C) is favorable for the formation of quasi-cylindrical nanotubes with larger diameters, while lower temperature (1000°C) enhances the formation of bamboo-like nanotubes with smaller diameters; the yield of nanotubes decreases with the rise of reaction temperature. The nanotubes grow via a combination mechanism of solid-liquid-solid (SLS) and vapor-liquid-solid (VLS) models.

  7. Protein secondary structure of Green Lynx spider dragline silk investigated by solid-state NMR and X-ray diffraction. (United States)

    Xu, Dian; Shi, Xiangyan; Thompson, Forrest; Weber, Warner S; Mou, Qiushi; Yarger, Jeffery L


    In this study, the secondary structure of the major ampullate silk from Peucetia viridans (Green Lynx) spiders is characterized by X-ray diffraction and solid-state NMR spectroscopy. From X-ray diffraction measurement, β-sheet nanocrystallites were observed and found to be highly oriented along the fiber axis, with an orientational order, fc≈0.98. The size of the nanocrystallites was determined to be on average 2.5nm×3.3nm×3.8nm. Besides a prominent nanocrystalline region, a partially oriented amorphous region was also observed with an fa≈0.89. Two-dimensional (13)C-(13)C through-space and through-bond solid-state NMR experiments were employed to elucidate structure details of P. viridans silk proteins. It reveals that β-sheet nanocrystallites constitutes 40.0±1.2% of the protein and are dominated by alanine-rich repetitive motifs. Furthermore, based upon the NMR data, 18±1% of alanine, 60±2% glycine and 54±2% serine are incorporated into helical conformations. Copyright © 2015 Elsevier B.V. All rights reserved.

  8. Bottom-up and top-down solid-state NMR approaches for bacterial biofilm matrix composition (United States)

    Cegelski, Lynette


    The genomics and proteomics revolutions have been enormously successful in providing crucial "parts lists" for biological systems. Yet, formidable challenges exist in generating complete descriptions of how the parts function and assemble into macromolecular complexes and whole-cell assemblies. Bacterial biofilms are complex multicellular bacterial communities protected by a slime-like extracellular matrix that confers protection to environmental stress and enhances resistance to antibiotics and host defenses. As a non-crystalline, insoluble, heterogeneous assembly, the biofilm extracellular matrix poses a challenge to compositional analysis by conventional methods. In this perspective, bottom-up and top-down solid-state NMR approaches are described for defining chemical composition in complex macrosystems. The "sum-of-the-parts" bottom-up approach was introduced to examine the amyloid-integrated biofilms formed by Escherichia coli and permitted the first determination of the composition of the intact extracellular matrix from a bacterial biofilm. An alternative top-down approach was developed to define composition in Vibrio cholerae biofilms and relied on an extensive panel of NMR measurements to tease out specific carbon pools from a single sample of the intact extracellular matrix. These two approaches are widely applicable to other heterogeneous assemblies. For bacterial biofilms, quantitative parameters of matrix composition are needed to understand how biofilms are assembled, to improve the development of biofilm inhibitors, and to dissect inhibitor modes of action. Solid-state NMR approaches will also be invaluable in obtaining parameters of matrix architecture.

  9. Cellular solid-state NMR on large prokaryotic and eukaryotic membrane protein complexes

    NARCIS (Netherlands)

    Kaplan, M.|info:eu-repo/dai/nl/339459735


    Unraveling the structure and dynamics of biomolecules is pivotal to understand their function. Hitherto, structural biology has been dependent on data obtained under in-vitro circumstances thereby neglecting the influence of the natural environment. Here, we developed a solid-state Nuclear Magnetic

  10. Structure determination of membrane proteins in their native phospholipid bilayer environment by rotationally aligned solid-state NMR spectroscopy. (United States)

    Opella, Stanley J


    One of the most important topics in experimental structural biology is determining the structures of membrane proteins. These structures represent one-third of all of the information expressed from a genome, distinguished by their locations within the phospholipid bilayer of cells, organelles, or enveloped viruses. Their highly hydrophobic nature and insolubility in aqueous media means that they require an amphipathic environment. They have unique functions in transport, catalysis, channel formation, and signaling. Researchers are particularly interested in G-protein coupled receptors (GPCRs) because they modulate many biological processes, and about half of the approximately 800 of these proteins within the human genome are or can be turned into drug receptors that affect a wide range of diseases. Because of experimental difficulties, researchers have studied membrane proteins using a wide variety of artificial media that mimic membranes, such as mixed organic solvents or detergents. More sophisticated mimics include bilayer discs (bicelles) and the lipid cubic phase (LCP), but both of these contain a very large detergent component, which can disrupt the stability and function of membrane proteins. To have confidence in the resulting structures and their biological functions and to avoid disrupting these delicate proteins, the structures of membrane proteins should be determined in their native environment of liquid crystalline phospholipid bilayers under physiological conditions. This Account describes a recently developed general method for determining the structures of unmodified membrane proteins in phospholipid bilayers by solid-state NMR spectroscopy. Because it relies on the natural, rapid rotational diffusion of these proteins about the bilayer normal, this method is referred to as rotationally aligned (RA) solid-state NMR. This technique elaborates on oriented sample (OS) solid-state NMR, its complementary predecessor. These methods exploit the power of

  11. Nano-mole scale sequential signal assignment by 1 H-detected protein solid-state NMR

    KAUST Repository

    Wang, Songlin


    We present a 3D 1H-detected solid-state NMR (SSNMR) approach for main-chain signal assignments of 10-100 nmol of fully protonated proteins using ultra-fast magic-angle spinning (MAS) at ∼80 kHz by a novel spectral-editing method, which permits drastic spectral simplification. The approach offers ∼110 fold time saving over a traditional 3D 13C-detected SSNMR approach. This journal is © The Royal Society of Chemistry 2015.

  12. Proton clouds to measure long-range contacts between nonexchangeable side chain protons in solid-state NMR. (United States)

    Sinnige, Tessa; Daniëls, Mark; Baldus, Marc; Weingarth, Markus


    We show that selective labeling of proteins with protonated amino acids embedded in a perdeuterated matrix, dubbed 'proton clouds', provides general access to long-range contacts between nonexchangeable side chain protons in proton-detected solid-state NMR, which is important to study protein tertiary structure. Proton-cloud labeling significantly improves spectral resolution by simultaneously reducing proton line width and spectral crowding despite a high local proton density in clouds. The approach is amenable to almost all canonical amino acids. Our method is demonstrated on ubiquitin and the β-barrel membrane protein BamA.

  13. 1H-detected solid-state NMR of proteins entrapped in bioinspired silica: a new tool for biomaterials characterization (United States)

    Ravera, Enrico; Cerofolini, Linda; Martelli, Tommaso; Louka, Alexandra; Fragai, Marco; Luchinat, Claudio


    Proton-detection in solid-state NMR, enabled by high magnetic fields (>18 T) and fast magic angle spinning (>50 kHz), allows for the acquisition of traditional 1H-15N experiments on systems that are too big to be observed in solution. Among those, proteins entrapped in a bioinspired silica matrix are an attractive target that is receiving a large share of attention. We demonstrate that 1H-detected SSNMR provides a novel approach to the rapid assessment of structural integrity in proteins entrapped in bioinspired silica.

  14. Toward a structure determination method for biomineral-associated protein using combined solid- state NMR and computational structure prediction. (United States)

    Masica, David L; Ash, Jason T; Ndao, Moise; Drobny, Gary P; Gray, Jeffrey J


    Protein-biomineral interactions are paramount to materials production in biology, including the mineral phase of hard tissue. Unfortunately, the structure of biomineral-associated proteins cannot be determined by X-ray crystallography or solution nuclear magnetic resonance (NMR). Here we report a method for determining the structure of biomineral-associated proteins. The method combines solid-state NMR (ssNMR) and ssNMR-biased computational structure prediction. In addition, the algorithm is able to identify lattice geometries most compatible with ssNMR constraints, representing a quantitative, novel method for investigating crystal-face binding specificity. We use this method to determine most of the structure of human salivary statherin interacting with the mineral phase of tooth enamel. Computation and experiment converge on an ensemble of related structures and identify preferential binding at three crystal surfaces. The work represents a significant advance toward determining structure of biomineral-adsorbed protein using experimentally biased structure prediction. This method is generally applicable to proteins that can be chemically synthesized. Copyright © 2010 Elsevier Ltd. All rights reserved.

  15. Molecular composition of recycled organic wastes, as determined by solid-state 13C NMR and elemental analyses. (United States)

    Eldridge, S M; Chen, C R; Xu, Z H; Nelson, P N; Boyd, S E; Meszaros, I; Chan, K Y


    Using solid state (13)C NMR data and elemental composition in a molecular mixing model, we estimated the molecular components of the organic matter in 16 recycled organic (RO) wastes representative of the major materials generated in the Sydney basin area. Close correspondence was found between the measured NMR signal intensities and those predicted by the model for all RO wastes except for poultry manure char. Molecular nature of the organic matter differed widely between the RO wastes. As a proportion of organic C, carbohydrate C ranged from 0.07 to 0.63, protein C from composition data has great potential as a predictor of RO waste soil carbon and nutrient outcomes. Copyright © 2013 Elsevier Ltd. All rights reserved.

  16. Powder crystallography of pharmaceutical materials by combined crystal structure prediction and solid-state 1H NMR spectroscopy. (United States)

    Baias, Maria; Widdifield, Cory M; Dumez, Jean-Nicolas; Thompson, Hugh P G; Cooper, Timothy G; Salager, Elodie; Bassil, Sirena; Stein, Robin S; Lesage, Anne; Day, Graeme M; Emsley, Lyndon


    A protocol for the ab initio crystal structure determination of powdered solids at natural isotopic abundance by combining solid-state NMR spectroscopy, crystal structure prediction, and DFT chemical shift calculations was evaluated to determine the crystal structures of four small drug molecules: cocaine, flutamide, flufenamic acid, and theophylline. For cocaine, flutamide and flufenamic acid, we find that the assigned (1)H isotropic chemical shifts provide sufficient discrimination to determine the correct structures from a set of predicted structures using the root-mean-square deviation (rmsd) between experimentally determined and calculated chemical shifts. In most cases unassigned shifts could not be used to determine the structures. This method requires no prior knowledge of the crystal structure, and was used to determine the correct crystal structure to within an atomic rmsd of less than 0.12 Å with respect to the known reference structure. For theophylline, the NMR spectra are too simple to allow for unambiguous structure selection.

  17. High resolution solid-state NMR spectroscopy of the Yersinia pestis outer membrane protein Ail in lipid membranes

    Energy Technology Data Exchange (ETDEWEB)

    Yao, Yong; Dutta, Samit Kumar [Sanford Burnham Prebys Medical Discovery Institute (United States); Park, Sang Ho; Rai, Ratan [University of California San Diego, Department of Chemistry and Biochemistry (United States); Fujimoto, L. Miya; Bobkov, Andrey A. [Sanford Burnham Prebys Medical Discovery Institute (United States); Opella, Stanley J. [University of California San Diego, Department of Chemistry and Biochemistry (United States); Marassi, Francesca M., E-mail: [Sanford Burnham Prebys Medical Discovery Institute (United States)


    The outer membrane protein Ail (Adhesion invasion locus) is one of the most abundant proteins on the cell surface of Yersinia pestis during human infection. Its functions are expressed through interactions with a variety of human host proteins, and are essential for microbial virulence. Structures of Ail have been determined by X-ray diffraction and solution NMR spectroscopy, but those samples contained detergents that interfere with functionality, thus, precluding analysis of the structural basis for Ail’s biological activity. Here, we demonstrate that high-resolution solid-state NMR spectra can be obtained from samples of Ail in detergent-free phospholipid liposomes, prepared with a lipid to protein molar ratio of 100. The spectra, obtained with {sup 13}C or {sup 1}H detection, have very narrow line widths (0.40–0.60 ppm for {sup 13}C, 0.11–0.15 ppm for {sup 1}H, and 0.46–0.64 ppm for {sup 15}N) that are consistent with a high level of sample homogeneity. The spectra enable resonance assignments to be obtained for N, CO, CA and CB atomic sites from 75 out of 156 residues in the sequence of Ail, including 80% of the transmembrane region. The {sup 1}H-detected solid-state NMR {sup 1}H/{sup 15}N correlation spectra obtained for Ail in liposomes compare very favorably with the solution NMR {sup 1}H/{sup 15}N TROSY spectra obtained for Ail in nanodiscs prepared with a similar lipid to protein molar ratio. These results set the stage for studies of the molecular basis of the functional interactions of Ail with its protein partners from human host cells, as well as the development of drugs targeting Ail.

  18. Investigating fatty acids inserted into magnetically aligned phospholipid bilayers using EPR and solid-state NMR spectroscopy (United States)

    Nusair, Nisreen A.; Tiburu, Elvis K.; Dave, Paresh C.; Lorigan, Gary A.


    This is the first time 2H solid-state NMR spectroscopy and spin-labeled EPR spectroscopy have been utilized to probe the structural orientation and dynamics of a stearic acid incorporated into magnetically aligned phospholipid bilayers or bicelles. The data gleaned from the two different techniques provide a more complete description of the bilayer membrane system. Both methods provided similar qualitative information on the phospholipid bilayer, high order, and low motion for the hydrocarbon segment close to the carboxyl groups of the stearic acid and less order and more rapid motion at the end towards the terminal methyl groups. However, the segmental order parameters differed markedly due to the different orientations that the nitroxide and C-D bond axes transform with the various stearic acid acyl chain conformations, and because of the difference in dynamic sensitivity between NMR and EPR over the timescales examined. 5-, 7-, 12-, and 16-doxylstearic acids spin-labels were used in the EPR experiments and stearic acid-d 35 was used in the solid-state NMR experiments. The influence of the addition of cholesterol and the variation of temperature on the fatty acid hydrocarbon chain ordering in the DMPC/DHPC phospholipid bilayers was also studied. Cholesterol increased the degree of ordering of the hydrocarbon chains. Conversely, as the temperature of the magnetically aligned phospholipid bilayers increased, the order parameters decreased due to the higher random motion of the acyl chain of the stearic acid. The results indicate that magnetically aligned phospholipid bilayers are an excellent model membrane system and can be used for both NMR and EPR studies.

  19. Local environment and composition of magnesium gallium layered double hydroxides determined from solid-state 1H and 71Ga NMR spectroscopy

    DEFF Research Database (Denmark)

    Boisen Staal, Line; Lipton, Andrew S.; Zorin, Vadim


    Ordering of gallium(III) in a series of magnesium gallium (MgGa) layered double hydroxides (LDHs), [Mg1−xGax(OH)2(NO3)x·yH2O] was investigated using solid-state 1H and 71Ga NMR spectroscopy as well as powder X-ray diffraction. Three different proton environments from Mg3single bondOH, Mg2Gasingle...... analysis show that the synthesized MgGa LDH׳s had a lower Mg:Ga ratio than that of the starting reactant solution. The origin of this is the formation of soluble [Ga(OH)4]− complexes formed during synthesis, and not due to formation of insoluble gallium (oxy)hydroxides. No sign of Gasingle bondOsingle bond...

  20. αB-Crystallin. A Hybrid Solid-State/Solution-State NMR Investigation Reveals Structural Aspects of the Heterogeneous Oligomer

    Energy Technology Data Exchange (ETDEWEB)

    Jehle, Stefan [Freie Univ., Berlin (Germany); Leibniz Inst. for Molecular Pharmacology, Berlin (Germany); van Rossum, Barth [Leibniz Inst. for Molecular Pharmacology, Berlin (Germany); Stout, Joseph R. [Univ. of Washington, Seattle, WA (United States); Noguchi, Satoshi M. [Univ. of Washington, Seattle, WA (United States); Falber, Katja [Leibniz Inst. for Molecular Pharmacology, Berlin (Germany); Rehbein, Kristina [Leibniz Inst. for Molecular Pharmacology, Berlin (Germany); Oschkinat, Hartmut [Freie Univ., Berlin (Germany); Leibniz Inst. for Molecular Pharmacology, Berlin (Germany); Klevit, Rachel E. [Univ. of Washington, Seattle, WA (United States); Rajagopal, Ponni [Univ. of Washington, Seattle, WA (United States)


    Atomic-level structural information on αB-Crystallin (αB), a prominent member of the small heat-shock protein family, has been a challenge to obtain due its polydisperse oligomeric nature. We show that magic-angle spinning solid-state NMR can be used to obtain high-resolution information on an ~580-kDa human αB assembled from 175-residue 20-kDa subunits. An ~100-residue α-crystallin domain is common to all small heat-shock proteins, and solution-state NMR was performed on two different α- crystallin domain constructs isolated from αB. In vitro, the chaperone-like activities of full-length αB and the isolated α-crystallin domain are identical. Chemical shifts of the backbone and Cβ resonances have been obtained for residues 64–162 (α-crystallin domain plus part of the C-terminus) in αB and the isolated α-crystallin domain by solid-state and solution-state NMR, respectively. Both sets of data strongly predict six β-strands in the α-crystallin domain. A majority of residues in the α-crystallin domain have similar chemical shifts in both solid-state and solution-state, indicating similar structures for the domain in its isolated and oligomeric forms. Sites of intersubunit interaction are identified from chemical shift differences that cluster to specific regions of the α-crystallin domain. Multiple signals are observed for the resonances of M68 in the oligomer, identifying the region containing this residue as existing in heterogeneous environments within αB. Evidence for a novel dimerization motif in the human α-crystallin domain is obtained by a comparison of (i) solid-state and solution-state chemical shift data and (ii) 1H–15N heteronuclear single quantum coherence spectra as a function of pH. The isolated α-crystallin domain undergoes a dimer–monomer transition over the pH range 7.5–6.8. This steep pHdependent switch may be important for αB to function optimally (e.g., to preserve the filament integrity

  1. Tracing bacterial metabolism using multi-nuclear (1H, 2H, and 13C) Solid State NMR: Realizing an Idea Initiated by James Scott (United States)

    Cody, G.; Fogel, M. L.; Jin, K.; Griffen, P.; Steele, A.; Wang, Y.


    NMR experiments, most notably in the spectral region corresponding to glycogen H and C, respectively. Interestingly, whereas in both experiments the predominant site of incorporation was in the membrane lipids, the line width of the aliphatic-D resonance in the D2O enriched experiment is 67 % wider than that observed in the D-glucose enriched experiment. This difference could be due to greater residual 1H-2H dipolar coupling in membrane lipids synthesized with 10 % D2O due to D being incorporated during NADP(D) reduction of the fatty acid precursor during synthesis and the H-glucose being the source of carbon and hydrogen starting with acetyl-CoA. In the case of the D-glucose experiment, the narrower absorption line may be consistent with individual FA's being more homogeneously deuterated. Analysis of the membrane lipids is currently being performed via GCMS in order to gain potentially more insight to guide interpretation of the 2H solid state NMR spectra.

  2. Solid state NMR studies of oligourea foldamers: interaction of 15N-labelled amphiphilic helices with oriented lipid membranes. (United States)

    Aisenbrey, Christopher; Pendem, Nagendar; Guichard, Gilles; Bechinger, Burkhard


    Synthetic oligomers that are derived from natural polypeptide sequences, albeit with unnatural building blocks, have attracted considerable interest in mimicking bioactive peptides and proteins. Many of those compounds adopt stable folds in aqueous environments that resemble protein structural elements. Here we have chemically prepared aliphatic oligoureas and labeled them at selected positions with (15)N for structural investigations using solid-state NMR spectroscopy. In the first step, the main tensor elements and the molecular alignment of the (15)N chemical shift tensor were analyzed. This was possible by using a two-dimensional heteronuclear chemical shift/dipolar coupling correlation experiment on a model compound that represents the chemical, and thereby also the chemical shift characteristics, of the urea bond. In the next step (15)N labeled versions of an amphipathic oligourea, that exert potent antimicrobial activities and that adopt stable helical structures in aqueous environments, were prepared. These compounds were reconstituted into oriented phospholipid bilayers and the (15)N chemical shift and (1)H-(15)N dipolar couplings of two labeled sites were determined by solid-state NMR spectroscopy. The data are indicative of an alignment of this helix parallel to the membrane surface in excellent agreement with the amphipathic character of the foldamer and consistent with previous models explaining the antimicrobial activities of α-peptides.

  3. Characterization of Zn-containing metal-organic frameworks by solid-state 67Zn NMR spectroscopy and computational modeling. (United States)

    Sutrisno, Andre; Terskikh, Victor V; Shi, Qi; Song, Zhengwei; Dong, Jinxiang; Ding, San Yuan; Wang, Wei; Provost, Bianca R; Daff, Thomas D; Woo, Tom K; Huang, Yining


    Metal-organic frameworks (MOFs) are an extremely important class of porous materials with many applications. The metal centers in many important MOFs are zinc cations. However, their Zn environments have not been characterized directly by (67)Zn solid-state NMR (SSNMR) spectroscopy. This is because (67)Zn (I=5/2) is unreceptive with many unfavorable NMR characteristics, leading to very low sensitivity. In this work, we report, for the first time, a (67)Zn natural abundance SSNMR spectroscopic study of several representative zeolitic imidazolate frameworks (ZIFs) and MOFs at an ultrahigh magnetic field of 21.1 T. Our work demonstrates that (67)Zn magic-angle spinning (MAS) NMR spectra are highly sensitive to the local Zn environment and can differentiate non-equivalent Zn sites. The (67)Zn NMR parameters can be predicted by theoretical calculations. Through the study of MOF-5 desolvation, we show that with the aid of computational modeling, (67)Zn NMR spectroscopy can provide valuable structural information on the MOF systems with structures that are not well described. Using ZIF-8 as an example, we further demonstrate that (67)Zn NMR spectroscopy is highly sensitive to the guest molecules present inside the cavities. Our work also shows that a combination of (67)Zn NMR data and molecular dynamics simulation can reveal detailed information on the distribution and the dynamics of the guest species. The present work establishes (67)Zn SSNMR spectroscopy as a new tool complementary to X-ray diffraction for solving outstanding structural problems and for determining the structures of many new MOFs yet to come. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Regenerated silk fibers: Structural studies and solid state NMR techniques for efficient multiple distance determinations in proteins (United States)

    Liivak, Oskar


    Material Science is the science of understanding the relationship between the molecular level structure of a material and its macroscopic properties. Such research requires both the ability to determine molecular structure and the ability to control and modify the molecular structure. The present research into silks, especially the dragline silk from the spider Nephila clavipes , is occurring at a time when these two criteria are beginning to be met for proteins like spider silk. Genetic engineering has evolved to the point where material scientists have full control over the primary sequence of amino acids that comprise proteins. In addition, solid state nuclear magnetic resonance (NMR) techniques exist which allow us to probe molecular structure. This work applies solid state NMR to the study of the structure of silk fibers. In particular, we focus on techniques of fiber regeneration from solution. The purpose is not only to develop the techniques by which genetically engineered fibers could be spun into fibers for mass production but also as a tool into fundamental silk research. Results on these regenerated fibers show a correlation between the fraction of the silk's alanine residues which are in the β-sheet conformation and the ultimate tensile strength of the fibers. In addition, in a clever mating of the fiber regeneration technique and the solid state NMR distance measurement experiment, rotational echo double resonance (REDOR), we investigate the supramolecular topology of the alanine β-sheet crystals. Even though the REDOR technique has failings for the complicated ISn spin systems found in the silk samples, a qualitative analysis does indicate that the β-sheet crystals are intermolecular. Finally, we investigate a new class of REDOR-like experiments which are designed to overcome the failings of REDOR in ISn spin systems. Experimental data is shown to validate these ideas. An alternate pulse sequence is also introduced and verified with experimental

  5. Characterisation of different polymorphs of tris(8-hydroxyquinolinatoaluminium(III using solid-state NMR and DFT calculations

    Directory of Open Access Journals (Sweden)

    Periasamy N


    Full Text Available Abstract Background Organic light emitting devices (OLED are becoming important and characterisation of them, in terms of structure, charge distribution, and intermolecular interactions, is important. Tris(8-hydroxyquinolinato-aluminium(III, known as Alq3, an organomettalic complex has become a reference material of great importance in OLED. It is important to elucidate the structural details of Alq3 in its various isomeric and solvated forms. Solid-state nuclear magnetic resonance (NMR is a useful tool for this which can also complement the information obtained with X-ray diffraction studies. Results We report here 27Al one-dimensional (1D and two-dimensional (2D multiple-quantum magic-angle spinning (MQMAS NMR studies of the meridional (α-phase and the facial (δ-phase isomeric forms of Alq3. Quadrupolar parameters are estimated from the 1D spectra under MAS and anisotropic slices of the 2D spectra and also calculated using DFT (density functional theory quantum-chemical calculations. We have also studied solvated phase of Alq3 containing ethanol in its lattice. We show that both the XRD patterns and the quadrupolar parameters of the solvated phase are different from both the α-phase and the δ-phase, although the fluorescence emission shows no substantial difference between the α-phase and the solvated phase. Moreover, we have shown that after the removal of ethanol from the matrix the solvated Alq3 has similar XRD patterns and quadrupolar parameters to that of the α-phase. Conclusion The 2D MQMAS experiments have shown that all the different modifications of Alq3 have 27Al in single unique crystallographic site. The quadrupolar parameters predicted using the DFT calculation under the isodensity polarisable continuum model resemble closely the experimentally obtained values. The solvated phase of Alq3 containing ethanol has structural difference from the α-phase of Alq3 (containing meridional isomer from the solid-state NMR studies

  6. Rapid and accurate determination of the lignin content of lignocellulosic biomass by solid-state NMR. (United States)

    Fu, Li; McCallum, Scott A; Miao, Jianjun; Hart, Courtney; Tudryn, Gregory J; Zhang, Fuming; Linhardt, Robert J


    Biofuels and biomaterials, produced from lignocellulosic feedstock, require facile access to cellulose and hemicellulose to be competitive with petroleum processing and sugar-based fermentation. Physical-chemical barriers resulting from lignin complicates the hydrolysis biomass into fermentable sugars. Thus, the amount of lignin within a substrate is critical in determining biomass processing. The application of 13 C cross-polarization, magic-angle spinning, and solid-state nuclear magnetic resonance for the direct quantification of lignin content in biomass is examined. Using a standard curve constructed from pristine lignin and cellulose, the lignin content of a biomass sample is accurately determined through direct measurement without chemical or enzymatic pre-treatment.

  7. Aspects of solid state 13C CPMAS NMR spectroscopy in coals from the Balkan peninsula

    Directory of Open Access Journals (Sweden)



    Full Text Available The cross-polarized magic-angle-spinning NMR (CPMAS-NMR technique was used in this work to assess the carbon distribution in coals of different rank (peat, lignite, xylite, sub-bituminous coal from important deposits in Greece and Bulgaria. The technique is assumed to be only semiquantitative, due to a number of interferences, such as spinning side bands (SSB in the spectra, paramagnetic species in the samples, and low or remote protonation of aromatic carbons. The Bulgarian sub-bituminous coal shows the greatest amounts of aromatic structures. The lignite sample from the Drama basin, Northern Greece, is relatively unaltered and largely unweathered, and shows the greatest amounts of aliphatic groups. The 13C-NMR spectra of Pliocene lignites from endemic areas in Serbia and Montenegro and Bosnia, taken from published papers, show significantly more intense resonances for methoxyl, phenolic, and polysaccharide moieties compared to the Drama lignite NMR spectrum. Xylite reveals high contents of carbohydrates.

  8. Quantitative solid-state NMR imaging of synthetic calcium phosphate implants. (United States)

    Ramanathan, C; Ackerman, J L


    It is shown that solid-state phosphorus-31 nuclear magnetic resonance imaging can be used to measure quantitatively the mass of hydroxyapatite (HA), a synthetic calcium phosphate used as an orthopedic implant material, in the presence of bone. A three-dimensional projection reconstruction technique was used to produce solid-state images from 998 free induction decays sampled in the presence of a fixed amplitude field gradient whose direction was varied uniformly over the unit sphere. Chemical selection is achieved using T1 contrast, as the synthetic calcium phosphate has a shorter T1 (1.8 sec at 4.7 T) compared with the bone (approximately 15 sec at 4.7 T in vivo, 42 sec ex vivo). Experimental results demonstrating the linear relationship between image intensity and HA density in phantoms containing HA and silicon (IV) oxide, and HA and bone are shown. Chemically pure images of bone mineral and synthetic HA have been computed from images of New Zealand White rabbits acquired in vivo at two different recycle times. The technique can be used to follow noninvasively the resorption and remodeling of calcium phosphate implants in vivo.

  9. Solid-state NMR and computational insights into the crystal structure of silicocarnotite-based bioceramic materials synthesized mechanochemically. (United States)

    Andreev, A S; Bulina, N V; Chaikina, M V; Prosanov, I Yu; Terskikh, V V; Lapina, O B

    In this work, we report the results of a detailed structural study of a promising bioceramic material silicocarnotite Ca5(PO4)2SiO4 (SC) synthesized from mechanochemically treated nanosized silicon-substituted hydroxyapatite by annealing at 1000°C. This novel synthetic approach represents an attractive and efficient route towards large-scale manufacturing of the silicocarnotite-based bioceramics. A combination of solid-state nuclear magnetic resonance (NMR), powder X-ray crystallography and density function theory (DFT) calculations has been implemented to characterize the phase composition of the prepared composite materials and to gain insight into the crystal structure of silicocarnotite. The phase composition analysis based on the multinuclear solid-state NMR has been found in agreement with X-ray powder diffraction indicating the minority phases of CaO (5-6wt%) and residual silicon-apatite (7-8wt%), while the rest of the material being a fairly crystalline silicocarnotite phase (86-88wt%). A combination of computational (CASTEP) and experimental methods was used to address the anionic site disorder in the silicocarnotite crystal structure. Distorted [OPO3] pyramids have appeared as an important structural motif in the SC crystal structure. The ratio between regular [PO4] and distorted [OPO3] tetrahedra is found between 2:1 and 3:1 based on XRD experiments and CASTEP calculations. The natural abundance (43)Ca magic angle spinning NMR spectra of silicocarnotite are reported for the first time. Copyright © 2017 Elsevier Inc. All rights reserved.

  10. A suite of solid-state NMR experiments for RNA intranucleotide resonance assignment in a 21 kDa protein-RNA complex. (United States)

    Marchanka, Alexander; Simon, Bernd; Carlomagno, Teresa


    Intranucleotide resonance of the 26mer box C/D RNA in complex with the L7Ae protein were assigned by solid-state NMR (ssNMR; see picture) spectroscopy. This investigation opens the way for studying RNA in large protein-RNA complexes by ssNMR spectroscopy. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Solid-state NMR studies of bacteriorhodopsin and the purple membrane

    CERN Document Server

    Mason, A J


    proteins. This technique may prove particularly useful when studying large proteins that are difficult to orient where the MAS lineshapes will remain relatively unaffected in comparison with current static NMR methods. Finally the MAOSS method was extended to the study of the lipid components of the purple membrane and the feasibility of determining structural constraints from phospholipid headgroups was assessed. The potential of using sup 3 sup 1 P NMR to observe qualitative protein-lipid interactions in both the purple membrane and reconstituted membranes containing bovine rhodopsin was also demonstrated. Following the demonstration of a new MAS NMR method for resolving orientational constraints in uni-axially oriented biological membranes (Glaubitz and Watts, 1998), experiments were performed to realise the potential of the new method on large, oriented membrane proteins. Using bacteriorhodopsin in the purple membrane as a paradigm for large membrane proteins, the protein was specifically labelled with de...

  12. Solid-state multiple quantum NMR in quantum information processing: exactly solvable models. (United States)

    Fel'dman, E B; Pyrkov, A N; Zenchuk, A I


    Multiple quantum (MQ) NMR is an effective tool for the generation of a large cluster of correlated particles, which, in turn, represent a basis for quantum information processing devices. Studying the available exactly solvable models clarifies many aspects of the quantum information. In this study, we consider two exactly solvable models in the MQ NMR experiment: (i) the isolated system of two spin-1/2 particles (dimers) and (ii) the large system of equivalent spin-1/2 particles in a nanopore. The former model is used to describe the quantum correlations and their relations with the MQ NMR coherences, whereas the latter helps one to model the creation and decay of large clusters of correlated particles.

  13. Spin-state-selective methods in solution- and solid-state biomolecular 13C NMR. (United States)

    Felli, Isabella C; Pierattelli, Roberta


    Spin-state-selective methods to achieve homonuclear decoupling in the direct acquisition dimension of (13)C detected NMR experiments have been one of the key contributors to converting (13)C detected NMR experiments into really useful tools for studying biomolecules. We discuss here in detail the various methods that have been proposed, summarize the large array of new experiments that have been developed and present applications to different kinds of proteins in different aggregation states. Copyright © 2014 Elsevier B.V. All rights reserved.

  14. A multinuclear solid state NMR spectroscopic study of the structural evolution of disordered calcium silicate sol-gel biomaterials. (United States)

    Lin, Zhongjie; Jones, Julian R; Hanna, John V; Smith, Mark E


    Disordered sol-gel prepared calcium silicate biomaterials show significant, composition dependent ability to bond with bone. Bone bonding is attributed to rapid hydroxycarbonate apatite (HCA) formation on the glass surface after immersion in body fluid (or implantation). Atomic scale details of the development of the structure of (CaO)x(SiO2)1-x (x = 0.2, 0.3 and 0.5) under heat treatment and subsequent dissolution in simulated body fluid (SBF) are revealed through a multinuclear solid state NMR approach using one-dimensional (17)O, (29)Si, (31)P and (1)H. Central to this study is the combination of conventional static and magic angle spinning (MAS) and two-dimensional (2D) triple quantum (3Q) (17)O NMR experiments that can readily distinguish and quantify the bridging (BOs) and non-bridging (NBOs) oxygens in the silicate network. Although soluble calcium is present in the sol, the (17)O NMR results reveal that the sol-gel produced network structure is initially dominated by BOs after gelation, aging and drying (e.g. at 120 °C), indicating a nanoscale mixture of the calcium salt and a predominantly silicate network. Only once the calcium salt is decomposed at elevated temperatures do the Ca(2+) ions become available to break BO. Apatite forming ability in SBF depends strongly on the surface OH and calcium content. The presence of calcium aids HCA formation via promotion of surface hydration and the ready availability of Ca(2+) ions. (17)O NMR shows the rapid loss of NBOs charge balanced by calcium as it is leached into the SBF. The formation of nanocrystalline, partially ordered HCA can be detected via(31)P NMR. This data indicates the importance of achieving the right balance of BO/NBO for optimal biochemical response and network properties.

  15. Solid State NMR Investigations of Chain Dynamics and Network Order in Model Poly(dimethylsiloxane) Elastomers

    Energy Technology Data Exchange (ETDEWEB)

    Lewicki, J P; Mayer, B P; Wilson, T S; Chinn, S C; Maxwell, R S


    This work is at a relatively early stage, however it has been demonstrated that we can reliably probe basic network architectures using the MQ-NMR technique. The initial results are in good agreement with what is known from standard network theory and will serve as a basis for the study of progressively increasing structural complexity in Siloxane network systems.

  16. Visualising substrate-fingermark interactions: Solid-state NMR spectroscopy of amino acid reagent development on cellulose substrates. (United States)

    Spindler, Xanthe; Shimmon, Ronald; Roux, Claude; Lennard, Chris


    Most spectroscopic studies of the reaction products formed by ninhydrin, 1,2-indanedione-zinc (Ind-Zn) and 1,8-diazafluoren-9-one (DFO) when reacted with amino acids or latent fingermarks on paper substrates are focused on visible absorption or luminescence spectroscopy. In addition, structural elucidation studies are typically limited to solution-based mass spectrometry or liquid nuclear magnetic resonance (NMR) spectroscopy, which does not provide an accurate representation of the fingermark development process on common paper substrates. The research presented in this article demonstrates that solid-state carbon-13 magic angle spinning NMR ((13)C-MAS-NMR) is a technique that can not only be utilised for structural studies of fingermark enhancement reagents, but is a promising technique for characterising the effect of paper chemistry on fingermark deposition and enhancement. The latter opens up a research area that has been under-explored to date but has the potential to improve our understanding of how fingermark secretions and enhancement reagents interact with paper substrates. Copyright © 2015 Elsevier Ireland Ltd. All rights reserved.

  17. Molecular composition of recycled organic wastes, as determined by solid-state {sup 13}C NMR and elemental analyses

    Energy Technology Data Exchange (ETDEWEB)

    Eldridge, S.M., E-mail: [Environmental Futures Centre, School of Environment, Griffith University, Nathan, QLD 4111 (Australia); NSW Department of Primary Industries, Bruxner Highway, Wollongbar, NSW 2477 (Australia); Chen, C.R. [Environmental Futures Centre, School of Environment, Griffith University, Nathan, QLD 4111 (Australia); Xu, Z.H. [Environmental Futures Centre, School of Biomolecular and Physical Sciences, Griffith University, Nathan, QLD 4111 (Australia); Nelson, P.N. [School of Earth and Environmental Sciences, James Cook University, Cairns, QLD 4870 (Australia); Boyd, S.E. [Environmental Futures Centre, School of Biomolecular and Physical Sciences, Griffith University, Nathan, QLD 4111 (Australia); Meszaros, I. [Formerly NSW Department of Primary Industries, Richmond, NSW 2753 (Australia); Chan, K.Y. [Graduate School of Environment, Macquarie University, North Ryde, NSW 2109 (Australia); Formerly NSW Department of Primary Industries, Richmond, NSW 2753 (Australia)


    Highlights: • Model estimated the molecular C components well for most RO wastes. • Molecular nature of organic matter in RO wastes varied widely. • Molecular composition by NMR modelling preferable to extraction techniques. • Some model shortcomings in estimating molecular composition of biochars. • Waste molecular composition important for carbon/nutrient outcomes in soil. - Abstract: Using solid state {sup 13}C NMR data and elemental composition in a molecular mixing model, we estimated the molecular components of the organic matter in 16 recycled organic (RO) wastes representative of the major materials generated in the Sydney basin area. Close correspondence was found between the measured NMR signal intensities and those predicted by the model for all RO wastes except for poultry manure char. Molecular nature of the organic matter differed widely between the RO wastes. As a proportion of organic C, carbohydrate C ranged from 0.07 to 0.63, protein C from <0.01 to 0.66, lignin C from <0.01 to 0.31, aliphatic C from 0.09 to 0.73, carbonyl C from 0.02 to 0.23, and char C from 0 to 0.45. This method is considered preferable to techniques involving imprecise extraction methods for RO wastes. Molecular composition data has great potential as a predictor of RO waste soil carbon and nutrient outcomes.

  18. Solid state NMR, MRI and Sir Peter Mansfield: (1) from broad lines to narrow and back again; and (2) a highly tenuous link to landmine detection. (United States)

    Garroway, A N


    The contributions of Sir Peter Mansfield to MRI are rooted in solid state NMR. I summarize some of the important contributions of Sir Peter to that field, provide a glimpse of the state of the art in multiple-pulse line-narrowing in the early 1970s, and indicate how the earliest MRI efforts at Nottingham flowed from solid state NMR. These line-narrowing methods, providing control over the Hamiltonian governing the dynamics of nuclear spins, continue to evolve and to find new uses. I indicate how some methods and ideas from solid state NMR of the 1970s are at present applied to the detection of explosives in landmines by nuclear quadrupole resonance (NQR).

  19. Methanol synthesis catalyst manufacturing using the green solid-state method

    Directory of Open Access Journals (Sweden)

    Neda Mirhosseini


    Full Text Available In this research study, methanol synthesis catalysts were manufactured with various mole ratios of metal carbonates (zinc, copper and aluminum carbonate and ammonium hydrogen carbonate via a green solid-state method that employed a ball mill apparatus. Some parameters for the catalyst preparation, such as Al mole percent, Cu/Zn mole ratio, rotations milling speeds and aging time, were optimized to obtain the maximum catalyst activity. The prepared catalysts were compared with the best quality industrial catalyst under the same temperature and pressure condition in a titanium tabular fixed bed reactor. This novel method has many advantages in comparison to the conventional method. The main advantage of the solid-state method is that the methanol synthesis catalyst can be produced without using solvent. Furthermore, this new method reduces operating costs due to the elimination of the filtration and washing steps. Methanol synthesis catalytic activity was maximized at an optimized mole ratio of Cu/Zn of 1.9234 and an Al mole percent of 8 at the maximum grinding speed (450 rpm during an aging time of 30 min, which showed higher activity (240 gCH3OH/kg cat.h in comparison with an industrial catalyst sample (218 gCH3OH/kg cat.h. The production of a green catalyst, which requires less water and results in higher catalyst activity, can be widely used for methanol synthesis catalytic applications.

  20. Hydration properties and phosphorous speciation in native, gelatinized and enzymatically modified potato starch analyzed by solid-state MAS NMR. (United States)

    Larsen, Flemming H; Kasprzak, Mirosław M; Lærke, Helle N; Knudsen, Knud Erik B; Pedersen, Sven; Jørgensen, Anne S; Blennow, Andreas


    Hydration of granular, gelatinized and molecularly modified states of potato starch in terms of molecular mobility were analyzed by (13)C and (31)P solid-state MAS NMR. Gelatinization (GEL) tremendously reduced the immobile fraction compared to native (NA) starch granules. This effect was enhanced by enzyme-assisted catalytic branching with branching enzyme (BE) or combined BE and β-amylase (BB) catalyzed exo-hydrolysis. Carbons of the glycosidic α-1,6 linkages required high hydration rates before adopting uniform chemical shifts indicating solid-state disorder and poor water accessibility. Comparative analysis of wheat and waxy maize starches demonstrated that starches were similar upon gelatinization independent of botanical origin and that the torsion angles of the glycosidic linkages were averages of the crystalline A and B type structures. In starch suspension phosphorous in immobile regions was only observed in NA starch. Moreover phosphorous was observed in a minor pH-insensitive form and as major phosphate in hydrated GEL and BE starches. Copyright © 2013 Elsevier Ltd. All rights reserved.

  1. Characterization of phosphate sequestration by a lanthanum modified bentonite clay: A solid-state NMR, EXAFS and PXRD study

    DEFF Research Database (Denmark)

    Dithmer, Line; Lipton, Andrew S; Reitzel, Kasper


    studies showed that at dissolved organic carbon (DOC) concentration above ca. 250 M the binding capacity was only 50 % of the theoretical value or even less. No other La or Pi phases were detected by SSNMR and EXAFS indicating the effect of DOC is kinetic. Moreover, 31P SSNMR showed that rhabdophane......Phosphate (Pi) sequestration by a lanthanum (La) exchanged clay mineral (La-Bentonite), which is extensively used in chemical lake restoration, was investigated on the molecular level using a combination of 31P and 139La solid state NMR spectroscopy (SSNMR), extended X-ray absorption spectroscopy...... formed upon Pi sequestration is in close proximity to the clay matrix....

  2. Mechanisms of peptide-induced pore formation in lipid bilayers investigated by oriented 31P solid-state NMR spectroscopy.

    Directory of Open Access Journals (Sweden)

    Kresten Bertelsen

    Full Text Available There is a considerable interest in understanding the function of antimicrobial peptides (AMPs, but the details of their mode of action is not fully understood. This motivates extensive efforts in determining structural and mechanistic parameters for AMP's interaction with lipid membranes. In this study we show that oriented-sample (31P solid-state NMR spectroscopy can be used to probe the membrane perturbations and disruption by AMPs. For two AMPs, alamethicin and novicidin, we observe that the majority of the lipids remain in a planar bilayer conformation but that a number of lipids are involved in the peptide anchoring. These lipids display reduced dynamics. Our study supports previous studies showing that alamethicin adopts a transmembrane arrangement without significant disturbance of the surrounding lipids, while novicidin forms toroidal pores at high concentrations leading to more extensive membrane disturbance.

  3. Effect of Ca:Mg ratio on precipitated P species identified using 31P solid state NMR (United States)

    Manimel Wadu, M.


    M.C.W. Manimel Wadu1, O.O Akinremi1, S. Kroeker2 1Department of Soil Science, University of Manitoba, Winnipeg, R3T 2N2, Canada 2Department of Chemistry, University of Manitoba, Winnipeg, R3T 2N2, Canada Agronomic efficiency of added P fertilizer is reduced by the precipitation reactions with the exchangeable Ca and Mg in calcareous soils. We hypothesized that the ratio of Ca to Mg on the soil exchange complex will affect the species of P that is precipitated and its solubility in the soil. A laboratory experiment was conducted using a model calcareous soil system which was composed of resin (Amberlite IRP69) and sand coated with CaCO3 packed into a column. The resin was pre saturated with Ca and Mg in order to achieve five different saturation ratios of Ca:Mg approximately as 100:0, 70:30, 50:50, 30:70 and 0:100. Monoammonium Phosphate was applied to the soil surface to simulate one-dimensional diffusive transport. The column was then incubated for 2 weeks. Chemical analysis for water and acid soluble P, pH, NH4, Ca and Mg was performed on 2mm sections of the soil to a depth of 10 cm. This paper will present and discuss the distribution of P along the soil column. Unlike similar studies that have speculated on the precipitation of P, this study will identify and quantify the P species that is formed using 31P solid state NMR technique. Such knowledge will be helpful in understanding the effect of Ca and Mg on P availability in calcareous system and the role of each cation on P precipitation. Key words: P fertilizers, Ca, Mg, model system, solid state NMR

  4. Uncovering the triggers for GPCR activation using solid-state NMR spectroscopy (United States)

    Kimata, Naoki; Reeves, Philip J.; Smith, Steven O.


    G protein-coupled receptors (GPCRs) span cell membranes with seven transmembrane helices and respond to a diverse array of extracellular signals. Crystal structures of GPCRs have provided key insights into the architecture of these receptors and the role of conserved residues. However, the question of how ligand binding induces the conformational changes that are essential for activation remains largely unanswered. Since the extracellular sequences and structures of GPCRs are not conserved between receptor subfamilies, it is likely that the initial molecular triggers for activation vary depending on the specific type of ligand and receptor. In this article, we describe NMR studies on the rhodopsin subfamily of GPCRs and propose a mechanism for how retinal isomerization switches the receptor to the active conformation. These results suggest a general approach for determining the triggers for activation in other GPCR subfamilies using NMR spectroscopy.

  5. Solid state {sup 13}C NMR analysis of Brazilian cretaceous ambers

    Energy Technology Data Exchange (ETDEWEB)

    Pereira, Ricardo; Azevedo, Debora A., E-mail: ricardopereira@iq.ufrj.b, E-mail: debora@iq.ufrj.b [Universidade Federal do Rio de Janeiro (IQ/UFRJ), Rio de Janeiro, RJ (Brazil). Inst. de Quimica. Lab. de Geoquimica Organica Molecular e Ambiental; San Gil, Rosane A.S. [Universidade Federal do Rio de Janeiro (IQ/UFRJ), RJ (Brazil). Inst. de Quimica. Lab. de RMN de Solidos; Carvalho, Ismar S. [Universidade Federal do Rio de Janeiro (UFRJ), RJ (Brazil). Inst. de Geociencias. Dept. de Geologia; Fernandes, Antonio Carlos S. [Museu Nacional (MN/UFRJ), RJ (Brazil). Dept. de Geologia e Paleontologia


    {sup 13}C cross polarization with magic angle spinning nuclear magnetic resonance ({sup 13}C CPMAS NMR) spectra have been obtained for the first time to three Cretaceous amber samples from South America. The samples were dated to Lower Cretaceous and collected in sediments from the Amazonas, Araripe and Reconcavo basins, Brazil. All samples have very similar spectra, consistent with a common paleobotanical source. Some aspects of the spectra suggest a relationship between Brazilian ambers and Araucariaceae family, such as intense resonances at 38-39 ppm. All samples are constituted by polylabdane structure associated to Class Ib resins, constituted by polymers of labdanoid diterpenes. Finally, information concerning some structural changes during maturation, such as isomerization of {Delta}{sup 8(17)} and {Delta}{sup 12(13)} unsaturations, were obtained by {sup 13}C NMR analyses. The results concerning botanical affinities are in accordance with previous results obtained by gas chromatography-mass spectrometry (GC-MS). (author)

  6. An efficient 2D 11B–11B solid-state NMR spectroscopy strategy for monitoring covalent self-assembly of boronic acid-derived compounds: the transformation and unique architecture of bortezomib molecules in the solid state

    Czech Academy of Sciences Publication Activity Database

    Brus, Jiří; Czernek, Jiří; Urbanová, Martina; Kobera, Libor; Jegorov, A.


    Roč. 19, č. 1 (2017), s. 487-495 ISSN 1463-9076 R&D Projects: GA ČR(CZ) GA14-03636S; GA ČR(CZ) GA16-04109S; GA MŠk(CZ) LO1507 Institutional support: RVO:61389013 Keywords : NMR crystalography * bortezomib * solid-state self-assembly Subject RIV: CD - Macromolecular Chemistry Impact factor: 4.123, year: 2016

  7. Solid-state Chemical Reaction Synthesis and Characterization of Lanthanum Tartrate Nanocrystallites Under Ultrasonication Spectra (United States)

    Li, Dao-hua; He, Shao-fen; Chen, Jie; Jiang, Cheng-yan; Yang, Cheng


    Under near room temperature, by using sodium tartrate, lanthanum trichloride, lanthanum acetate, and lanthanum nitrate as reactants, we synthesize the lanthanum tartrate nanocrystals in one step under the condition that the infrared lamp is irradiated and the polyethylene glycol 400 is used as the surfactant, where the synthesis method of nanoparticles by solid phase chemical reaction is used. Deionized water after washing with ethanol washes. Tartaric acid lanthanum crystalline powder is gotten, respectively. Analyze solid products phase using X-ray diffraction (XRD) and electron diffraction; characterize the functional groups structure with infrared spectra, and analyzethe change of functional groups in drugs before and after reaction; observe the size, shape, and size distribution of particlesby transmission electron microscopy(TEM). Testing 3 types of tartaric acid crystal powder of lanthanum are nano-crystallization, solid products are granular and relatively uniform in size, with an average particle diameter of about 40 nm, and the yield rate is approximately 92.3%. Furthermore, during the synthesis, the solid-state reaction conditions including raw materials, matching proportion of reactants, additions of inert substance, addition of trace solvents, surfactants and porphyrization time, etc, all have some influence on the morphology, particle size and size distribution of the final products. During the synthesis of the lanthanum tartrate nanocrystallites, the solid state reaction conditions such as changing reactant, matching proportion of reactant, adding inert substance, joining a little solvent or surface active solvent and grinding at different times may influence morphology, particle size and the size distribution of final products.

  8. 1H NMR spectra dataset and solid-state NMR data of cowpea (Vigna unguiculata)

    DEFF Research Database (Denmark)

    Alves Filho, Elenilson G.; Silva, Lorena M. A.; Teofilo, Elizita M.


    In this article the NMR data from chemical shifts, coupling constants, and structures of all the characterized compounds were provided, beyond a complementary PCA evaluation for the corresponding manuscript (E.G. Alves Filho, L.M.A. Silva, E.M. Teofilo, F.H. Larsen, E.S. de Brito, 2017) [3]. In a...

  9. Low-Temperature Synthesis of Actinide Tetraborides by Solid-State Metathesis Reactions

    Energy Technology Data Exchange (ETDEWEB)

    Lupinetti, Anthony J.; Garcia, Eduardo; Abney, Kent D.


    The synthesis of actinide tetraborides including uranium tetraboride (UB,), plutonium tetraboride (PUB,) and thorium tetraboride (ThB{sub 4}) by a solid-state metathesis reaction are demonstrated. The present method significantly lowers the temperature required to {approx_equal}850 C. As an example, when UCl{sub 4}, is reacted with an excess of MgB{sub 2}, at 850 C, crystalline UB, is formed. Powder X-ray diffraction and ICP-AES data support the reduction of UCl{sub 3}, as the initial step in the reaction. The UB, product is purified by washing water and drying.

  10. Preparation of highly and generally enriched mammalian tissues for solid state NMR

    Energy Technology Data Exchange (ETDEWEB)

    Wong, Veronica Wai Ching; Reid, David G.; Chow, Wing Ying; Rajan, Rakesh [University of Cambridge, Department of Chemistry (United Kingdom); Green, Maggie [University of Cambridge, Central Biomedical Resources, School of Clinical Medicine (United Kingdom); Brooks, Roger A. [University of Cambridge, Department of Trauma and Orthopaedic Surgery, Addenbrooke’s Hospital (United Kingdom); Duer, Melinda J., E-mail: [University of Cambridge, Department of Chemistry (United Kingdom)


    An appreciable level of isotope labelling is essential for future NMR structure elucidation of mammalian biomaterials, which are either poorly expressed, or unexpressable, using micro-organisms. We present a detailed protocol for high level {sup 13}C enrichment even in slow turnover murine biomaterials (fur keratin), using a customized diet supplemented with commercial labelled algal hydrolysate and formulated as a gel to minimize wastage, which female mice consumed during pregnancy and lactation. This procedure produced approximately eightfold higher fur keratin labelling in pups, exposed in utero and throughout life to label, than in adults exposed for the same period, showing both the effectiveness, and necessity, of this approach.

  11. The in-situ solid-state NMR spectroscopy investigation of alcoholic lactose suspensions. (United States)

    Crisp, J L; Dann, S E; Edgar, M; Blatchford, C G


    The polymorphic forms of lactose in alcoholic suspensions have been determined by (13)C CP-MAS NMR spectroscopy, employing hand-made glass inserts. Suspensions of alpha lactose monohydrate (Lalpha.H(2)O) with particle size between 2 and 200mum were prepared by 24h reflux or by storage for 28d in anhydrous ethanol without agitation. These suspensions were compared to an ethanolic sub-micron lactose suspension provided by a 3M Health Care (Loughborough). The (13)C CP-MAS NMR spectra indicated that Lalpha.H(2)O dehydrated to stable anhydrous alpha lactose polymorph (Lalpha(S)) whilst suspended in ethanol. In addition, strong ethanol (13)C resonances were observed for some samples, indicating a liquid-solid interaction between the ethanol and lactose surface. Replacement of ethanol with anhydrous methanol, n-butanol and 3-methylbutan-2-ol implied that the solvent mediated dehydration of Lalpha.H(2)O to Lalpha(S) occurs as a result of sterically controlled interactions. Copyright 2010 Elsevier Inc. All rights reserved.

  12. DNP-enhanced ultrawideline207Pb solid-state NMR spectroscopy: an application to cultural heritage science. (United States)

    Kobayashi, Takeshi; Perras, Frédéric A; Murphy, Anna; Yao, Yao; Catalano, Jaclyn; Centeno, Silvia A; Dybowski, Cecil; Zumbulyadis, Nicholas; Pruski, Marek


    Dynamic nuclear polarization (DNP) is used to enhance the (ultra)wideline 207 Pb solid-state NMR spectra of lead compounds of relevance in the preservation of cultural heritage objects. The DNP SSNMR experiments enabled, for the first time, the detection of the basic lead carbonate phase of the lead white pigment by 207 Pb SSNMR spectroscopy. Variable-temperature experiments revealed that the short T' 2 relaxation time of the basic lead carbonate phase hinders the acquisition of the NMR signal at room temperature. We additionally observe that the DNP enhancement is twice as large for lead palmitate (a lead soap, which is a degradation product implicated in the visible deterioration of lead-based oil paintings), than it is for the basic lead carbonate. This enhancement has allowed us to detect the formation of a lead soap in an aged paint film by 207 Pb SSNMR spectroscopy; which may aid in the detection of deterioration products in smaller samples removed from works of art.

  13. Grid-free powder averages: on the applications of the Fokker-Planck equation to solid state NMR. (United States)

    Edwards, Luke J; Savostyanov, D V; Nevzorov, A A; Concistrè, M; Pileio, G; Kuprov, Ilya


    We demonstrate that Fokker-Planck equations in which spatial coordinates are treated on the same conceptual level as spin coordinates yield a convenient formalism for treating magic angle spinning NMR experiments. In particular, time dependence disappears from the background Hamiltonian (sample spinning is treated as an interaction), spherical quadrature grids are avoided completely (coordinate distributions are a part of the formalism) and relaxation theory with any linear diffusion operator is easily adopted from the Stochastic Liouville Equation theory. The proposed formalism contains Floquet theory as a special case. The elimination of the spherical averaging grid comes at the cost of increased matrix dimensions, but we show that this can be mitigated by the use of state space restriction and tensor train techniques. It is also demonstrated that low correlation order basis sets apparently give accurate answers in powder-averaged MAS simulations, meaning that polynomially scaling simulation algorithms do exist for a large class of solid state NMR experiments. Copyright © 2013 Elsevier Inc. All rights reserved.

  14. sup 3 sup 1 P high resolution solid state NMR studies of phosphoorganic compounds of biological interest

    CERN Document Server

    Potrzebowski, M J; Kazmierski, S


    In this review several applications of sup 3 sup 1 P high resolution solid state NMR spectroscopy in structural studies of bioorganic samples is recorded. The problem of pseudopolymorphism of bis[6-O,6'-O-(1,2:3,4diisopropylidene-alpha-D-galactopyranosyl) phosphothionyl] disulfide (1) and application of sup 3 sup 1 P C/MAS experiment to investigate of this phenomenon is discussed. The influence of weak C-H--S intermolecular contacts on molecular packing of 1,6-anhydro-2-O-tosyl-4-S- (5,5-dimethyl-2-thioxa-1,3,2-dioxaphosphophorinan-2-= yl)-beta-D-glucopyranose (2) and S sub P , R sub P diastereomers of deoxyxylothymidyl-3'-O-acetylthymidyl (3',5')-O-(2-cyanoethyl) phosphorothioate (3) and their implication on sup 3 sup 1 P NMR spectra is shown. The final part of review describes the recent progress in structural studies of O-phosphorylated amino acids (serine, threonine, tyrosine), relationship between molecular structure and sup 3 sup 1 P chemical shift parameters delta sub i sub i and influence of hydrogen ...

  15. Solid state NMR and IR characterization of wood polymer structure in relation to tree provenance. (United States)

    Santoni, Ilaria; Callone, Emanuela; Sandak, Anna; Sandak, Jakub; Dirè, Sandra


    (13)C nuclear magnetic resonance and mid-infrared spectroscopies were used for characterizing changes in the chemical structure of wood polymers (cellulose, hemicellulose and lignin) in relation to the tree growth location. Samples of three provenances in Europe (Finland, Poland and Italy) were selected for studies. The requirement was to use untreated solid wood samples to minimize any manipulation to the nanostructure of native wood. The results confirm that the chemical and physical properties of samples belonging to the same wood species (Picea abies Karst.) differ due to the origin. Both FT-IR and dynamic NMR spectroscopies were able to correctly discriminate samples originating from three different provenances in Europe. Such methods might be very useful for both, research and understanding of wood microstructure and its variability due to the growth conditions. Copyright © 2014 Elsevier Ltd. All rights reserved.

  16. A solid-state NMR investigation of the structure of nanocrystalline hydroxyapatite. (United States)

    Jäger, Christian; Welzel, Thea; Meyer-Zaika, Wolfgang; Epple, Matthias


    Nanocrystalline hydroxyapatite (HAp) prepared by a precipitation route was investigated. The X-ray diffraction (XRD) powder patterns of the elongated nanocrystals with a typical diameter of about 10 nm and length of 30-50 nm (by transmission electron microscopy (TEM)) revealed the presence of HAp with significantly broadened XRD reflections. However, Ca deficiency was found, as the Ca/P ratio was 1.5 only (so-called calcium-deficient hydroxyapatite (CDHA)), and not 1.67. This Ca deficiency of nanocrystalline HAp is explained using NMR. It is shown unambiguously that (i) the nanocrystals consist of a crystalline core and a (disordered) surface region with a relative phosphate content of about 1:1, (ii) the crystalline core is HAp, and (iii) the surface region is dominated by hydrogen phosphate anions (with no hydroxyapatite-like structural motif) and structural water (hydrate). From the relative phosphate content and taking into account the crystal shape, the thickness of the surface layer along the main crystal axis could be estimated to be about 1 nm, and the average chemical composition of the surface layer has been determined. Finally, a Ca/P ratio of 1.52 was estimated from the NMR data that compares well with the value of 1.51 from chemical analysis. The important consequences are that the surface of nanocrystalline HAp has nothing in common with the bulk composition and that the chemistry of such materials (e.g. the binding of protein molecules to phosphate surfaces) must be reconsidered. 2006 John Wiley & Sons, Ltd.

  17. Low Temperature Solid-State Synthesis and Characterization of LaBO3

    Directory of Open Access Journals (Sweden)

    Azmi Seyhun KIPÇAK


    Full Text Available Rare earth (lanthanide series borates, possess high vacuum ultraviolet (VUV transparency, large electronic band gaps, chemical and environmental stability and exceptionally large optical damage thresholds and used in the development of plasma display panels (PDPs. In this study the synthesis of lanthanum borates via solid-state method is studied. For this purpose, lanthanum oxide (La2O3 and boric acid (H3BO3 are used for as lanthanum and boron sources, respectively. Different elemental molar ratios of La to B (between 3:1 to 1:6 as La2O3:H3BO3 were reacted by solid-state method at the reaction temperatures between 500°C - 700°C with the constant reaction time of 4 h. Following the synthesis, characterizations of the synthesized products are conducted by X-ray diffraction (XRD, Fourier transform infrared spectroscopy (FT-IR, Raman spectroscopy and scanning electron microscope (SEM. From the results of the experiments, three types of lanthanum borates of; La3BO6, LaBO3 and La(BO23 were observed at different reaction parameters. Among these three types of lanthanum borates LaBO3 phase were obtained as a major phase.

  18. Sensitivity-enhanced solid-state NMR detection of expansin's target in plant cell walls

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Tuo [Iowa State Univ., Ames, IA (United States); Park, Yong Bum [Pennsylvania State Univ., State College, PA (United States); Caporini, Marc A. [Bruker Biospin Corporation, Billerica, MA (United States); Rosay, Melanie [Bruker Biospin Corporation, Billerica, MA (United States); Zhong, Linghao [Pennsylvania State Univ., State College, PA (United States); Cosgrove, Daniel J. [Pennsylvania State Univ., State College, PA (United States); Hong, Mei [Iowa State Univ., Ames, IA (United States)


    Structure determination of protein binding to noncrystalline macromolecular assemblies such as plant cell walls (CWs) poses a significant structural biology challenge. CWs are loosened during growth by expansin proteins, which weaken the noncovalent network formed by cellulose, hemicellulose, and pectins, but the CW target of expansins has remained elusive because of the minute amount of the protein required for activity and the complex nature of the CW. Using solid-state NMR spectroscopy, combined with sensitivity-enhancing dynamic nuclear polarization (DNP) and differential isotopic labeling of expansin and polysaccharides, we have now determined the functional binding target of expansin in the Arabidopsis thaliana CW. By transferring the electron polarization of a biradical dopant to the nuclei, DNP allowed selective detection of 13C spin diffusion from trace concentrations of 13C, 15N-labeled expansin in the CW to nearby polysaccharides. From the spin diffusion data of wild-type and mutant expansins, we conclude that to loosen the CW, expansin binds highly specific cellulose domains enriched in xyloglucan, whereas more abundant binding to pectins is unrelated to activity. Molecular dynamics simulations indicate short 13C-13C distances of 4–6 Å between a hydrophobic surface of the cellulose microfibril and an aromatic motif on the expansin surface, consistent with the observed NMR signals. DNP-enhanced 2D 13C correlation spectra further reveal that the expansin-bound cellulose has altered conformation and is enriched in xyloglucan, thus providing unique insight into the mechanism of CW loosening. DNP-enhanced NMR provides a powerful, generalizable approach for investigating protein binding to complex macromolecular targets.

  19. Solid-state 51V MAS NMR spectroscopy determines component concentration and crystal phase in co-crystallised mixtures of vanadium complexes

    DEFF Research Database (Denmark)

    Nielsen, Ulla Gro; Hazell, Alan Charles; Skibsted, Jørgen Bengaard


    resonances are sensitive to intermolecular interactions specific to each crystal phase. The solid-state V-51 MAS NMR spectroscopic data show that the different phases do not co-precipitate but the concentration of the solute (which can be either 1 or 2) can vary. Thus co-crystallised mixtures of 1 and 2 can...

  20. Exploration of structure and function in biomolecules through solid-state NMR and computational methods (United States)

    Heider, Elizabeth M.

    Solid-State Nuclear Magnetic Resonance (SSNMR) spectroscopy and quantum mechanical calculations are powerful analysis tools. Leveraged independently, each method yields important nuclear and molecular information. Used in concert, SSNMR and computational techniques provide complementary data about the structure of solids. These methods are particularly useful in characterizing the structures of microcrystalline organic compounds and revealing mechanisms of biological activity. Such applications may possess special relevance in analysis of pharmaceutical products; 90% of all pharmaceuticals are marketed as solids and bioactivity is strongly linked with molecular conformation. Accordingly, this dissertation employs both SSNMR and quantum mechanical computation to study three bioactive molecules: citrinin, two forms of Atrasentan (Abt-627), and paclitaxel (Taxol RTM). First, a computational study is utilized to determine the mechanism for unusual antioxidant activity in citrinin. Here, molecular geometries and bond dissociation enthalpies (BDE) of the citrinin O--H groups are calculated from first principles (ab initio). The total molecular Hamiltonian is determined by approximating the individual contributors to energy including electronic energy and contributions from modes of molecular vibration. This study of citrinin clearly identifies specific reaction sites in the active form, establishing the central role of intramolecular hydrogen bonding in this activity. Notably, it is discovered that citrinin itself is not the active species. Instead, a pair of hydrated Michael addition products of citrinin act as radical scavengers via O--H bond dissociation. Next, two separate compounds of the anticancer drug Abt-627 (form I and form II) are examined via SSNMR. The three principal values of the 13C diagonalized chemical shift tensor are acquired through the high resolution 2D experiment, FIREMAT. Isotropic chemical shift assignments are made utilizing both dipolar

  1. On the exactness of effective Floquet Hamiltonians employed in solid-state NMR spectroscopy (United States)

    Garg, Rajat; Ramachandran, Ramesh


    Development of theoretical models based on analytic theory has remained an active pursuit in molecular spectroscopy for its utility both in the design of experiments as well as in the interpretation of spectroscopic data. In particular, the role of "Effective Hamiltonians" in the evolution of theoretical frameworks is well known across all forms of spectroscopy. Nevertheless, a constant revalidation of the approximations employed in the theoretical frameworks is necessitated by the constant improvements on the experimental front in addition to the complexity posed by the systems under study. Here in this article, we confine our discussion to the derivation of effective Floquet Hamiltonians based on the contact transformation procedure. While the importance of the effective Floquet Hamiltonians in the qualitative description of NMR experiments has been realized in simpler cases, its extension in quantifying spectral data deserves a cautious approach. With this objective, the validity of the approximations employed in the derivation of the effective Floquet Hamiltonians is re-examined through a comparison with exact numerical methods under differing experimental conditions. The limitations arising from the existing analytic methods are outlined along with remedial measures for improving the accuracy of the derived effective Floquet Hamiltonians.

  2. Solid state NMR and bioequivalence comparison of the pharmacokinetic parameters of two formulations of clindamycin

    KAUST Repository

    Al-Talla, Zeyad


    Objective: The purpose of this study was to compare the pharmacokinetic parameters and determine the bioequivalence of a generic formulation of clindamycin that is sold in the local markets in the Middle East (Clindox® 150 mg capsule; test) with a reference formulation (Dalacin C® 150 mg capsule) in healthy adult male volunteers. Methods: A single-dose, open-label, 2-period crossover study was conducted. Healthy male volunteers were randomly assigned to oral administration of a single treatment of the reference and test formulations. The same groups were given the alternate formulation. After dosing, serial blood samples were withdrawn for a period of 24 h. Serum harvested from the blood samples was analyzed for clindamycin by high performance liquid chromatography (HPLC) with ultraviolet detection. Pharmacokinetic parameters, including AUC0-∞, AUC 0-t, Cmax, Ke, tmax and t 1/2 were determined from the serum concentrations for both formulations (test and reference). The products were tested for bioequivalence after log-transformation of the data. Results: 24 healthy adult male volunteers from Jordan (mean [SD] age, 28.8 (7.7) years (range 19-45 years); height, 175.8 (10.6) cm (range 159.0-192.0 cm); weight, 75.6 (11.0) kg (range 58-101 kg); and body mass index, 24.4 (1.8) kg/m2 (range 21.3-28 kg/m2)) were enrolled in and completed the study. The 13C NMR spectra for both Dalacin C® and Clindox® showed 18 distinct lines associated with the 18 different carbon atoms. Conclusion: The statistical comparison suggested that Clindox® capsules are bioequivalent to Dalacin C® capsules. The 13C CPMAS results confirmed that the two drugs exhibit typical clindamycin spectra. ©2011 Dustri-Verlag Dr. K. Feistle.

  3. Intermolecular protein-RNA interactions revealed by 2D 31P-15N magic angle spinning solid-state NMR spectroscopy. (United States)

    Jehle, Stefan; Falb, Melanie; Kirkpatrick, John P; Oschkinat, Hartmut; van Rossum, Barth-Jan; Althoff, Gerhard; Carlomagno, Teresa


    The structural investigation of large RNP complexes by X-ray crystallography can be a difficult task due to the flexibility of the RNA and of the protein-RNA interfaces, which may hinder crystallization. In these cases, NMR spectroscopy is an attractive alternative to crystallography, although the large size of typical RNP complexes may limit the applicability of solution NMR. Solid-state NMR spectroscopy, however, is not subject to any intrinsic limitations with respect to the size of the object under investigation, with restrictions imposed solely by the sensitivity of the instrumentation. In addition, it does not require large, well-ordered crystals and can therefore be applied to flexible, partially disordered complexes. Here we show for the first time that solid-state NMR spectroscopy can be used to probe intermolecular interactions at the protein-RNA interface in RNP complexes. Distances between the (15)N nuclei of the protein backbone and the (31)P nuclei of the RNA backbone can be measured in TEDOR experiments and used as restraints in structure calculations. The distance measurement is accurate, as proven for the test case of the L7Ae-box C/D RNA complex, for which a crystal structure is available. The results presented here reveal the as yet unexplored potential of solid-state NMR spectroscopy in the investigation of large RNP complexes.

  4. Structural Basis for Asymmetric Conductance of the Influenza M2 Proton Channel Investigated by Solid-State NMR Spectroscopy. (United States)

    Mandala, Venkata S; Liao, Shu-Yu; Kwon, Byungsu; Hong, Mei


    The influenza M2 protein forms an acid-activated proton channel that is essential for virus replication. The transmembrane H37 selects for protons under low external pH while W41 ensures proton conduction only from the N terminus to the C terminus and prevents reverse current under low internal pH. Here, we address the molecular basis for this asymmetric conduction by investigating the structure and dynamics of a mutant channel, W41F, which permits reverse current under low internal pH. Solid-state NMR experiments show that W41F M2 retains the pH-dependent α-helical conformations and tetrameric structure of the wild-type (WT) channel but has significantly altered protonation and tautomeric equilibria at H37. At high pH, the H37 structure is shifted toward the π tautomer and less cationic tetrads, consistent with faster forward deprotonation to the C terminus. At low pH, the mutant channel contains more cationic tetrads than the WT channel, consistent with faster reverse protonation from the C terminus. 15N NMR spectra allow the extraction of four H37 pKas and show that the pKas are more clustered in the mutant channel compared to WT M2. Moreover, binding of the antiviral drug, amantadine, at the N-terminal pore at low pH did not convert all histidines to the neutral state, as seen in WT M2, but left half of all histidines cationic, unambiguously demonstrating C-terminal protonation of H37 in the mutant. These results indicate that asymmetric conduction in WT M2 is due to W41 inhibition of C-terminal acid activation by H37. When Trp is replaced by Phe, protons can be transferred to H37 bidirectionally with distinct rate constants. Copyright © 2017 Elsevier Ltd. All rights reserved.

  5. Operando Solid-State NMR Observation of Solvent-Mediated Adsorption-Reaction of Carbohydrates in Zeolites

    Energy Technology Data Exchange (ETDEWEB)

    Qi, Long; Alamillo, Ricardo; Elliott, William A.; Andersen, Amity; Hoyt, David W.; Walter, Eric D.; Han, Kee Sung; Washton, Nancy M.; Rioux, Robert M.; Dumesic, James A.; Scott, Susannah L.


    In the liquid-phase catalytic processing of molecules using heterogeneous catalysts - an important strategy for obtaining renewable chemicals from biomass - many of the key reactions occur at solid-liquid interfaces. In particular, glucose isomerization occurs when the glucose is adsorbed in the micropores of a zeolite catalyst. Since solvent molecules are coadsorbed, the catalytic activity depends strongly and often nonmonotonically on the solvent composition. For glucose isomerization catalyzed by NaX and NaY zeolites, there is an initial steep decline when water is mixed with a small amount of the organic cosolvent γ-valerolactone (GVL), followed by a dramatic and surprising recovery as the GVL content in the mixed solvent increases. Here we elucidate the origin of this complex solvent effect using operando solid-state NMR spectroscopy. The glucopyranose tautomers immobilized in the zeolite pores were observed and their transformations into fructose and mannose followed in real time. The microheterogeneity of the solvent system, manifested by a nonmonotonic trend in the mixing enthalpy, influences the mobility and adsorption behavior of the carbohydrates, water, and GVL, which were studied using pulsed-field gradient (PFG) NMR diffusivity measurements. At low GVL concentrations, glucose is depleted in the zeolite pores relative to the solution phase and changes in the local structure of coadsorbed water serve to further suppress the isomerization rate. At higher GVL concentrations, this lower intrinsic reactivity is largely compensated by strong glucose partitioning into the pores, resulting in dramatic (up to 32×) enhancements in the local sugar concentration at the solid-liquid interface.

  6. Solid State C-13 and H-2 NMR Investigations of Paramagnetic Ni(II)(acac)(2)L-2 Complexes

    DEFF Research Database (Denmark)

    Lennartson, A.; Christensen, Lene Ulrikke; McKenzie, C. J.


    Nine structurally related paramagnetic acetylacetonato nickel(II) complexes: [Ni(acac)(2)] and trans-[Ni(acac)(2)(X)(2)]nH/D2O, X = H2O, D2O, NH3, MeOH, PMePh2, PMe2Ph, or [dppe](1/2), n = 0 or 1, dppe = 1,2-his(diphenylphosphino)ethane, as well as cis-[Ni(F-6-acac)(2)(D2O)(2)], F-6-acac = hexafl......Nine structurally related paramagnetic acetylacetonato nickel(II) complexes: [Ni(acac)(2)] and trans-[Ni(acac)(2)(X)(2)]nH/D2O, X = H2O, D2O, NH3, MeOH, PMePh2, PMe2Ph, or [dppe](1/2), n = 0 or 1, dppe = 1,2-his(diphenylphosphino)ethane, as well as cis-[Ni(F-6-acac)(2)(D2O)(2)], F-6-acac...... = hexafluoroacetylonato, have been characterized by solid state C-13 MAS NMR spectroscopy. H-2 MAS NMR was used to probe the local hydrogen bonding network in [Ni(acac)(2)(D2O)(2)]D2O and cis-[Ni(F-6-acac)(2)(D2O)(2)]. The complexes serve to benchmark the paramagnetic shift, which can be associated with the resonances...... of atoms of the coordinated ligands. The methine (CH) and methyl (CH3) have characteristic combinations of the isotropic shift (delta) and anisotropy parameters (d, eta). The size of the anisotropy (d), which is the sum of the chemical shift anisotropy (CSA) and the paramagnetic electron-nuclei dipolar...

  7. Early Stages of Biomineral Formation—A Solid-State NMR Investigation of the Mandibles of Minipigs

    Directory of Open Access Journals (Sweden)

    Anastasia Vyalikh


    Full Text Available Solid-state nuclear magnetic resonance (NMR spectroscopy allows for the identification of inorganic species during the biomineral formation, when crystallite particles visible in direct imaging techniques have not yet been formed. The bone blocks surrounding dental implants in minipigs were dissected after the healing periods of two, four, and eight weeks, and newly formed tissues formed around the implants were investigated ex vivo. Two-dimensional 31P-1H heteronuclear correlation (HETCOR spectroscopy is based on the distance-dependent heteronuclear dipolar coupling between phosphate- and hydrogen-containing species and provides sufficient spectral resolution for the identification of different phosphate minerals. The nature of inorganic species present at different mineralization stages has been determined based on the 31P chemical shift information. After a healing time of two weeks, pre-stages of mineralization with a rather unstructured distribution of structural motives were found. After four weeks, different structures, which can be described as nanocrystals exhibiting a high surface-to-volume ratio were detected. They grew and, after eight weeks, showed chemical structures similar to those of matured bone. In addition to hydroxyapatite, amorphous calcium phosphate, and octacalcium phosphate, observed in a reference sample of mature bone, signatures of ß-tricalcium phosphate and brushite-like structures were determined at the earlier stages of bone healing.

  8. Solid state NMR of isotope labelled murine fur: a powerful tool to study atomic level keratin structure and treatment effects

    Energy Technology Data Exchange (ETDEWEB)

    Wong, Wai Ching Veronica; Narkevicius, Aurimas; Chow, Wing Ying; Reid, David G.; Rajan, Rakesh [University of Cambridge, Department of Chemistry (United Kingdom); Brooks, Roger A. [University of Cambridge, Department of Trauma and Orthopaedic Surgery, Addenbrooke’s Hospital (United Kingdom); Green, Maggie [University of Cambridge, Central Biomedical Resources, School of Clinical Medicine (United Kingdom); Duer, Melinda J., E-mail: [University of Cambridge, Department of Chemistry (United Kingdom)


    We have prepared mouse fur extensively {sup 13}C,{sup 15}N-labelled in all amino acid types enabling application of 2D solid state NMR techniques which establish covalent and spatial proximities within, and in favorable cases between, residues. {sup 13}C double quantum–single quantum correlation and proton driven spin diffusion techniques are particularly useful for resolving certain amino acid types. Unlike 1D experiments on isotopically normal material, the 2D methods allow the chemical shifts of entire spin systems of numerous residue types to be determined, particularly those with one or more distinctively shifted atoms such as Gly, Ser, Thr, Tyr, Phe, Val, Leu, Ile and Pro. Also the partial resolution of the amide signals into two signal envelopes comprising of α-helical, and β-sheet/random coil components, enables resolution of otherwise overlapped α-carbon signals into two distinct cross peak families corresponding to these respective secondary structural regions. The increase in resolution conferred by extensive labelling offers new opportunities to study the chemical fate and structural environments of specific atom and amino acid types under the influence of commercial processes, and therapeutic or cosmetic treatments.

  9. Operando Solid-State NMR Observation of Solvent-Mediated Adsorption-Reaction of Carbohydrates in Zeolites

    Energy Technology Data Exchange (ETDEWEB)

    Qi, Long; Alamillo, Ricardo [Department; Elliott, William A.; Andersen, Amity [Environmental; Hoyt, David W. [Environmental; Walter, Eric D. [Environmental; Han, Kee Sung [Environmental; Washton, Nancy M. [Environmental; Rioux, Robert M.; Dumesic, James A. [Department; Scott, Susannah L.


    Liquid-phase processing of molecules using heterogeneous catalysts – an important strategy for obtaining renewable chemicals sustainably from biomass – involves reactions that occur at solid-liquid interfaces. In glucose isomerization catalyzed by basic faujasite zeolites, the catalytic activity depends strongly on the solvent composition: initially, it declines precipitously when water is mixed with a small amount of the organic co-solvent γ-valerolactone (GVL), then recovers as the GVL content increases. Using solid-state 13C NMR spectroscopy, we observed glucose isomers located inside the zeolite pores directly, and followed their transformations into fructose and mannose in real time. At low GVL concentrations, glucose is depleted in the zeolite pores relative to the liquid phase, while higher GVL concentrations in solution drive glucose inside the pores, resulting in up to a 32 enhancement in the local glucose concentration. Although their populations exchange rapidly, molecules present at the reactive interface experience a significantly different environment from the bulk solution.

  10. Advanced solid-state NMR techniques for characterization of membrane protein structure and dynamics: application to Anabaena Sensory Rhodopsin. (United States)

    Ward, Meaghan E; Brown, Leonid S; Ladizhansky, Vladimir


    Studies of the structure, dynamics, and function of membrane proteins (MPs) have long been considered one of the main applications of solid-state NMR (SSNMR). Advances in instrumentation, and the plethora of new SSNMR methodologies developed over the past decade have resulted in a number of high-resolution structures and structural models of both bitopic and polytopic α-helical MPs. The necessity to retain lipids in the sample, the high proportion of one type of secondary structure, differential dynamics, and the possibility of local disorder in the loop regions all create challenges for structure determination. In this Perspective article we describe our recent efforts directed at determining the structure and functional dynamics of Anabaena Sensory Rhodopsin, a heptahelical transmembrane (7TM) protein. We review some of the established and emerging methods which can be utilized for SSNMR-based structure determination, with a particular focus on those used for ASR, a bacterial protein which shares its 7TM architecture with G-protein coupled receptors. Copyright © 2014 Elsevier Inc. All rights reserved.

  11. Integrating solid-state NMR and computational modeling to investigate the structure and dynamics of membrane-associated ghrelin.

    Directory of Open Access Journals (Sweden)

    Gerrit Vortmeier

    Full Text Available The peptide hormone ghrelin activates the growth hormone secretagogue receptor 1a, also known as the ghrelin receptor. This 28-residue peptide is acylated at Ser3 and is the only peptide hormone in the human body that is lipid-modified by an octanoyl group. Little is known about the structure and dynamics of membrane-associated ghrelin. We carried out solid-state NMR studies of ghrelin in lipid vesicles, followed by computational modeling of the peptide using Rosetta. Isotropic chemical shift data of isotopically labeled ghrelin provide information about the peptide's secondary structure. Spin diffusion experiments indicate that ghrelin binds to membranes via its lipidated Ser3. Further, Phe4, as well as electrostatics involving the peptide's positively charged residues and lipid polar headgroups, contribute to the binding energy. Other than the lipid anchor, ghrelin is highly flexible and mobile at the membrane surface. This observation is supported by our predicted model ensemble, which is in good agreement with experimentally determined chemical shifts. In the final ensemble of models, residues 8-17 form an α-helix, while residues 21-23 and 26-27 often adopt a polyproline II helical conformation. These helices appear to assist the peptide in forming an amphipathic conformation so that it can bind to the membrane.

  12. Integrating Solid-State NMR and Computational Modeling to Investigate the Structure and Dynamics of Membrane-Associated Ghrelin (United States)

    Els-Heindl, Sylvia; Chollet, Constance; Scheidt, Holger A.; Beck-Sickinger, Annette G.; Meiler, Jens; Huster, Daniel


    The peptide hormone ghrelin activates the growth hormone secretagogue receptor 1a, also known as the ghrelin receptor. This 28-residue peptide is acylated at Ser3 and is the only peptide hormone in the human body that is lipid-modified by an octanoyl group. Little is known about the structure and dynamics of membrane-associated ghrelin. We carried out solid-state NMR studies of ghrelin in lipid vesicles, followed by computational modeling of the peptide using Rosetta. Isotropic chemical shift data of isotopically labeled ghrelin provide information about the peptide’s secondary structure. Spin diffusion experiments indicate that ghrelin binds to membranes via its lipidated Ser3. Further, Phe4, as well as electrostatics involving the peptide’s positively charged residues and lipid polar headgroups, contribute to the binding energy. Other than the lipid anchor, ghrelin is highly flexible and mobile at the membrane surface. This observation is supported by our predicted model ensemble, which is in good agreement with experimentally determined chemical shifts. In the final ensemble of models, residues 8–17 form an α-helix, while residues 21–23 and 26–27 often adopt a polyproline II helical conformation. These helices appear to assist the peptide in forming an amphipathic conformation so that it can bind to the membrane. PMID:25803439

  13. 2D {sup 31}P solid state NMR spectroscopy, electronic structure and thermochemistry of PbP{sub 7}

    Energy Technology Data Exchange (ETDEWEB)

    Benndorf, Christopher [Institut für Anorganische und Analytische Chemie, Universität Münster, Corrensstraße 30, 48149 Münster (Germany); Institut für Physikalische Chemie, Universität Münster, Corrensstraße 30, 48149 Münster (Germany); Hohmann, Andrea; Schmidt, Peer [Brandenburgische Technische Universität Cottbus-Senftenberg, Fakultät für Naturwissenschaften, Postfach 101548, 01958 Senftenberg (Germany); Eckert, Hellmut, E-mail: [Institut für Physikalische Chemie, Universität Münster, Corrensstraße 30, 48149 Münster (Germany); Instituto de Física de Sao Carlos, Universidade de Sao Paulo, CEP 369, Sao Carlos, SP 13560-590 (Brazil); Johrendt, Dirk [Department Chemie, Ludwig-Maximilians-Universität München, Butenandtstraße 5-13, D-81377 München (Germany); and others


    Phase pure polycrystalline PbP{sub 7} was prepared from the elements via a lead flux. Crystalline pieces with edge-lengths up to 1 mm were obtained. The assignment of the previously published {sup 31}P solid state NMR spectrum to the seven distinct crystallographic sites was accomplished by radio-frequency driven dipolar recoupling (RFDR) experiments. As commonly found in other solid polyphosphides there is no obvious correlation between the {sup 31}P chemical shift and structural parameters. PbP{sub 7} decomposes incongruently under release of phosphorus forming liquid lead as remainder. The thermal decomposition starts at T>550 K with a vapor pressure almost similar to that of red phosphorus. Electronic structure calculations reveal PbP{sub 7} as a semiconductor according to the Zintl description and clearly shows the stereo-active Pb-6s{sup 2} lone pairs in the electron localization function ELF. - Graphical abstract: Coordination of the lead atoms in PbP{sub 7}.

  14. Solid-state and solution /sup 13/C NMR in the conformational analysis of methadone-hydrochloride and related narcotic analgesics

    Energy Technology Data Exchange (ETDEWEB)

    Sumner, S.C.J.


    Solid state and solution /sup 13/C NMR have been used to study the conformations of the racemic mixtures and single enantiomers of methadone hydrochloride, alpha and beta methadol hydrochloride, and alpha and beta acetylmethadol hydrochloride. The NMR spectra acquired for the compounds as solids, and in polar and nonpolar solvents are compared, in order to determine the conformation of the molecules in solution. To determine the reliability of assigning solution conformations by comparing solution and solid state chemical shift data, three bond coupling constants measured in solution are compared with those calculated from X-ray data. The conformations of the racemic mixture and plus enantiomer of methadone hydrochloride have been shown to be very similar in the solid state, where minor differences in conformation can be seen by comparing NMR spectra obtained for the solids. Also shown is that the molecules of methadone hydrochloride have conformations in polar and in nonpolar solvents which are very similar to the conformation of the molecules in the solid state.

  15. Detection of low-level PTFE contamination: An application of solid-state NMR to structure elucidation in the pharmaceutical industry. (United States)

    Pham, Tran N; Day, Caroline J; Edwards, Andrew J; Wood, Helen R; Lynch, Ian R; Watson, Simon A; Bretonnet, Anne-Sophie Z; Vogt, Frederick G


    We report a novel use of solid-state ¹⁹F nuclear magnetic resonance to detect and quantify polytetrafluoroethylene contamination from laboratory equipment, which due to low quantity (up to 1% w/w) and insolubility remained undetected by standard analytical techniques. Solid-state ¹⁹F NMR is shown to be highly sensitive to such fluoropolymers (detection limit 0.02% w/w), and is demonstrated as a useful analytical tool for structure elucidation of unknown solid materials. Copyright © 2010 Elsevier B.V. All rights reserved.

  16. Cryogenic solid state NMR studies of fibrils of the Alzheimer's disease amyloid-{beta} peptide: perspectives for DNP

    Energy Technology Data Exchange (ETDEWEB)

    Lopez del Amo, Juan-Miguel [CIC Energigune (Spain); Schneider, Dennis [Bruker BioSpin (Germany); Loquet, Antoine; Lange, Adam [Max-Planck-Institut fuer Biophysikalische Chemie (Germany); Reif, Bernd, E-mail: [Deutsches Forschungszentrum fuer Gesundheit und Umwelt, Helmholtz-Zentrum Muenchen (HMGU) (Germany)


    Dynamic Nuclear Polarization solid-state NMR holds the potential to enable a dramatic increase in sensitivity by exploiting the large magnetic moment of the electron. However, applications to biological solids are hampered in uniformly isotopically enriched biomacromolecules due to line broadening which yields a limited spectral resolution at cryogenic temperatures. We show here that high magnetic fields allow to overcome the broadening of resonance lines often experienced at liquid nitrogen temperatures. For a fibril sample of the Alzheimer's disease {beta}-amyloid peptide, we find similar line widths at low temperature and at room temperature. The presented results open new perspectives for structural investigations in the solid-state.

  17. Synthesis of Mesoporous Silica Monoliths — A Novel Approach Towards Fabrication of Solid-State Optical Sensors for Environmental Applications (United States)

    Prabhakaran, D.; Subashini, C.; Akhila Maheswari, M.


    Mesoporous silica monoliths are an attractive area of research owing to their high specific surface area, uniform channels and mesoporous size (2-30nm). This paper deals with the direct templating synthesis of a mesoporous worm-like silica monolithic material using F127 — a triblock copolymer, by micro-emulsion technique using trimethyl benzene (TMB), as the solvent. The synthesized silica monolith is characterized using SEM-EDAX, XRD, BET, NMR and FT-IR. The monolith shows an ordered worm-like mesoporous structure with tuneable through pores, an excellent host for the anchoring of chromo-ionophores for the naked-eye metal ion-sensing. The mesoporous monoliths were loaded with 4-dodecyl-6-(2-pyridylazo)-phenol (DPAP) ligand through direct immobilization, thereby acting as solid-state naked-eye colorimetric ion-sensors for the sensing toxic Pb(II) ions at parts-per-billion (ppb) level in various industrial and environmental systems. The influence of various experimental parameters such as solution pH, limiting ligand loading concentration, amount of monolith material, matrix tolerance level, limit of detection and quantification has been studied and optimized.

  18. In situ solid-state NMR and XRD studies of the ADOR process and the unusual structure of zeolite IPC-6 (United States)

    Morris, Samuel A.; Bignami, Giulia P. M.; Tian, Yuyang; Navarro, Marta; Firth, Daniel S.; Čejka, Jiří; Wheatley, Paul S.; Dawson, Daniel M.; Slawinski, Wojciech A.; Wragg, David S.; Morris, Russell E.; Ashbrook, Sharon E.


    The assembly-disassembly-organization-reassembly (ADOR) mechanism is a recent method for preparing inorganic framework materials and, in particular, zeolites. This flexible approach has enabled the synthesis of isoreticular families of zeolites with unprecedented continuous control over porosity, and the design and preparation of materials that would have been difficult—or even impossible—to obtain using traditional hydrothermal techniques. Applying the ADOR process to a parent zeolite with the UTL framework topology, for example, has led to six previously unknown zeolites (named IPC-n, where n = 2, 4, 6, 7, 9 and 10). To realize the full potential of the ADOR method, however, a further understanding of the complex mechanism at play is needed. Here, we probe the disassembly, organization and reassembly steps of the ADOR process through a combination of in situ solid-state NMR spectroscopy and powder X-ray diffraction experiments. We further use the insight gained to explain the formation of the unusual structure of zeolite IPC-6.

  19. A solid state NMR study of layered double hydroxides intercalated with para-amino salicylate, a tuberculosis drug

    DEFF Research Database (Denmark)

    Jensen, Nicholai Daugaard; Bjerring, Morten; Nielsen, Ulla Gro


    ), elemental analysis and IR-spectroscopy to gain insight into the bulk and atomic level structure of these LDHs especially with a view to the purity of the LDH-PAS materials and the concentration of impurities. The intercalations of PAS in MgAl-, ZnAl-, and CaAl-LDH's were confirmed by 13C SSNMR and PXRD....... Moreover, 13C MAS NMR and infra-red spectroscopy show that PAS did not decompose during synthesis. Large amounts (20-41%) of amorphous aluminum impurities were detected in the structure using 27Al single pulse and 3QMAS NMR spectra, which in combination with 1H single and double quantum experiments also...

  20. Sensitivity and Resolution Enhanced Solid-State NMR for Paramagnetic Systems and Biomolecules under Very Fast Magic Angle Spinning

    KAUST Repository

    Parthasarathy, Sudhakar


    Recent research in fast magic angle spinning (MAS) methods has drastically improved the resolution and sensitivity of NMR spectroscopy of biomolecules and materials in solids. In this Account, we summarize recent and ongoing developments in this area by presenting (13)C and (1)H solid-state NMR (SSNMR) studies on paramagnetic systems and biomolecules under fast MAS from our laboratories. First, we describe how very fast MAS (VFMAS) at the spinning speed of at least 20 kHz allows us to overcome major difficulties in (1)H and (13)C high-resolution SSNMR of paramagnetic systems. As a result, we can enhance both sensitivity and resolution by up to a few orders of magnitude. Using fast recycling (∼ms/scan) with short (1)H T1 values, we can perform (1)H SSNMR microanalysis of paramagnetic systems on the microgram scale with greatly improved sensitivity over that observed for diamagnetic systems. Second, we discuss how VFMAS at a spinning speed greater than ∼40 kHz can enhance the sensitivity and resolution of (13)C biomolecular SSNMR measurements. Low-power (1)H decoupling schemes under VFMAS offer excellent spectral resolution for (13)C SSNMR by nominal (1)H RF irradiation at ∼10 kHz. By combining the VFMAS approach with enhanced (1)H T1 relaxation by paramagnetic doping, we can achieve extremely fast recycling in modern biomolecular SSNMR experiments. Experiments with (13)C-labeled ubiquitin doped with 10 mM Cu-EDTA demonstrate how effectively this new approach, called paramagnetic assisted condensed data collection (PACC), enhances the sensitivity. Lastly, we examine (13)C SSNMR measurements for biomolecules under faster MAS at a higher field. Our preliminary (13)C SSNMR data of Aβ amyloid fibrils and GB1 microcrystals acquired at (1)H NMR frequencies of 750-800 MHz suggest that the combined use of the PACC approach and ultrahigh fields could allow for routine multidimensional SSNMR analyses of proteins at the 50-200 nmol level. Also, we briefly discuss the

  1. 51V Solid-state NMR and Density-Functional Theory Studies of Eight-Coordinate Non-Oxo Vanadium Complexes: Oxidized Amavadin (United States)

    Ooms, Kristopher J.; Bolte, Stephanie E.; Baruah, Bharat; Choudhary, Muhammad Aziz; Crans, Debbie C.; Polenova, Tatyana


    SUMMARY Using 51V magic angle spinning solid-state NMR spectroscopy and Density Functional Theory calculations we have characterized the chemical shift and quadrupolar coupling parameters for two eight-coordinate vanadium complexes, [PPh4][V(V)(HIDPA)2] and [PPh4][V(V)(HIDA)2]; HIDPA = 2,2′-(hydroxyimino)dipropionate and HIDA = 2,2′-(hydroxyimino)diacetate. The coordination geometry under examination is the less common non-oxo eight coordinate distorted dodecahedral geometry that has not been previously investigated by solid-state NMR spectroscopy. Both complexes were isolated by oxidizing their reduced forms: [V(IV)(HIDPA)2]2- and [V(IV)(HIDA)2]2-. V(IV)(HIDPA)22- is also known as amavadin, a vanadium-containing natural product present in the Amanita muscaria mushroom and responsible for vanadium accumulation in nature. The quadrupolar coupling constants, CQ, are found to be moderate, 5.0 to 6.4 MHz while the chemical shift anisotropies are relatively small for vanadium complexes, −420 and 360 ppm. The isotropic chemical shifts in the solid state are −220 and −228 ppm for the two compounds, and near the chemical shifts observed in solution. Presumably this is a consequence of the combined effects of the increased coordination number and the absence of oxo groups. Density Functional Theory calculations of the electric field gradient parameters are in good agreement with the NMR results while the chemical shift parameters show some deviation from the experimental values. Future work on this unusual coordination geometry and a combined analysis by solid-state NMR and Density Functional Theory should provide a better understanding of the correlations between experimental NMR parameters and the local structure of the vanadium centers. PMID:19421628

  2. ¹³C solid-state NMR analysis of the most common pharmaceutical excipients used in solid drug formulations, Part I: Chemical shifts assignment. (United States)

    Pisklak, Dariusz Maciej; Zielińska-Pisklak, Monika Agnieszka; Szeleszczuk, Łukasz; Wawer, Iwona


    Solid-state NMR is an excellent and useful method for analyzing solid-state forms of drugs. In the (13)C CP/MAS NMR spectra of the solid dosage forms many of the signals originate from the excipients and should be distinguished from those of active pharmaceutical ingredient (API). In this work the most common pharmaceutical excipients used in the solid drug formulations: anhydrous α-lactose, α-lactose monohydrate, mannitol, sucrose, sorbitol, sodium starch glycolate type A and B, starch of different origin, microcrystalline cellulose, hypromellose, ethylcellulose, methylcellulose, hydroxyethylcellulose, sodium alginate, magnesium stearate, sodium laurilsulfate and Kollidon(®) were analyzed. Their (13)C CP/MAS NMR spectra were recorded and the signals were assigned, employing the results (R(2): 0.948-0.998) of GIPAW calculations and theoretical chemical shifts. The (13)C ssNMR spectra for some of the studied excipients have not been published before while for the other signals in the spectra they were not properly assigned or the assignments were not correct. The results summarize and complement the data on the (13)C ssNMR analysis of the most common pharmaceutical excipients and are essential for further NMR studies of API-excipient interactions in the pharmaceutical formulations. Copyright © 2016 Elsevier B.V. All rights reserved.

  3. Solid State Division

    Energy Technology Data Exchange (ETDEWEB)

    Green, P.H.; Watson, D.M. (eds.)


    This report contains brief discussions on work done in the Solid State Division of Oak Ridge National Laboratory. The topics covered are: Theoretical Solid State Physics; Neutron scattering; Physical properties of materials; The synthesis and characterization of materials; Ion beam and laser processing; and Structure of solids and surfaces. (LSP)

  4. Polydisperse methyl β-cyclodextrin–epichlorohydrin polymers: variable contact time 13C CP-MAS solid-state NMR characterization (United States)

    Mallard, Isabelle; Baudelet, Davy; Castiglione, Franca; Ferro, Monica; Panzeri, Walter; Ragg, Enzio


    Summary The polymerization of partially methylated β-cyclodextrin (CRYSMEB) with epichlorohydrin was carried out in the presence of a known amount of toluene as imprinting agent. Three different preparations (D1, D2 and D3) of imprinted polymers were obtained and characterized by solid-state 13C NMR spectroscopy under cross-polarization magic angle spinning (CP-MAS) conditions. The polymers were prepared by using the same synthetic conditions but with different molar ratios of imprinting agent/monomer, leading to morphologically equivalent materials but with different absorption properties. The main purpose of the work was to find a suitable spectroscopic descriptor accounting for the different imprinting process in three homogeneous polymeric networks. The polymers were characterized by studying the kinetics of the cross-polarization process. This approach is based on variable contact time CP-MAS spectra, referred to as VCP-MAS. The analysis of the VCP-MAS spectra provided two relaxation parameters: T CH (the CP time constant) and T 1ρ (the proton spin-lattice relaxation time in the rotating frame). The results and the analysis presented in the paper pointed out that T CH is sensitive to the imprinting process, showing variations related to the toluene/cyclodextrin molar ratio used for the preparation of the materials. Conversely, the observed values of T 1ρ did not show dramatic variations with the imprinting protocol, but rather confirmed that the three polymers are morphologically similar. Thus the combined use of T CH and T 1ρ can be helpful for the characterization and fine tuning of imprinted polymeric matrices. PMID:26877800

  5. Water-polysaccharide interactions in the primary cell wall of Arabidopsis thaliana from polarization transfer solid-state NMR. (United States)

    White, Paul B; Wang, Tuo; Park, Yong Bum; Cosgrove, Daniel J; Hong, Mei


    Polysaccharide-rich plant cell walls are hydrated under functional conditions, but the molecular interactions between water and polysaccharides in the wall have not been investigated. In this work, we employ polarization transfer solid-state NMR techniques to study the hydration of primary-wall polysaccharides of the model plant, Arabidopsis thaliana. By transferring water (1)H polarization to polysaccharides through distance- and mobility-dependent (1)H-(1)H dipolar couplings and detecting it through polysaccharide (13)C signals, we obtain information about water proximity to cellulose, hemicellulose, and pectins as well as water mobility. Both intact and partially extracted cell wall samples are studied. Our results show that water-pectin polarization transfer is much faster than water-cellulose polarization transfer in all samples, but the extent of extraction has a profound impact on the water-polysaccharide spin diffusion. Removal of calcium ions and the consequent extraction of homogalacturonan (HG) significantly slowed down spin diffusion, while further extraction of matrix polysaccharides restored the spin diffusion rate. These trends are observed in cell walls with similar water content, thus they reflect inherent differences in the mobility and spatial distribution of water. Combined with quantitative analysis of the polysaccharide contents, our results indicate that calcium ions and HG gelation increase the amount of bound water, which facilitates spin diffusion, while calcium removal disrupts the gel and gives rise to highly dynamic water, which slows down spin diffusion. The recovery of spin diffusion rates after more extensive extraction is attributed to increased water-exposed surface areas of the polysaccharides. Water-pectin spin diffusion precedes water-cellulose spin diffusion, lending support to the single-network model of plant primary walls in which a substantial fraction of the cellulose surface is surrounded by pectins.

  6. Amyloid Hydrogen Bonding Polymorphism Evaluated by (15)N{(17)O}REAPDOR Solid-State NMR and Ultra-High Resolution Fourier Transform Ion Cyclotron Resonance Mass Spectrometry. (United States)

    Wei, Juan; Antzutkin, Oleg N; Filippov, Andrei V; Iuga, Dinu; Lam, Pui Yiu; Barrow, Mark P; Dupree, Ray; Brown, Steven P; O'Connor, Peter B


    A combined approach, using Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) and solid-state NMR (Nuclear Magnetic Resonance), shows a high degree of polymorphism exhibited by Aβ species in forming hydrogen-bonded networks. Two Alzheimer's Aβ peptides, Ac-Aβ(16-22)-NH2 and Aβ(11-25), selectively labeled with (17)O and (15)N at specific amino acid residues were investigated. The total amount of peptides labeled with (17)O as measured by FTICR-MS enabled the interpretation of dephasing observed in (15)N{(17)O}REAPDOR solid-state NMR experiments. Specifically, about one-third of the Aβ peptides were found to be involved in the formation of a specific >C═(17)O···H-(15)N hydrogen bond with their neighbor peptide molecules, and we hypothesize that the rest of the molecules undergo ± n off-registry shifts in their hydrogen bonding networks.

  7. (25)Mg Solid-State NMR: A Sensitive Probe of Adsorbing Guest Molecules on a Metal Center in Metal-Organic Framework CPO-27-Mg. (United States)

    Xu, Jun; Terskikh, Victor V; Huang, Yining


    Metal-organic frameworks (MOFs) have excellent adsorption capability. To understand their adsorptive properties requires detailed information on the host-guest interaction. The information on MOF desolvation (or activation) is also crucial because the very first step of many applications requires removal of the solvent molecules occluded inside of the pores. Unfortunately, such information is not always available from powder XRD data. Solid-state NMR is an excellent complementary technique to XRD. CPO-27-Mg is a MOF with unusual adsorption ability. The adsorption involves a direct interaction between Mg and guest species. Herein, we present, for the first time, a natural abundance (25)Mg solid-state NMR study of CPO-27-Mg at an ultrahigh magnetic field of 21.1 T. The results provide new physical insights into the effects of dehydration/rehydration and adsorption of guest species on the Mg local environment.

  8. Mechanism of formation of humus coatings on mineral surfaces 3. Composition of adsorbed organic acids from compost leachate on alumina by solid-state 13C NMR (United States)

    Wershaw, R. L.; Llaguno, E.C.; Leenheer, J.A.


    The adsorption of compost leachate DOC on alumina is used as a model for elucidation of the mechanism of formation of natural organic coatings on hydrous metal oxide surfaces in soils and sediments. Compost leachate DOC is composed mainly of organic acid molecules. The solid-state 13C NMR spectra of these organic acids indicate that they are very similar in composition to aquatic humic substances. Changes in the solid-state 13C NMR spectra of compost leachate DOC fractions adsorbed on alumina indicate that the DOC molecules are most likely adsorbed on metal oxide surfaces through a combination of polar and hydrophobic interaction mechanisms. This combination of polar and hydrophobic mechanism leads to the formation of bilayer coatings of the leachate molecules on the oxide surfaces.

  9. A General Solid-State Synthesis of Chemically-Doped Fluorescent Graphene Quantum Dots for Bioimaging and Optoelectronic Applications

    KAUST Repository

    Ma, Chong-Bo


    Graphene quantum dots (GQDs) have attracted increasing interest because of their excellent properties such as strong photoluminescence, excellent biocompatibility and low cost. Herein, we develop a general method for the synthesis of doped and undoped GQDs, which relies on direct carbonization of organic precursors at solid state.

  10. Characteristics and degradation of carbon and phosphorus from aquatic macrophytes in lakes: Insights from solid-state {sup 13}C NMR and solution {sup 31}P NMR spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Shasha [College of Water Sciences, Beijing Normal University, Beijing 100875 (China); State Key Laboratory of Environment Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing 100012 (China); Zhu, Yuanrong, E-mail: [State Key Laboratory of Environment Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing 100012 (China); Meng, Wei, E-mail: [State Key Laboratory of Environment Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing 100012 (China); He, Zhongqi [USDA-ARS Southern Regional Research Center, 1100 Robert E Lee Blvd, New Orleans, LA 70124 (United States); Feng, Weiying [College of Water Sciences, Beijing Normal University, Beijing 100875 (China); State Key Laboratory of Environment Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing 100012 (China); Zhang, Chen [State Key Laboratory of Environment Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing 100012 (China); Giesy, John P. [State Key Laboratory of Environment Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing 100012 (China); Department of Biomedical and Veterinary Biosciences and Toxicology Centre, University of Saskatchewan, Saskatoon, Saskatchewan (Canada)


    Water extractable organic matter (WEOM) derived from macrophytes plays an important role in biogeochemical cycling of nutrients, including carbon (C), nitrogen (N) and phosphorus (P) in lakes. However, reports of their composition and degradation in natural waters are scarce. Therefore, compositions and degradation of WEOM derived from six aquatic macrophytes species of Tai Lake, China, were investigated by use of solid-state {sup 13}C NMR and solution {sup 31}P NMR spectroscopy. Carbohydrates were the predominant constituents of WEOM fractions, followed by carboxylic acid. Orthophosphate (ortho-P) was the dominant form of P (78.7% of total dissolved P) in the water extracts, followed by monoester P (mono-P) (20.6%) and little diester P (0.65%). The proportion of mono-P in total P species increased with the percentage of O-alkyl and O–C–O increasing in the WEOM, which is likely due to degradation and dissolution of biological membranes and RNA from aquatic plants. Whereas the proportion of mono-P decreased with alkyl-C, NCH/OCH{sub 3} and COO/N–C=O increasing, which may be owing to the insoluble compounds including C functional groups of alkyl-C, NCH/OCH{sub 3} and COO/N–C=O, such as aliphatic biopolymers, lignin and peptides. Based on the results of this study and information in the literature about water column and sediment, we propose that WEOM, dominated by polysaccharides, are the most labile and bioavailable component in debris of macrophytes. Additionally, these WEOMs would also be a potential source for bioavailable organic P (e.g., RNA, DNA and phytate) for lakes. - Highlights: • WEOM derived from aquatic macrophytes was characterized. • C and P in WEOM were characterized by solid {sup 13}C NMR and solution {sup 31}P NMR. • Degradation and transformation of macrophyte-derived C and P were investigated. • Macrophyte-derived WEOM are important source for bioavailable nutrients in lakes.

  11. Solid-state NMR analysis of a peptide (Gly-Pro-Gly-Gly-Ala)6-Gly derived from a flagelliform silk sequence of Nephila clavipes. (United States)

    Ohgo, Kosuke; Kawase, Taiji; Ashida, Jun; Asakura, Tetsuo


    Solid-state NMR is especially useful when the structures of peptides and proteins should be analyzed by taking into account the structural distribution, that is, the distribution of the torsion angle of the individual residue. In this study, two-dimensional spin-diffusion solid-state NMR spectra of 13C-double-labeled model peptides (GPGGA)6G of flagelliform silk were observed for studying the local structure in the solid state. The spin-diffusion NMR spectra calculated by assuming the torsion angles of the beta-spiral structure exclusively could not reproduce the observed spectra. In contrast, the spectra calculated by taking into account the statistical distribution of the torsion angles of the individual central residues in the sequences Ala-Gly-Pro, Gly-Pro-Gly, Pro-Gly-Gly, Gly-Gly-Ala, and Gly-Ala-Gly from PDB data could reproduce the observed spectra well. This indicates that the statistical distribution of the torsion angles should be considered for the structural model of (GPGGA)6G similar to the case of the model peptide of elastin.

  12. Characteristics and degradation of carbon and phosphorus from aquatic macrophytes in lakes: Insights from solid-state (13)C NMR and solution (31)P NMR spectroscopy. (United States)

    Liu, Shasha; Zhu, Yuanrong; Meng, Wei; He, Zhongqi; Feng, Weiying; Zhang, Chen; Giesy, John P


    Water extractable organic matter (WEOM) derived from macrophytes plays an important role in biogeochemical cycling of nutrients, including carbon (C), nitrogen (N) and phosphorus (P) in lakes. However, reports of their composition and degradation in natural waters are scarce. Therefore, compositions and degradation of WEOM derived from six aquatic macrophytes species of Tai Lake, China, were investigated by use of solid-state (13)C NMR and solution (31)P NMR spectroscopy. Carbohydrates were the predominant constituents of WEOM fractions, followed by carboxylic acid. Orthophosphate (ortho-P) was the dominant form of P (78.7% of total dissolved P) in the water extracts, followed by monoester P (mono-P) (20.6%) and little diester P (0.65%). The proportion of mono-P in total P species increased with the percentage of O-alkyl and O-C-O increasing in the WEOM, which is likely due to degradation and dissolution of biological membranes and RNA from aquatic plants. Whereas the proportion of mono-P decreased with alkyl-C, NCH/OCH3 and COO/N-C=O increasing, which may be owing to the insoluble compounds including C functional groups of alkyl-C, NCH/OCH3 and COO/N-C=O, such as aliphatic biopolymers, lignin and peptides. Based on the results of this study and information in the literature about water column and sediment, we propose that WEOM, dominated by polysaccharides, are the most labile and bioavailable component in debris of macrophytes. Additionally, these WEOMs would also be a potential source for bioavailable organic P (e.g., RNA, DNA and phytate) for lakes. Copyright © 2015 Elsevier B.V. All rights reserved.

  13. La{sub 3}Cu{sub 4}P{sub 4}O{sub 2} and La{sub 5}Cu{sub 4}P{sub 4}O{sub 4}Cl{sub 2}. Synthesis, structure and {sup 31}P solid state NMR spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Bartsch, Timo; Eul, Matthias; Poettgen, Rainer [Muenster Univ. (Germany). Inst. fuer Anorganische und Analytische Chemie; Benndorf, Christopher; Eckert, Hellmut [Muenster Univ. (Germany). Inst. fuer Physikalische Chemie; Sao Paulo Univ., Sao Carlos, SP (Brazil). Inst. of Physics


    The phosphide oxides La{sub 3}Cu{sub 4}P{sub 4}O{sub 2} and La{sub 5}Cu{sub 4}P{sub 4}O{sub 4}Cl{sub 2} were synthesized from lanthanum, copper(I) oxide, red phosphorus, and lanthanum(III) chloride through a ceramic technique. Single crystals can be grown in a NaCl/KCl flux. Both structures were refined from single crystal X-ray diffractometer data: I4/mmm, a = 403.89(4), c = 2681.7(3) pm, wR2 = 0.0660, 269 F{sup 2} values, 19 variables for La{sub 3}Cu{sub 4}P{sub 4}O{sub 2} and a = 407.52(5), c = 4056.8(7) pm, wR2 = 0.0905, 426 F{sup 2} values, 27 variables for La{sub 5}Cu{sub 4}P{sub 4}O{sub 4}Cl{sub 2}. Refinement of the occupancy parameters revealed full occupancy for the oxygen sites in both compounds. The structures are composed of cationic (La{sub 2}O{sub 2}){sup 2+} layers and covalently bonded (Cu{sub 4}P{sub 4}){sup 5-} polyanionic layers with metallic characteristics, and an additional La{sup 3+} between two adjacent (Cu{sub 4}P{sub 4}){sup 5-} layers. The structure of La{sub 5}Cu{sub 4}P{sub 4}O{sub 4}Cl{sub 2} comprises two additional LaOCl slabs per unit cell. Temperature-dependent magnetic susceptibility studies revealed Pauli paramagnetism. The phosphide substructure of La{sub 3}Cu{sub 4}P{sub 4}O{sub 2} was studied by {sup 31}P solid state NMR spectroscopy. By using a suitable dipolar re-coupling approach the two distinct resonances belonging to the P{sub 2}{sup 4-} and the P{sup 3-} units could be identified.

  14. Solid-State 13C NMR Spectroscopy Applied to the Study of Carbon Blacks and Carbon Deposits Obtained by Plasma Pyrolysis of Natural Gas

    Directory of Open Access Journals (Sweden)

    Jair C. C. Freitas


    Full Text Available Solid-state 13C nuclear magnetic resonance (NMR spectroscopy was used in this work to analyze the physical and chemical properties of plasma blacks and carbon deposits produced by thermal cracking of natural gas using different types of plasma reactors. In a typical configuration with a double-chamber reactor, N2 or Ar was injected as plasma working gas in the first chamber and natural gas was injected in the second chamber, inside the arc column. The solid residue was collected at different points throughout the plasma apparatus and analyzed by 13C solid-state NMR spectroscopy, using either cross polarization (CP or direct polarization (DP, combined with magic angle spinning (MAS. The 13C CP/MAS NMR spectra of a number of plasma blacks produced in the N2 plasma reactor showed two resonance bands, broadly identified as associated with aromatic and aliphatic groups, with indication of the presence of oxygen- and nitrogen-containing groups in the aliphatic region of the spectrum. In contrast to DP experiments, only a small fraction of 13C nuclei in the plasma blacks are effectively cross-polarized from nearby 1H nuclei and are thus observed in spectra recorded with CP. 13C NMR spectra are thus useful to distinguish between different types of carbon species in plasma blacks and allow a selective study of groups spatially close to hydrogen in the material.

  15. Extensive de novo solid-state NMR assignments of the 33 kDa C-terminal domain of the Ure2 prion

    Energy Technology Data Exchange (ETDEWEB)

    Habenstein, Birgit [UMR 5086 CNRS/Universite de Lyon 1, Institut de Biologie et Chimie des Proteines (France); Wasmer, Christian [Harvard Medical School (United States); Bousset, Luc; Sourigues, Yannick [UPR 3082 CNRS, Laboratoire d' Enzymologie et Biochimie Structurales (France); Schuetz, Anne [ETH Zurich, Physical Chemistry (Switzerland); Loquet, Antoine [Max Planck Institute for Biophysical Chemistry (Germany); Meier, Beat H., E-mail: [ETH Zurich, Physical Chemistry (Switzerland); Melki, Ronald, E-mail: [UPR 3082 CNRS, Laboratoire d' Enzymologie et Biochimie Structurales (France); Boeckmann, Anja, E-mail: [UMR 5086 CNRS/Universite de Lyon 1, Institut de Biologie et Chimie des Proteines (France)


    We present the de novo resonance assignments for the crystalline 33 kDa C-terminal domain of the Ure2 prion using an optimized set of five 3D solid-state NMR spectra. We obtained, using a single uniformly {sup 13}C, {sup 15}N labeled protein sample, sequential chemical-shift information for 74% of the N, C{alpha}, C{beta} triples, and for 80% of further side-chain resonances for these spin systems. We describe the procedures and protocols devised, and discuss possibilities and limitations of the assignment of this largest protein assigned today by solid-state NMR, and for which no solution-state NMR shifts were available. A comparison of the NMR chemical shifts with crystallographic data reveals that regions with high crystallographic B-factors are particularly difficult to assign. While the secondary structure elements derived from the chemical shift data correspond mainly to those present in the X-ray crystal structure, we detect an additional helical element and structural variability in the protein crystal, most probably originating from the different molecules in the asymmetric unit, with the observation of doubled resonances in several parts, including entire stretches, of the protein. Our results provide the point of departure towards an atomic-resolution structural analysis of the C-terminal Ure2p domain in the context of the full-length prion fibrils.

  16. A study of tin dioxide and antimony tetroxide supported vanadium oxide catalysts by solid-state 51V and 1H NMR techniques. (United States)

    Reddy, B M; Mastikhin, V M


    A series of vanadia catalysts with various V2O5 loadings supported on SnO2 and alpha-Sb2O4 are investigated by the application of X-ray diffraction and solid-state 51V and 1H NMR techniques. XRD results show no evidence for the formation of a crystalline vanadia phase on both supports. However, the 51V NMR spectra of the catalysts reveal the existence of two types of vanadia species on the surface of the support: one due to a dispersed vanadia phase at lower vanadia loadings and the other due to a crystalline vanadia phase at higher vanadium content. The quantity of the dispersed vanadia phase, however, depends on the nature of the support material. The 1H NMR results provide evidence for the existence or non-existence of a metal oxide support interaction through the support surface hydroxyl groups.

  17. Hydration properties and phosphorous speciation in native, gelatinized and enzymatically modified potato starch analyzed by solid-state MAS NMR

    DEFF Research Database (Denmark)

    Larsen, Flemming Hofmann; Kasprzak, Miroslaw Marek; Lærke, Helle Nygaard


    by enzyme-assisted catalytic branching with branching enzyme (BE) or combined BE and β-amylase (BB) catalyzed exo-hydrolysis. Carbons of the glycosidic α-1,6 linkages required high hydration rates before adopting uniform chemical shifts indicating solid-state disorder and poor water accessibility...

  18. Multiple Acquisition of Magic Angle Spinning Solid-State NMR Experiments Using One Receiver: Application to Microcrystalline and Membrane Protein Preparations (United States)

    Gopinath, T.; Veglia, Gianluigi


    Solid-State NMR spectroscopy of proteins is a notoriously low-throughput technique. Relatively low-sensitivity and poor resolution of protein samples require long acquisition times for multidimensional NMR experiments. To speed up data acquisition, we developed a family of experiments called Polarization Optimized Experiments (POE), in which we utilized the orphan spin operators that are discarded in classical multidimensional NMR experiments, recovering them to allow simultaneous acquisition of multiple 2D and 3D experiments, all while using conventional probes with spectrometers equipped with one receiver. POEs allow the concatenation of multiple 2D or 3D pulse sequences into a single experiment, thus potentially combining all of the aforementioned advances, boosting the capability of ssNMR spectrometers at least two-fold without the addition of any hardware. In this Perspective, we describe the first generation of POEs, such as dual acquisition MAS (or DUMAS) methods, and then illustrate the evolution of these experiments into MEIOSIS, a method that enables the simultaneous acquisition of multiple 2D and 3D spectra. Using these new pulse schemes for the solid-state NMR investigation of biopolymers makes it possible to obtain sequential resonance assignments, as well as distance restraints, in about half the experimental time. While designed for acquisition of heteronuclei, these new experiments can be easily implemented for proton detection and coupled with other recent advancements, such as dynamic polarization, to improve signal to noise. Finally, we illustrate the application of these methods to microcrystalline protein preparations as well as single and multi-span membrane proteins reconstituted in lipid membranes. PMID:25797011

  19. Synthesis and NMR Elucidation of Novel Pentacycloundecane ...

    African Journals Online (AJOL)

    Herein we report the synthesis and NMR elucidation of five novel pentacycloundecane (PCU)-derived short peptides as potential HIV protease inhibitors. 1H and 13C spectral analysis show major overlapping of methine resonance of the PCU 'cage' thereby making it extremely difficult to assign the NMR signals. Attachment ...

  20. All-Solid-State Mechanochemical Synthesis and Post-Synthetic Transformation of Inorganic Perovskite-type Halides. (United States)

    Pal, Provas; Saha, Sujoy; Banik, Ananya; Sarkar, Arka; Biswas, Kanishka


    All-inorganic and hybrid perovskite type halides are generally synthesized by solution-based methods, with the help of long chain organic capping ligands, complex organometallic precursors, and high boiling organic solvents. Herein, a room temperature, solvent-free, general, and scalable all-solid-state mechanochemical synthesis is demonstrated for different inorganic perovskite type halides, with versatile structural connectivity in three (3D), two (2D), and zero (0D) dimensions. 3D CsPbBr 3 , 2D CsPb 2 Br 5 , 0D Cs 4 PbBr 6 , 3D CsPbCl 3 , 2D CsPb 2 Cl 5 , 0D Cs 4 PbCl 6 , 3D CsPbI 3 , and 3D RbPbI 3 have all been synthesized by this method. The all-solid-state synthesis is materialized through an inorganic retrosynthetic approach, which directs the decision on the solid-state precursors (e.g., CsX and PbX 2 (X=Cl/Br/I) with desired stoichiometric ratios. Moreover, post-synthetic structural transformations from 3D to 2D and 0D perovskite halides were performed by the same mechanochemical synthetic approach at room temperature. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Study of water dynamics in the soaking, steaming, and solid-state fermentation of glutinous rice by LF-NMR: a novel monitoring approach. (United States)

    Li, Teng; Tu, Chuanhai; Rui, Xin; Gao, Yangwen; Li, Wei; Wang, Kun; Xiao, Yu; Dong, Mingsheng


    Solid-state fermentation (SSF) of starchy grain is a traditional technique for food and alcoholic beverage production in East Asia. In the present study, low-field nuclear magnetic resonance (LF-NMR) was introduced for the elucidation of water dynamics and microstructure alternations during the soaking, steaming, and SSF of glutinous rice as a rapid real-time monitoring method. Three different proton fractions with different mobilities were identified based on the degree of interaction between biopolymers and water. Soaking and steaming significantly changed the proton distribution of the sample. The different phases of SSF were reflected by the T2 parameters. In addition, the variations in the T2 parameters were explained by the microstructure changes of rice induced by SSF. The fermentation time and T2 parameters were sigmoidally correlated. Thus, LF-NMR may be an effective real-time monitoring method for SSF in starch systems.

  2. Specific molecular structure changes and radical evolution during biomass-polyethylene terephthalate co-pyrolysis detected by (13)C and (1)H solid-state NMR. (United States)

    Ko, Kwang-Hyun; Sahajwalla, Veena; Rawal, Aditya


    Co-pyrolysis of biomass with polyethylene terephthalate (PET) was studied as a function of blend ratio and co-pyrolysis temperature by (13)C and (1)H solid-state nuclear magnetic resonance (NMR). The (13)C NMR spectra showed that upon heating to 400°C in presence of the biomass, the formation of crystallites in PET was completely suppressed and that at higher temperatures there was increased formation and growth of the polycyclic aromatic hydrocarbons (PAHs). This change in the PET degradation behaviour was attributed to the presence of radicals formed in char from biomass. The measurement of the (1)H-T1 relaxation enabled monitoring the changes in the concentrations of radicals formed, as a function of the blend ratios and the co-pyrolysis temperatures. It indicated that the increase in the radical concentrations correlated well with the increased degradation of the PET and growth of PAHs. Copyright © 2014. Published by Elsevier Ltd.

  3. Solid-State synthesis of POPD@AgNPs nanocomposites for electrochemical sensors

    CSIR Research Space (South Africa)

    Paulraj, P


    Full Text Available In the present work, Poly(o-phenylenediamine) (POPD) stabilized silver nanoparticles (POPD@AgNPs) nanocomposites was synthesized by solid state oxidative polymerization method using o-phenylenediamine dihydrochloride (oPD-HCl) as monomer and silver...

  4. Chemical and nanometer-scale structure of kerogen and its change during thermal maturation investigated by advanced solid-state 13C NMR spectroscopy (United States)

    Mao, J.; Fang, X.; Lan, Y.; Schimmelmann, A.; Mastalerz, Maria; Xu, L.; Schmidt-Rohr, K.


    We have used advanced and quantitative solid-state nuclear magnetic resonance (NMR) techniques to investigate structural changes in a series of type II kerogen samples from the New Albany Shale across a range of maturity (vitrinite reflectance R0 from 0.29% to 1.27%). Specific functional groups such as CH3, CH2, alkyl CH, aromatic CH, aromatic C-O, and other nonprotonated aromatics, as well as "oil prone" and "gas prone" carbons, have been quantified by 13C NMR; atomic H/C and O/C ratios calculated from the NMR data agree with elemental analysis. Relationships between NMR structural parameters and vitrinite reflectance, a proxy for thermal maturity, were evaluated. The aromatic cluster size is probed in terms of the fraction of aromatic carbons that are protonated (???30%) and the average distance of aromatic C from the nearest protons in long-range H-C dephasing, both of which do not increase much with maturation, in spite of a great increase in aromaticity. The aromatic clusters in the most mature sample consist of ???30 carbons, and of ???20 carbons in the least mature samples. Proof of many links between alkyl chains and aromatic rings is provided by short-range and long-range 1H-13C correlation NMR. The alkyl segments provide most H in the samples; even at a carbon aromaticity of 83%, the fraction of aromatic H is only 38%. While aromaticity increases with thermal maturity, most other NMR structural parameters, including the aromatic C-O fractions, decrease. Aromaticity is confirmed as an excellent NMR structural parameter for assessing thermal maturity. In this series of samples, thermal maturation mostly increases aromaticity by reducing the length of the alkyl chains attached to the aromatic cores, not by pronounced growth of the size of the fused aromatic ring clusters. ?? 2010 Elsevier Ltd. All rights reserved.

  5. Comparative analysis of the orientation of transmembrane peptides using solid-state (2)H- and (15)N-NMR: mobility matters. (United States)

    Grage, Stephan L; Strandberg, Erik; Wadhwani, Parvesh; Esteban-Martín, Santiago; Salgado, Jesús; Ulrich, Anne S


    Many solid-state nuclear magnetic resonance (NMR) approaches for membrane proteins rely on orientation-dependent parameters, from which the alignment of peptide segments in the lipid bilayer can be calculated. Molecules embedded in liquid-crystalline membranes, such as monomeric helices, are highly mobile, leading to partial averaging of the measured NMR parameters. These dynamic effects need to be taken into account to avoid misinterpretation of NMR data. Here, we compare two common NMR approaches: (2)H-NMR quadrupolar waves, and separated local field (15)N-(1)H polarization inversion spin exchange at magic angle (PISEMA) spectra, in order to identify their strengths and drawbacks for correctly determining the orientation and mobility of α-helical transmembrane peptides. We first analyzed the model peptide WLP23 in oriented dimyristoylphosphatidylcholine (DMPC) membranes and then contrasted it with published data on GWALP23 in dilauroylphosphatidylcholine (DLPC). We only obtained consistent tilt angles from the two methods when taking dynamics into account. Interestingly, the two related peptides differ fundamentally in their mobility. Although both helices adopt the same tilt in their respective bilayers (~20°), WLP23 undergoes extensive fluctuations in its azimuthal rotation angle, whereas GWALP23 is much less dynamic. Both alternative NMR methods are suitable for characterizing orientation and dynamics, yet they can be optimally used to address different aspects. PISEMA spectra immediately reveal the presence of large-amplitude rotational fluctuations, which are not directly seen by (2)H-NMR. On the other hand, PISEMA was unable to define the azimuthal rotation angle in the case of the highly dynamic WLP23, though the helix tilt could still be determined, irrespective of any dynamics parameters.

  6. ¹³C solid-state NMR analysis of the most common pharmaceutical excipients used in solid drug formulations Part II: CP kinetics and relaxation analysis. (United States)

    Pisklak, Dariusz Maciej; Zielińska-Pisklak, Monika; Szeleszczuk, Łukasz; Wawer, Iwona


    Excipients used in the solid drug formulations differ in their NMR relaxation and (13)C cross-polarization (CP) kinetics parameters. Therefore, experimental parameters like contact time of cross-polarization and repetition time have a major impact on the registered solid state NMR spectra and in consequence on the results of the NMR analysis. In this work the CP kinetics and relaxation of the most common pharmaceutical excipients: anhydrous α-lactose, α-lactose monohydrate, mannitol, sucrose, sorbitol, sodium starch glycolate type A and B, starch of different origin, microcrystalline cellulose, hypromellose, ethylcellulose, methylcellulose, hydroxyethylcellulose, sodium alginate, magnesium stearate, sodium laurilsulfate and Kollidon(®) were analyzed. The studied excipients differ significantly in their optimum repetition time (from 5 s to 1200 s) and T(1ρ)(I) parameters (from 2 ms to 73 ms). The practical use of those differences in the excipients composition analysis was demonstrated on the example of commercially available tablets containing indapamide as an API. The information presented in this article will help to choose the correct acquisition parameters and also will save the time and effort needed for their optimization in the NMR analysis of the solid drug formulations. Copyright © 2016 Elsevier B.V. All rights reserved.

  7. Comparing quantum-chemical calculation methods for structural investigation of zeolite crystal structures by solid-state NMR spectroscopy. (United States)

    Brouwer, Darren H; Moudrakovski, Igor L; Darton, Richard J; Morris, Russell E


    Combining quantum-chemical calculations and ultrahigh-field NMR measurements of (29)Si chemical shielding (CS) tensors has provided a powerful approach for probing the fine details of zeolite crystal structures. In previous work, the quantum-chemical calculations have been performed on 'molecular fragments' extracted from the zeolite crystal structure using Hartree-Fock methods (as implemented in Gaussian). Using recently acquired ultrahigh-field (29) Si NMR data for the pure silica zeolite ITQ-4, we report the results of calculations using recently developed quantum-chemical calculation methods for periodic crystalline solids (as implemented in CAmbridge Serial Total Energy Package (CASTEP) and compare these calculations to those calculated with Gaussian. Furthermore, in the context of NMR crystallography of zeolites, we report the completion of the NMR crystallography of the zeolite ITQ-4, which was previously solved from NMR data. We compare three options for the 'refinement' of zeolite crystal structures from 'NMR-solved' structures: (i) a simple target-distance based geometry optimization, (ii) refinement of atomic coordinates in which the differences between experimental and calculated (29)Si CS tensors are minimized, and (iii) refinement of atomic coordinates to minimize the total energy of the lattice using CASTEP quantum-chemical calculations. All three refinement approaches give structures that are in remarkably good agreement with the single-crystal X-ray diffraction structure of ITQ-4. Copyright © 2010 John Wiley & Sons, Ltd.

  8. Optimization of solid-state synthesis process of advanced ceramics materials: influence of mixing conditions.

    Directory of Open Access Journals (Sweden)

    Sakri Adel


    Full Text Available In this paper, the effect of mixing process on solid state reaction of solid oxide material mixture was studied. Lead piezoelectric ceramic specimens 0.5 Pb(Zn1/3,Sb2/3O3-0.5 Pb0.98La0.02(Zr0.48,Ti0.52O3 prepared by different mixing procedures, were conducted under different conditions such as order, combination and mixing time. The phase formation, composition nature, structural properties of powder mixture was analyzed by X-ray diffraction. The obtained results for different mixing processes make the solid state reaction method more selective, taking into consideration the attraction forces between the reactants and the electronegativity of oxide reactants.

  9. The determination of phosphorus containing compounds in dental casting investment products by 31P solid-state MAS-NMR spectroscopy. (United States)

    Scrimgeour, Sheelagh N; Chudek, John A; Lloyd, Charles H


    To use (31)P solid-state MAS-NMR to determine the phosphorus compounds that occur in dental casting investment material: (a) as-received, (b) after setting and (c) after burn-out and discover whether such compounds are the same in each material across a product range. [(1)H] High powered decoupling (HPDC) and [(1)H] cross-polarization (CP) (31)P solid-state MAS-NMR spectroscopy at a resonance frequency of 121.4 MHz were used. Six commercial products were examined. Manufacturer's instructions were followed and a special liquid was used without dilution. All products contain ammonium dihydrogen phosphate as the acid phosphate required for the setting reaction. All set by the formation of struvite and significant amounts of amorphous magnesium orthophosphate. In three products, lesser amounts of newberyite were present and in another the equivalent amorphous compound was formed. When burnt-out, magnesium metaphosphate or pyrophosphate was the dominant matrix compound. A higher burn-out temperature favoured pyrophosphate formation. Farringtonite was present to a lesser extent with the metaphosphate. Compounds that were not detected in earlier X-ray powder diffraction spectroscopy studies were detected by NMR, notably amorphous and glassy compounds (magnesium orthophosphate in set investment and magnesium metaphosphate in burnt-out material). The variation between products was significant and far greater than expected from the published scientific literature. Since the formation of compounds is affected by technical procedure and ambient conditions, these findings could offer some insight into the cause of the unpredictability of expansion measurements between laboratories. Further research is being undertaken.

  10. A solid-state 23Na NMR study of monovalent cation binding to double-stranded DNA at low relative humidity. (United States)

    Wong, Alan; Yan, Zhimin; Huang, Yining; Wu, Gang


    We report a solid-state (23)Na NMR study of monovalent cation (Li(+), Na(+), K(+), Rb(+), Cs(+) and NH(4) (+)) binding to double-stranded calf thymus DNA (CT DNA) at low relative humidity, ca 0-10%. Results from (23)Na--(31)P rotational echo double resonance (REDOR) NMR experiments firmly establish that, at low relative humidity, monovalent cations are directly bound to the phosphate group of CT DNA and are partially dehydrated. On the basis of solid-state (23)Na NMR titration experiments, we obtain quantitative thermodynamic parameters concerning the cation-binding affinity for the phosphate group of CT DNA. The free energy difference (DeltaG degrees ) between M(+) and Na(+) ions is as follows: Li(+) (-1.0 kcal mol(-1)), K(+) (7.2 kcal mol(-1)), NH(4) (+) (1.0 kcal mol(-1)), Rb(+) (4.5 kcal mol(-1)) and Cs(+) (1.5 kcal mol(-1)). These results suggest that, at low relative humidity, the binding affinity of monovalent cations for the phosphate group of CT DNA follows the order: Li(+) > Na(+) > NH(4) (+) > Cs(+) > Rb(+) > K(+). This sequence is drastically different from that observed for CT DNA in solution. This discrepancy is attributed to the different modes of cation binding in dry and wet states of DNA. In the wet state of DNA, cations are fully hydrated. Our results suggest that the free energy balance between direct cation-phosphate contact and dehydration interactions is important. The reported experimental results on relative ion-binding affinity for the DNA backbone may be used for testing theoretical treatment of cation-phosphate interactions in DNA. Copyright (c) 2008 John Wiley & Sons, Ltd.

  11. Synthesis, Structure and Solid State Properties of Cyclohexanemethylamine Substituted Phenalenyl Based Molecular Conductor

    Directory of Open Access Journals (Sweden)

    Robert C. Haddon


    Full Text Available We report the preparation, crystallization and solid state characterization of a cyclohexanemethylamine substituted spirobiphenalenyl radical; in the solid state the compound is iso-structural with its dehydro-analog (benzylamine-substitued compound, and the molecules packed in a one-dimensional fashion that we refer to as a π-step stack. Neighboring molecules in the stack interact via the overlap of one pair of active (spin bearing carbon atoms per phenalenyl unit. The magnetic susceptibility measurement indicates that in the solid state the radical remains paramagnetic and the fraction of Curie spins is 0.75 per molecule. We use the analytical form of the Bonner-Fisher model for the S = 1/2 antiferromagnetic Heisenberg chain of isotropically interacting spins with intrachain spin coupling constant J = 6.3 cm−1, to fit the experimentally observed paramagnetism [χp (T] in the temperature range 4–330 K. The measured room temperature conductivity (σRT = 2.4 × 10–3 S/cm is comparable with that of the iso-structural benzyl radical, even though the calculated band dispersions are smaller than that of the unsaturated analog.

  12. Solid-state 13C NMR studies of a large fossil gymnosperm from the Yallourn Open Cut, Latrobe Valley, Australia (United States)

    Bates, A.L.; Hatcher, P.G.


    A series of samples taken from the cross section of a 3-m-diameter fossilized gymnospermous log (Araucariaceae) in the Yallourn Seam of the Australian brown coals was examined by solid state 13C nuclear magnetic resonance to delineate chemical changes related to the combined processes of peatification and coalification. The results show that cellulosic materials were degraded and lost on the periphery of the log, however, the degree of such degradation in the central core is substantially less. The lignin is uniformly altered by coalification reactions to a macromolecular substance displaying decreased aryl ether linkages but significantly greater amounts of carbon linkages compared to modern lignin. Changes in the methoxyl carbon contents of lignin in cross section reveal demethylation reactions, but these do not appear to be related to degree of carbon linking. Both the degredation of cellulosic materials and demethylation of lignin appear to be early diagenetic processes occurring during peatification independently of the coalification reactions. ?? 1989.

  13. Structure and Dynamics of Polymer-Ceramic Interface in Li1.5Al0.5Ge1.5P3O12/Polyether Solid Electrolyte:A Solid-State NMR Study

    Directory of Open Access Journals (Sweden)

    JIANG Ting-ting


    Full Text Available All solid state lithium-ion batteries have the advantages of high safety, long cycle life and high energy density, as compared with the conventional lithium-ion batteries, and have been attracting more and more research interest. Solid electrolyte is a crucial component of all solid state lithium-ion batteries, which largely determine the performance of the batteries. In this work, a polymer-lithium-ceramics complex was designed and synthesized. The structure and dynamics of the polymer-ceramic interface was studied with solid-state NMR techniques.

  14. Solid state 13C NMR analysis of shales and coals from Laramide Basins. Final report, March 1, 1995--March 31, 1996

    Energy Technology Data Exchange (ETDEWEB)

    Miknis, F.P.; Jiao, Z.S.; Zhao, Hanqing; Surdam, R.C.


    This Western Research Institute (WRI) jointly sponsored research (JSR) project augmented and complemented research conducted by the University of Wyoming Institute For Energy Research for the Gas Research Institute. The project, {open_quotes}A New Innovative Exploitation Strategy for Gas Accumulations Within Pressure Compartments,{close_quotes} was a continuation of a project funded by the GRI Pressure Compartmentalization Program that began in 1990. That project, {open_quotes}Analysis of Pressure Chambers and Seals in the Powder River Basin, Wyoming and Montana,{close_quotes} characterized a new class of hydrocarbon traps, the discovery of which can provide an impetus to revitalize the domestic petroleum industry. In support of the UW Institute For Energy Research`s program on pressure compartmentalization, solid-state {sup 13}C NMR measurements were made on sets of shales and coals from different Laramide basins in North America. NMR measurements were made on samples taken from different formations and depths of burial in the Alberta, Bighorn, Denver, San Juan, Washakie, and Wind River basins. The carbon aromaticity determined by NMR was shown to increase with depth of burial and increased maturation. In general, the NMR data were in agreement with other maturational indicators, such as vitrinite reflectance, illite/smectite ratio, and production indices. NMR measurements were also obtained on residues from hydrous pyrolysis experiments on Almond and Lance Formation coals from the Washakie Basin. These data were used in conjunction with mass and elemental balance data to obtain information about the extent of carbon aromatization that occurs during artificial maturation. The data indicated that 41 and 50% of the original aliphatic carbon in the Almond and Lance coals, respectively, aromatized during hydrous pyrolysis.

  15. A molecular dynamics study of the effects of fast molecular motions on solid-state NMR parameters

    Czech Academy of Sciences Publication Activity Database

    Dračínský, Martin; Hodgkinson, P.


    Roč. 15, č. 43 (2013), s. 8705-8712 ISSN 1466-8033 Grant - others:Seventh Framework Programme of the European Union(XE) FP7-299242 People Institutional support: RVO:61388963 Keywords : molecular dynamics * DFT calculations * NMR spectroscopy Subject RIV: CC - Organic Chemistry Impact factor: 3.858, year: 2013

  16. Solid-state {sup 27}Al and {sup 29}Si NMR investigations on Si-substituted hydrogarnets

    Energy Technology Data Exchange (ETDEWEB)

    Rivas Mercury, J.M. [Instituto de Ceramica y Vidrio, CSIC, Kelsen, 5, 28049 Cantoblanco-Madrid (Spain); Pena, P. [Instituto de Ceramica y Vidrio, CSIC, Kelsen, 5, 28049 Cantoblanco-Madrid (Spain)]. E-mail:; Aza, A.H. de [Instituto de Ceramica y Vidrio, CSIC, Kelsen, 5, 28049 Cantoblanco-Madrid (Spain); Turrillas, X. [Instituto de Ciencias de la Construccion Eduardo Torroja, CSIC, Serrano Galvache, 4, 28033 Madrid (Spain); Sobrados, I. [Instituto de Ciencia de Materiales, CSIC, Sor Juana Ines de la Cruz, 3, 28049 Cantoblanco-Madrid (Spain); Sanz, J. [Instituto de Ciencia de Materiales, CSIC, Sor Juana Ines de la Cruz, 3, 28049 Cantoblanco-Madrid (Spain)


    Partially deuterated Ca{sub 3}Al{sub 2}(SiO{sub 4}){sub 3-x}(OH){sub 4x} hydrates prepared by a reaction in the presence of D{sub 2}O of synthetic tricalcium aluminate with different amounts of amorphous silica were characterized by {sup 29}Si and {sup 27}Al magic-angle spinning nuclear magnetic resonance (NMR) spectroscopy. The {sup 29}Si NMR spectroscopy was used for quantifying the non-reacted silica and the resulting hydrated products. The incorporation of Si into Ca{sub 3}Al{sub 2}(SiO{sub 4}){sub 3-x}(OH){sub 4x} was followed by {sup 27}Al NMR spectroscopy: Si:OH ratios were determined quantitatively from octahedral Al signals ascribed to Al(OH){sub 6} and Al(OSi)(OH){sub 5} environments. The NMR data obtained were consistent with the concentrations of the Al and Si species deduced from transmission electron microscopy energy-dispersive spectrometry and Rietveld analysis of both X-ray and neutron diffraction data.

  17. Closed-cycle cold helium magic-angle spinning for sensitivity-enhanced multi-dimensional solid-state NMR (United States)

    Matsuki, Yoh; Nakamura, Shinji; Fukui, Shigeo; Suematsu, Hiroto; Fujiwara, Toshimichi


    Magic-angle spinning (MAS) NMR is a powerful tool for studying molecular structure and dynamics, but suffers from its low sensitivity. Here, we developed a novel helium-cooling MAS NMR probe system adopting a closed-loop gas recirculation mechanism. In addition to the sensitivity gain due to low temperature, the present system has enabled highly stable MAS (vR = 4-12 kHz) at cryogenic temperatures (T = 35-120 K) for over a week without consuming helium at a cost for electricity of 16 kW/h. High-resolution 1D and 2D data were recorded for a crystalline tri-peptide sample at T = 40 K and B0 = 16.4 T, where an order of magnitude of sensitivity gain was demonstrated versus room temperature measurement. The low-cost and long-term stable MAS strongly promotes broader application of the brute-force sensitivity-enhanced multi-dimensional MAS NMR, as well as dynamic nuclear polarization (DNP)-enhanced NMR in a temperature range lower than 100 K.

  18. Closed-cycle cold helium magic-angle spinning for sensitivity-enhanced multi-dimensional solid-state NMR. (United States)

    Matsuki, Yoh; Nakamura, Shinji; Fukui, Shigeo; Suematsu, Hiroto; Fujiwara, Toshimichi


    Magic-angle spinning (MAS) NMR is a powerful tool for studying molecular structure and dynamics, but suffers from its low sensitivity. Here, we developed a novel helium-cooling MAS NMR probe system adopting a closed-loop gas recirculation mechanism. In addition to the sensitivity gain due to low temperature, the present system has enabled highly stable MAS (vR=4-12 kHz) at cryogenic temperatures (T=35-120 K) for over a week without consuming helium at a cost for electricity of 16 kW/h. High-resolution 1D and 2D data were recorded for a crystalline tri-peptide sample at T=40 K and B0=16.4 T, where an order of magnitude of sensitivity gain was demonstrated versus room temperature measurement. The low-cost and long-term stable MAS strongly promotes broader application of the brute-force sensitivity-enhanced multi-dimensional MAS NMR, as well as dynamic nuclear polarization (DNP)-enhanced NMR in a temperature range lower than 100 K. Copyright © 2015 The Authors. Published by Elsevier Inc. All rights reserved.

  19. Insight into the Supramolecular Architecture of Intact Diatom Biosilica from DNP-Supported Solid-State NMR Spectroscopy

    NARCIS (Netherlands)

    Jantschke, Anne; Koers, Eline; Mance, Deni; Weingarth, Markus; Brunner, Eike; Baldus, Marc


    Diatom biosilica is an inorganic/organic hybrid with interesting properties. The molecular architecture of the organic material at the atomic and nanometer scale has so far remained unknown, in particular for intact biosilica. A DNP-supported ssNMR approach assisted by microscopy, MS, and MD

  20. Specific binding of a naturally occurring amyloidogenic fragment of Streptococcus mutans adhesin P1 to intact P1 on the cell surface characterized by solid state NMR spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Tang, Wenxing; Bhatt, Avni [University of Florida, Department of Biochemistry and Molecular Biology, College of Medicine (United States); Smith, Adam N. [University of Florida, Department of Chemistry, College of Liberal Arts and Sciences (United States); Crowley, Paula J.; Brady, L. Jeannine, E-mail: [University of Florida, Department of Oral Biology, College of Dentistry (United States); Long, Joanna R., E-mail: [University of Florida, Department of Biochemistry and Molecular Biology, College of Medicine (United States)


    The P1 adhesin (aka Antigen I/II or PAc) of the cariogenic bacterium Streptococcus mutans is a cell surface-localized protein involved in sucrose-independent adhesion and colonization of the tooth surface. The immunoreactive and adhesive properties of S. mutans suggest an unusual functional quaternary ultrastructure comprised of intact P1 covalently attached to the cell wall and interacting with non-covalently associated proteolytic fragments thereof, particularly the ∼57-kDa C-terminal fragment C123 previously identified as Antigen II. S. mutans is capable of amyloid formation when grown in a biofilm and P1 is among its amyloidogenic proteins. The C123 fragment of P1 readily forms amyloid fibers in vitro suggesting it may play a role in the formation of functional amyloid during biofilm development. Using wild-type and P1-deficient strains of S. mutans, we demonstrate that solid state NMR (ssNMR) spectroscopy can be used to (1) globally characterize cell walls isolated from a Gram-positive bacterium and (2) characterize the specific binding of heterologously expressed, isotopically-enriched C123 to cell wall-anchored P1. Our results lay the groundwork for future high-resolution characterization of the C123/P1 ultrastructure and subsequent steps in biofilm formation via ssNMR spectroscopy, and they support an emerging model of S. mutans colonization whereby quaternary P1-C123 interactions confer adhesive properties important to binding to immobilized human salivary agglutinin.

  1. High-resolution structure of the Shigella type-III secretion needle by solid-state NMR and cryo-electron microscopy. (United States)

    Demers, Jean-Philippe; Habenstein, Birgit; Loquet, Antoine; Kumar Vasa, Suresh; Giller, Karin; Becker, Stefan; Baker, David; Lange, Adam; Sgourakis, Nikolaos G


    We introduce a general hybrid approach for determining the structures of supramolecular assemblies. Cryo-electron microscopy (cryo-EM) data define the overall envelope of the assembly and rigid-body orientation of the subunits while solid-state nuclear magnetic resonance (ssNMR) chemical shifts and distance constraints define the local secondary structure, protein fold and inter-subunit interactions. Finally, Rosetta structure calculations provide a general framework to integrate the different sources of structural information. Combining a 7.7-Å cryo-EM density map and 996 ssNMR distance constraints, the structure of the type-III secretion system needle of Shigella flexneri is determined to a precision of 0.4 Å. The calculated structures are cross-validated using an independent data set of 691 ssNMR constraints and scanning transmission electron microscopy measurements. The hybrid model resolves the conformation of the non-conserved N terminus, which occupies a protrusion in the cryo-EM density, and reveals conserved pore residues forming a continuous pattern of electrostatic interactions, thereby suggesting a mechanism for effector protein translocation.

  2. High-resolution structure of the Shigella type-III secretion needle by solid-state NMR and cryo-electron microscopy (United States)

    Demers, Jean-Philippe; Habenstein, Birgit; Loquet, Antoine; Kumar Vasa, Suresh; Giller, Karin; Becker, Stefan; Baker, David; Lange, Adam; Sgourakis, Nikolaos G.


    We introduce a general hybrid approach for determining the structures of supramolecular assemblies. Cryo-electron microscopy (cryo-EM) data define the overall envelope of the assembly and rigid-body orientation of the subunits while solid-state nuclear magnetic resonance (ssNMR) chemical shifts and distance constraints define the local secondary structure, protein fold and inter-subunit interactions. Finally, Rosetta structure calculations provide a general framework to integrate the different sources of structural information. Combining a 7.7-Å cryo-EM density map and 996 ssNMR distance constraints, the structure of the type-III secretion system needle of Shigella flexneri is determined to a precision of 0.4 Å. The calculated structures are cross-validated using an independent data set of 691 ssNMR constraints and scanning transmission electron microscopy measurements. The hybrid model resolves the conformation of the non-conserved N terminus, which occupies a protrusion in the cryo-EM density, and reveals conserved pore residues forming a continuous pattern of electrostatic interactions, thereby suggesting a mechanism for effector protein translocation.

  3. Specific binding of a naturally occurring amyloidogenic fragment of Streptococcus mutans adhesin P1 to intact P1 on the cell surface characterized by solid state NMR spectroscopy. (United States)

    Tang, Wenxing; Bhatt, Avni; Smith, Adam N; Crowley, Paula J; Brady, L Jeannine; Long, Joanna R


    The P1 adhesin (aka Antigen I/II or PAc) of the cariogenic bacterium Streptococcus mutans is a cell surface-localized protein involved in sucrose-independent adhesion and colonization of the tooth surface. The immunoreactive and adhesive properties of S. mutans suggest an unusual functional quaternary ultrastructure comprised of intact P1 covalently attached to the cell wall and interacting with non-covalently associated proteolytic fragments thereof, particularly the ~57-kDa C-terminal fragment C123 previously identified as Antigen II. S. mutans is capable of amyloid formation when grown in a biofilm and P1 is among its amyloidogenic proteins. The C123 fragment of P1 readily forms amyloid fibers in vitro suggesting it may play a role in the formation of functional amyloid during biofilm development. Using wild-type and P1-deficient strains of S. mutans, we demonstrate that solid state NMR (ssNMR) spectroscopy can be used to (1) globally characterize cell walls isolated from a Gram-positive bacterium and (2) characterize the specific binding of heterologously expressed, isotopically-enriched C123 to cell wall-anchored P1. Our results lay the groundwork for future high-resolution characterization of the C123/P1 ultrastructure and subsequent steps in biofilm formation via ssNMR spectroscopy, and they support an emerging model of S. mutans colonization whereby quaternary P1-C123 interactions confer adhesive properties important to binding to immobilized human salivary agglutinin.

  4. Synthesis of dental enamel-like hydroxyapatite through solution mediated solid-state conversion. (United States)

    Zhang, Junling; Jiang, Dongliang; Zhang, Jingxian; Lin, Qingling; Huang, Zhengren


    An ordered dental enamel-like structure of hydroxyapatite (HAp) was achieved through a solution mediated solid-state conversion process with organic phosphate surfactant and gelatin as the mediating agent. Transmission electron microscopy (TEM) tests demonstrated uniform sizes in the obtained apatite nanorods which arranged in parallel to each other along the c-axis and formed organized microarchitectural units over 10 microm in size. The sizes of the synthetic hydroxyapatite nanorods were similar to that observed in enamel from human teeth. The formation and regulation of the orientation and size of HAp nanorods might lead to a better understanding of the biomineralization process for the preparation of high performance biomaterials.

  5. Polycomplexes of Hyaluronic Acid and Borates in a Solid State and Solution: Synthesis, Characterization and Perspectives of Application in Boron Neutron Capture Therapy

    Directory of Open Access Journals (Sweden)

    Alexander N. Zelenetskii


    Full Text Available In this report, we propose a new polyborate fragment synthesis strategy along the whole chain of the polysaccharide hyaluronic acid (HA to produce boron neutron capture therapy (BNCT compounds. Under high pressure and deformatory solid-state conditions, polymolecular system formation takes place due to association of phase-specific transition components into a more or less distinct microscopic organization. Fourier transform infrared (FTIR spectroscopy shows that HA and polyborates form a network of cyclic polychelate complexes. HA acts as a multidentate ligand using carboxylic and hydroxyl proton donor groups to link oxygen atoms in B–O–B bonds and borate-anions B–O(−: O–H···O, O–H···(−O. With free electron pairs in heteroatoms –O(:···B, –N(:···B, HA can act simultaneously as an electron donor. Nuclear magnetic resonance (NMR with 13C and 1H reveals a preserved complex interaction after both solubilizing and attenuating the HA-polyborate system. Stability of the product in water, low cost, ease of synthesis and scalability of manufacturing indicate that HA-polyborate complexes might have advantages over current chemotherapeutic approaches in creating therapeutic agents for BNCT.

  6. Very fast magic angle spinning (1)H-(14)N 2D solid-state NMR: sub-micro-liter sample data collection in a few minutes. (United States)

    Nishiyama, Yusuke; Endo, Yuki; Nemoto, Takahiro; Utsumi, Hiroaki; Yamauchi, Kazuo; Hioka, Katsuya; Asakura, Tetsuo


    Substantial resolution and sensitivity enhancements of solid-state (1)H detected (14)N HMQC NMR spectra at very fast MAS rates up to 80 kHz, in a 1mm MAS rotor, are presented. Very fast MAS enhances the (1)H transverse relaxation time and efficiently decouples the (1)H-(14)N interactions, both effects leading to resolution enhancement. The micro-coil contributes to the sensitivity increase via strong (14)N rf fields and high sensitivity per unit volume. (1)H-(14)N HMQC 2D spectra of glycine and glycyl-L-alanine at 70 kHz MAS at 11.7 T are observed in a few minutes with a sample volume of 0.8 μL. Copyright © 2010 Elsevier Inc. All rights reserved.

  7. Investigation of Pozzolanic Reaction in Nanosilica-Cement Blended Pastes Based on Solid-State Kinetic Models and 29Si MAS NMR (United States)

    Moon, Jiho; Reda Taha, Mahmoud M.; Youm, Kwang-Soo; Kim, Jung J.


    The incorporation of pozzolanic materials in concrete has many beneficial effects to enhance the mechanical properties of concrete. The calcium silicate hydrates in cement matrix of concrete increase by pozzolanic reaction of silicates and calcium hydroxide. The fine pozzolanic particles fill spaces between clinker grains, thereby resulting in a denser cement matrix and interfacial transition zone between cement matrix and aggregates; this lowers the permeability and increases the compressive strength of concrete. In this study, Ordinary Portland Cement (OPC) was mixed with 1% and 3% nanosilica by weight to produce cement pastes with water to binder ratio (w/b) of 0.45. The specimens were cured for 7 days. 29Si nuclear magnetic resonance (NMR) experiments are conducted and conversion fraction of nanosilica is extracted. The results are compared with a solid-state kinetic model. It seems that pozzolanic reaction of nanosilica depends on the concentration of calcium hydroxide. PMID:28787904

  8. Investigation of Pozzolanic Reaction in Nanosilica-Cement Blended Pastes Based on Solid-State Kinetic Models and 29Si MAS NMR. (United States)

    Moon, Jiho; Taha, Mahmoud M Reda; Youm, Kwang-Soo; Kim, Jung J


    The incorporation of pozzolanic materials in concrete has many beneficial effects to enhance the mechanical properties of concrete. The calcium silicate hydrates in cement matrix of concrete increase by pozzolanic reaction of silicates and calcium hydroxide. The fine pozzolanic particles fill spaces between clinker grains, thereby resulting in a denser cement matrix and interfacial transition zone between cement matrix and aggregates; this lowers the permeability and increases the compressive strength of concrete. In this study, Ordinary Portland Cement (OPC) was mixed with 1% and 3% nanosilica by weight to produce cement pastes with water to binder ratio (w/b) of 0.45. The specimens were cured for 7 days. 29Si nuclear magnetic resonance (NMR) experiments are conducted and conversion fraction of nanosilica is extracted. The results are compared with a solid-state kinetic model. It seems that pozzolanic reaction of nanosilica depends on the concentration of calcium hydroxide.

  9. Investigation of Pozzolanic Reaction in Nanosilica-Cement Blended Pastes Based on Solid-State Kinetic Models and 29Si MAS NMR

    Directory of Open Access Journals (Sweden)

    Jiho Moon


    Full Text Available The incorporation of pozzolanic materials in concrete has many beneficial effects to enhance the mechanical properties of concrete. The calcium silicate hydrates in cement matrix of concrete increase by pozzolanic reaction of silicates and calcium hydroxide. The fine pozzolanic particles fill spaces between clinker grains, thereby resulting in a denser cement matrix and interfacial transition zone between cement matrix and aggregates; this lowers the permeability and increases the compressive strength of concrete. In this study, Ordinary Portland Cement (OPC was mixed with 1% and 3% nanosilica by weight to produce cement pastes with water to binder ratio (w/b of 0.45. The specimens were cured for 7 days. 29Si nuclear magnetic resonance (NMR experiments are conducted and conversion fraction of nanosilica is extracted. The results are compared with a solid-state kinetic model. It seems that pozzolanic reaction of nanosilica depends on the concentration of calcium hydroxide.

  10. Solid-State Synthesis and Photocatalytic Activity of Polyterthiophene Derivatives/TiO2 Nanocomposites

    Directory of Open Access Journals (Sweden)

    Ruxangul Jamal


    Full Text Available Poly(3,4-propylenedioxy-2,2':5',2"-terthiophene/TiO2 and poly(3,4-(2,2-dimethylenepropylenedioxy-2,2':5',2"-terthiophene/TiO2 nanocomposites were synthesized by a simple solid-state method. Additionally, the poly(3,4-propylenedioxy thiophene/TiO2 and poly(3,4-2,2-dimethylenepropylenedioxythiophene/TiO2 nanocomposites were synthesized in a similar manner for comparison. The structure and morphology were characterized by Fourier transform infrared (FTIR, ultraviolet-visible (UV-Vis absorption spectroscopy, X-ray diffraction (XRD and transmission electron microscopy (TEM. The photocatalytic activities of the nanocomposites were examined through the degradation processes of a methylene blue (MB solution under UV light and sunlight irradiation. The results of FTIR and UV-Vis spectra showed that the composites were successfully synthesized by solid-state method and the poly(3,4-propylenedioxy-2,2':5',2"-terthiophene/TiO2 and poly(3,4-(2,2-dimethylenepropylenedioxy-2,2':5',2"-terthiophene/TiO2 nanocomposite had a higher oxidation degree and conjugation length than others. The results also indicated that the TiO2 had no effect on the crystallinity of composites, but was well embedded in the polymer matrix. Additionally, the highest degradation efficiency of 90.5% occurred in the case of the poly(3,4-propylenedioxy-2,2':5',2"-terthiophene/TiO2 nanocomposite.

  11. (31)P solid-state MAS-NMR spectroscopy of the compounds that form in phosphate-bonded dental casting investment materials during setting. (United States)

    Scrimgeour, Sheelagh N; Chudek, John A; Cowper, George A; Lloyd, Charles H


    To use (31)P solid-state MAS-NMR to determine which compounds form in phosphate-bonded dental casting investment material during setting, when the ambient temperature is altered. To determine whether they differ in material originating at the center of the mix from material that adheres to the mixing bowl wall. (1)H high powered decoupled (HPDC) and (1)H cross polarized (CP) (31)P solid-state MAS-NMR spectroscopy were used at a resonance frequency of 121.4MHz to determine molecular structure. Four commercial products were examined. Manufacturer's instructions were followed and special liquid used without dilution. Ambient temperature was between 18 and 37 degrees C. Molecular structures change with ambient temperature and product. Amorphous Mg(3)(PO(4))(2) or struvite dominate with newberyite, cattiite, amorphous Mg(2)P(2)O(7) and amorphous MgHPO(4) present as minor phases. Exceptionally, amorphous MgHPO(4) dominates. Differences in structure were found in material taken from the center of the mix compared with that scraped from the bowl wall, but the incidence may be specific to the product/mixer combination and not a general effect. The formation of compounds in phosphate-bonded investment can be affected by ambient temperature. This effect and the use of material adhering to the bowl wall (instead of that from the center of the mix) are possible causes for the unpredictability of setting expansion measurements between laboratories. There is variation between products. When phosphate-bonded investment is required for casting, a consistent ambient temperature must be used and it would be wise to mix sufficient material to avoid scraping the bowl.

  12. Selective excitation enables assignment of proton resonances and {sup 1}H-{sup 1}H distance measurement in ultrafast magic angle spinning solid state NMR spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Rongchun; Ramamoorthy, Ayyalusamy, E-mail: [Biophysics and Department of Chemistry, The University of Michigan, Ann Arbor, Michigan 48109-1055 (United States)


    Remarkable developments in ultrafast magic angle spinning (MAS) solid-state NMR spectroscopy enabled proton-based high-resolution multidimensional experiments on solids. To fully utilize the benefits rendered by proton-based ultrafast MAS experiments, assignment of {sup 1}H resonances becomes absolutely necessary. Herein, we propose an approach to identify different proton peaks by using dipolar-coupled heteronuclei such as {sup 13}C or {sup 15}N. In this method, after the initial preparation of proton magnetization and cross-polarization to {sup 13}C nuclei, transverse magnetization of desired {sup 13}C nuclei is selectively prepared by using DANTE (Delays Alternating with Nutations for Tailored Excitation) sequence and then, it is transferred to bonded protons with a short-contact-time cross polarization. Our experimental results demonstrate that protons bonded to specific {sup 13}C atoms can be identified and overlapping proton peaks can also be assigned. In contrast to the regular 2D HETCOR experiment, only a few 1D experiments are required for the complete assignment of peaks in the proton spectrum. Furthermore, the finite-pulse radio frequency driven recoupling sequence could be incorporated right after the selection of specific proton signals to monitor the intensity buildup for other proton signals. This enables the extraction of {sup 1}H-{sup 1}H distances between different pairs of protons. Therefore, we believe that the proposed method will greatly aid in fast assignment of peaks in proton spectra and will be useful in the development of proton-based multi-dimensional solid-state NMR experiments to study atomic-level resolution structure and dynamics of solids.

  13. Analysis of the mechanical properties and characterization by solid state 13C NMR of recycled EVA copolymer/silica composites

    Directory of Open Access Journals (Sweden)

    Giovanni Chaves Stael


    Full Text Available The incorporation of micrometer sized silica particles on poly (ethylene-co-vinyl acetate - EVA - residues from the footwear industry was evaluated. The effects of the processing parameters - temperature and mixing ratio - on the mechanical behavior of molded plates of neat recycled EVA and EVA/silica composites were also investigated. The mechanical properties measured by the tensile test, the fractographic analysis by scanning electron microscopy (SEM, and the 13C Nuclear Magnetic Resonance (NMR showed a reduced EVA to silica compatibility. Therefore, incorporation of untreated silica to recycled EVA copolymer produced a slight decrease on the mechanical performance of EVA/silica composites in respect to neat EVA copolymer. The NMR analysis also shows that the crosslinking process on recycled EVA may be occurring at the carbonyl group.

  14. (17)O DOR and other solid-state NMR studies concerning the basic properties of zeolites LSX. (United States)

    Schneider, Denis; Toufar, Helge; Samoson, Ago; Freude, Dieter


    We demonstrate complementary (1)H, (17)O, (27)Al and (29)Si measurements for basic low-silica-X zeolites, which were unloaded and pyrrole and formic acid-loaded. It was found that the acid-base-system is not stabile, if the loading exceeds one pyrrole molecule or two formic acid molecules per supercage.(17)O DOR NMR spectra exhibit at least four lines, which are broadened by a distribution of chemical shifts in a similar extend as the (29)Si MAS NMR spectra are broadened by distribution of Si-O-Al angles. A strong cation influence upon (17)O shifts was observed. But there was no strong influence of the acid molecules on the mean value of the (17)O shift of the spectra.

  15. Proton detection for signal enhancement in solid-state NMR experiments on mobile species in membrane proteins

    Energy Technology Data Exchange (ETDEWEB)

    Ward, Meaghan E.; Ritz, Emily [University of Guelph, Department of Physics (Canada); Ahmed, Mumdooh A. M. [Suez University, The Department of Physics, Faculty of Science (Egypt); Bamm, Vladimir V.; Harauz, George [University of Guelph, Biophysics Interdepartmental Group (Canada); Brown, Leonid S.; Ladizhansky, Vladimir, E-mail: [University of Guelph, Department of Physics (Canada)


    Direct proton detection is becoming an increasingly popular method for enhancing sensitivity in solid-state nuclear magnetic resonance spectroscopy. Generally, these experiments require extensive deuteration of the protein, fast magic angle spinning (MAS), or a combination of both. Here, we implement direct proton detection to selectively observe the mobile entities in fully-protonated membrane proteins at moderate MAS frequencies. We demonstrate this method on two proteins that exhibit different motional regimes. Myelin basic protein is an intrinsically-disordered, peripherally membrane-associated protein that is highly flexible, whereas Anabaena sensory rhodopsin is composed of seven rigid transmembrane α-helices connected by mobile loop regions. In both cases, we observe narrow proton linewidths and, on average, a 10× increase in sensitivity in 2D insensitive nuclear enhancement of polarization transfer-based HSQC experiments when proton detection is compared to carbon detection. We further show that our proton-detected experiments can be easily extended to three dimensions and used to build complete amino acid systems, including sidechain protons, and obtain inter-residue correlations. Additionally, we detect signals which do not correspond to amino acids, but rather to lipids and/or carbohydrates which interact strongly with membrane proteins.

  16. Optimizing symmetry-based recoupling sequences in solid-state NMR by pulse-transient compensation and asynchronous implementation. (United States)

    Hellwagner, Johannes; Sharma, Kshama; Tan, Kong Ooi; Wittmann, Johannes J; Meier, Beat H; Madhu, P K; Ernst, Matthias


    Pulse imperfections like pulse transients and radio-frequency field maladjustment or inhomogeneity are the main sources of performance degradation and limited reproducibility in solid-state nuclear magnetic resonance experiments. We quantitatively analyze the influence of such imperfections on the performance of symmetry-based pulse sequences and describe how they can be compensated. Based on a triple-mode Floquet analysis, we develop a theoretical description of symmetry-based dipolar recoupling sequences, in particular, R26411, calculating first- and second-order effective Hamiltonians using real pulse shapes. We discuss the various origins of effective fields, namely, pulse transients, deviation from the ideal flip angle, and fictitious fields, and develop strategies to counteract them for the restoration of full transfer efficiency. We compare experimental applications of transient-compensated pulses and an asynchronous implementation of the sequence to a supercycle, SR26, which is known to be efficient in compensating higher-order error terms. We are able to show the superiority of R26 compared to the supercycle, SR26, given the ability to reduce experimental error on the pulse sequence by pulse-transient compensation and a complete theoretical understanding of the sequence.

  17. The G-protein-coupled neuropeptide Y receptor type 2 is highly dynamic in lipid membranes as revealed by solid-state NMR spectroscopy. (United States)

    Schmidt, Peter; Thomas, Lars; Müller, Paul; Scheidt, Holger A; Huster, Daniel


    In spite of the recent success in crystallizing several G-protein-coupled receptors (GPCRs), a comprehensive biophysical characterization of these molecules under physiological conditions also requires the study of the molecular dynamics of these proteins. The molecular mobility of the human neuropeptide Y receptor type 2 reconstituted into dimyristoylphosphatidylcholine (DMPC) membranes was investigated by means of solid-state NMR spectroscopy. Static (15) N NMR spectra show that the receptor performs axially symmetric motions in the membrane, and several residues undergo large amplitude fluctuations. This was confirmed by quantitative measurements of the motional (1) H,(13) C order parameter of the CH, CH2 , and CH3 groups. In directly polarized (13) C NMR experiments, these order parameters showed astonishingly low values of SCH =0.55, S CH 2=0.33, and S CH 3=0.17, which corresponds to segmental amplitudes of approximately 50° in the backbone and approximately 50-60° in the side chain. At physiological temperature, (2) H NMR spectra of the deuterated receptor showed a narrow component that is indicative of molecular order parameters of S≤0.3 superimposed with a very broad spectrum that could stem from the transmembrane α-helices. These results suggest that the crystal structures of GPCRs only represent a static snapshot of these highly mobile molecules, which undergo significant structural fluctuations with relatively large amplitudes in a liquid-crystalline membrane at physiological temperature. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Solid-state NMR spectroscopic studies on the interaction of sorbic acid with phospholipid membranes at different pH levels. (United States)

    Chu, Shidong; Hawes, John W; Lorigan, Gary A


    2H, 31P, and 1H-magic-angle-spinning (MAS) solid-state NMR spectroscopic methods were used to elucidate the interaction between sorbic acid, a widely used weak acid food preservative, and 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC) bilayers under both acidic and neutral pH conditions. The linewidth broadening observed in the 31P NMR powder pattern spectra and the changes in the 31P longitudinal relaxation time (T1) indicate interaction with the phospholipid headgroup upon titration of sorbic acid or decanoic acid into DMPC bilayers over the pH range from 3.0 to 7.4. The peak intensities of sorbic acid decrease upon addition of paramagnetic Mn2+ ions in DMPC bilayers as recorded in the 1H MAS NMR spectra, suggesting that sorbic acid molecules are in close proximity with the membrane/aqueous surface. No significant 2H quadrupolar splitting (DeltanuQ) changes are observed in the 2H NMR spectra of DMPC-d54 upon titration of sorbic acid, and the change of pH has a slight effect on DeltanuQ, indicating that sorbic acid has weak influence on the orientation order of the DMPC acyl chains in the fluid phase over the pH range from 3.0 to 7.4. This finding is in contrast to the results of the decanoic acid/DMPC-d54 systems, where DeltanuQ increases as the concentration of decanoic acid increases. Thus, in the membrane association process, sorbic acids are most likely interacting with the headgroups and shallowly embedded near the top of the phospholipid headgroups, rather than inserting deep into the acyl chains. Thus, antimicrobial mode of action for sorbic acid may be different from that of long-chain fatty acids.

  19. Combined methods for the determination of structure in disordered systems: Application of solid state NMR and diffraction methods to catalysis (United States)

    Chupas, Peter Joseph

    The research presented in this dissertation involves the use of a combination of experimental methods in the study of disordered heterogeneous catalysts, with the aim of determining active site structure. This research has used powder diffraction, including both the Rietveld and Pair Distribution Analysis (PDF) methods to probe the local, intermediate and long-range structure from atomic scale correlations to crystalline periodic order. Additionally, NMR spectroscopic methods have been applied to the study of local structure and correlations. Disordered heterogeneous catalyst systems have been investigated with the aim of determining how structure is implicated in reactivity. Our work has focused on aluminum fluorides and fluorinated aluminum oxide as catalysts in halocarbon reactions. These materials are widely used both in halocarbon reforming reactions but also as acid catalysts. Using the methods described above, a detailed model is developed to describe formation of catalytically active sites on fluorinated aluminum oxide. Systems with low levels of fluorine versus fully fluorinated systems have been investigated as well as transition metal doped systems, to explore various aspects of structure that may play a vital role in governing catalytic activity. NMR has allowed us to discriminate surface structure versus bulk structure, while powder diffraction methods have developed a more global model of catalyst structure. Additionally, the use of basic probe molecules combined with NMR is shown to be effective in the study of acid site structure, the active sites in these catalysts. In addition to the application of existing techniques to the study of catalysts, the work presented here also aims at developing new methodologies to study catalytic systems in-situ. Time-resolved PDF has been developed to study materials properties in-situ, as a function of temperature or reaction conditions. In conclusion, the work presented in this dissertation aims to illustrate how

  20. Multiple-quantum magic-angle spinning: high-resolution solid state NMR spectroscopy of half-integer quadrupolar nuclei

    CERN Document Server

    Goldbourt, A


    Experimental and theoretical aspects of the multiple-quantum magic-angle spinning experiment (MQMAS) are discussed in this review. The significance of this experiment, introduced by Frydman and Harwood, is in its ability to provide high-resolution NMR spectra of half-integer quadrupolar nuclei (I /geq 3/2). This technique has proved to be useful in various systems ranging from inorganic materials to biological samples. This review addresses the development of various pulse schemes aimed at improving the signal-to-noise ratio and anisotropic lineshapes. Representative spectra are shown to underscore the importance and applications of the MQMAS experiment. Refs. 97 (author)

  1. Development of Solid State NMR Methods for the Structural Characterization of Membrane Proteins: Applications to Understand Multiple Sclerosis

    Energy Technology Data Exchange (ETDEWEB)

    Cosman, M; Tran, A T; Ulloa, J; Maxwell, R S


    Multiple sclerosis (MS) is a relapsing-remitting disorder of the central nervous system that results in the loss of the myelin sheaths insulating nerve fibers (axons). Strong evidence suggests that MS is an autoimmune disease mediated by T-cell and antibody responses against myelin antigens. Myelin oligodendrocyte glycoprotein (MOG) is a 26 kD to 28 kD an integral membrane protein of the central nervous system implicated as a target for autoaggressive antibodies in MS. To date, the conformation of MOG in association with the myelin membrane is unknown and the exact nature of the interactions between this protein and disease-inducing immune responses have not been determined. Since membrane associated proteins are typically characterized by decreased correlation times, solution state NMR methodologies are often impracticable. Membrane proteins are also often difficult to crystallize for X-ray diffraction studies, Consequently, there is an urgent need to develop new structure characterization tools for this important class of biomolecules. The research described here overviews the initial stages of our effort to develop an integrated, NMR based approach to structural studies of MOG over the many structural domains it is postulated to posses. The structural knowledge gained about this important MS antigen in its native environment will contribute significantly to our understanding of its function in vivo. This project will also aid in the development of therapeutics to inhibit the antigedantibody interaction and thus prevent demyelination in MS patients.

  2. Solid-state NMR chemical-shift perturbations indicate domain reorientation of the DnaG primase in the primosome of Helicobacter pylori

    Energy Technology Data Exchange (ETDEWEB)

    Gardiennet, Carole [Université de Lorraine, CNRS, CRM2, UMR 7036 (France); Wiegand, Thomas [ETH Zurich, Physical Chemistry (Switzerland); Bazin, Alexandre [Université de Lyon 1, Molecular Microbiology and Structural Biochemistry, Labex Ecofect, UMR 5086 CNRS (France); Cadalbert, Riccardo [ETH Zurich, Physical Chemistry (Switzerland); Kunert, Britta; Lacabanne, Denis [Université de Lyon 1, Molecular Microbiology and Structural Biochemistry, Labex Ecofect, UMR 5086 CNRS (France); Gutsche, Irina [Université Grenoble Alpes, Institut de Biologie Structurale (IBS), CNRS, IBS, CEA, IBS (France); Terradot, Laurent, E-mail: [Université de Lyon 1, Molecular Microbiology and Structural Biochemistry, Labex Ecofect, UMR 5086 CNRS (France); Meier, Beat H., E-mail: [ETH Zurich, Physical Chemistry (Switzerland); Böckmann, Anja, E-mail: [Université de Lyon 1, Molecular Microbiology and Structural Biochemistry, Labex Ecofect, UMR 5086 CNRS (France)


    We here investigate the interactions between the DnaB helicase and the C-terminal domain of the corresponding DnaG primase of Helicobacter pylori using solid-state NMR. The difficult crystallization of this 387 kDa complex, where the two proteins interact in a six to three ratio, is circumvented by simple co-sedimentation of the two proteins directly into the MAS-NMR rotor. While the amount of information that can be extracted from such a large protein is still limited, we can assign a number of amino-acid residues experiencing significant chemical-shift perturbations upon helicase-primase complex formation. The location of these residues is used as a guide to model the interaction interface between the two proteins in the complex. Chemical-shift perturbations also reveal changes at the interaction interfaces of the hexameric HpDnaB assembly on HpDnaG binding. A structural model of the complex that explains the experimental findings is obtained.

  3. The use of a selective saturation pulse to suppress t1 noise in two-dimensional (1)H fast magic angle spinning solid-state NMR spectroscopy. (United States)

    Robertson, Aiden J; Pandey, Manoj Kumar; Marsh, Andrew; Nishiyama, Yusuke; Brown, Steven P


    A selective saturation pulse at fast magic angle spinning (MAS) frequencies (60+kHz) suppresses t1 noise in the indirect dimension of two-dimensional (1)H MAS NMR spectra. The method is applied to a synthetic nucleoside with an intense methyl (1)H signal due to triisopropylsilyl (TIPS) protecting groups. Enhanced performance in terms of suppressing the methyl signal while minimising the loss of signal intensity of nearby resonances of interest relies on reducing spin diffusion--this is quantified by comparing two-dimensional (1)H NOESY-like spin diffusion spectra recorded at 30-70 kHz MAS. For a saturation pulse centred at the methyl resonance, the effect of changing the nutation frequency at different MAS frequencies as well as the effect of changing the pulse duration is investigated. By applying a pulse of duration 30 ms and nutation frequency 725 Hz at 70 kHz MAS, a good compromise of significant suppression of the methyl resonance combined with the signal intensity of resonances greater than 5 ppm away from the methyl resonance being largely unaffected is achieved. The effectiveness of using a selective saturation pulse is demonstrated for both homonuclear (1)H-(1)H double quantum (DQ)/single quantum (SQ) MAS and (14)N-(1)H heteronuclear multiple quantum coherence (HMQC) two-dimensional solid-state NMR experiments. Copyright © 2015 The Authors. Published by Elsevier Inc. All rights reserved.

  4. SPAM-MQ-HETCOR: an improved method for heteronuclear correlation spectroscopy between quadrupolar and spin-1/2 nuclei in solid-state NMR. (United States)

    Wiench, Jerzy W; Tricot, Gregory; Delevoye, Laurent; Trebosc, Julien; Frye, James; Montagne, Lionel; Amoureux, Jean-Paul; Pruski, Marek


    The recently introduced concept of soft pulse added mixing (SPAM) is used in two-dimensional heteronuclear correlation (HETCOR) NMR experiments between half-integer quadrupolar and spin-1/2 nuclei. The experiments employ multiple quantum magic angle spinning (MQMAS) to remove the second order quadrupolar broadening and cross polarization (CP) or refocused INEPT for magnetization transfer. By using previously unexploited coherence pathways, the efficiency of SPAM-MQ-HETCOR NMR is increased by a factor of almost two without additional optimization. The sensitivity gain is demonstrated on a test sample, AlPO(4)-14, using CP and INEPT to correlate (27)Al and (31)P nuclei. SPAM-3Q-HETCOR is then applied to generate (27)Al-(31)P spectra of the devitrified 41Na(2)O-20.5Al(2)O(3)-38.5P(2)O(5) glass and the silicoaluminophosphate ECR-40. Finally, the method allowed the acquisition of the first high resolution solid-state correlation spectra between (27)Al and (29)Si.

  5. Solid state green synthesis and catalytic activity of CuO nanorods in thermal decomposition of potassium periodate (United States)

    Patel, Vinay Kumar; Bhattacharya, Shantanu


    The present study reports a facile solid state green synthesis process using the leaf extracts of Hibiscus rosa-sinensis to synthesize CuO nanorods with average diameters of 15-20 nm and lengths up to 100 nm. The as-synthesized CuO nanorods were characterized by x-ray diffraction, Fourier transform infrared spectroscopy, transmission electron microscopy and selected area electron diffraction. The formation mechanism of CuO nanorods has been explained by involving the individual role of amide I (amino groups) and carboxylate groups under excess hydroxyl ions released from NaOH. The catalytic activity of CuO nanorods in thermal decomposition of potassium periodate microparticles (µ-KIO4) microparticles was studied by thermo gravimetric analysis measurement. The original size (~100 µm) of commercially procured potassium periodate was reduced to microscale length scale to about one-tenth by PEG200 assisted emulsion process. The CuO nanorods prepared by solid state green route were found to catalyze the thermal decomposition of µ-KIO4 with a reduction of 18 °C in the final thermal decomposition temperature of potassium periodate.

  6. Large scale synthesis and formation mechanism of silver nanoparticles in solid-state reactions at ambient temperature

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Aiqin, E-mail: [State Laboratory of Surface and Interface Science and Technology, Henan Collaborative Innovation Center of Environmental Pollution Control and Ecological Restoration, Zhengzhou University of Light Industry, Zhengzhou 450002 (China); Tian, Yakun; Xiao, Yuanhua; Sun, Yuan [State Laboratory of Surface and Interface Science and Technology, Henan Collaborative Innovation Center of Environmental Pollution Control and Ecological Restoration, Zhengzhou University of Light Industry, Zhengzhou 450002 (China); Li, Feng [State Laboratory of Surface and Interface Science and Technology, Henan Collaborative Innovation Center of Environmental Pollution Control and Ecological Restoration, Zhengzhou University of Light Industry, Zhengzhou 450002 (China); American Advanced Nanotechnology, Houston, TX 77459 (United States)


    Highlights: • AgNPs were prepared by solid state reaction at ambient temperature. • Only silver nitrate and ascorbic acid were needed in this reaction. • The size of the AgNPs can be tuned conveniently. • Formation mechanism of the AgNPs was investigated. - Abstract: A one-step strategy for preparing Ag nanoparticles (AgNPs) on large scale is demonstrated successfully, based on solid-state reactions at ambient temperature. The environmentally friendly synthesis can be achieved by simply grinding AgNO{sub 3} and ascorbic acid (AA) for about 30 min without adding any solvent and organic protectors. The size of AgNPs can be readily controlled by adjusting the reaction parameters such as AgNO{sub 3}/AA molar ratio and reaction time. The nanostructures of AgNPs and their formation mechanism have been also investigated with XRD, FTIR, FESEM, HRTEM and HPLC–MS. It was found that AA can reduce Ag{sup +} into Ag{sup 0} to form AgNPs directly in accompanying with its first oxidation into 2,3-diketogulonic acid (2,3-DKG) and then a series of fragmentary species of 2,3-DKG.

  7. Synthesis and NMR Elucidation of Novel Pentacycloundecane ...

    African Journals Online (AJOL)



    Jan 24, 2012 ... Herein we report the synthesis and NMR elucidation of five novel pentacycloundecane (PCU)-derived short peptides as potential. HIV protease inhibitors. 1H and 13C spectral analysis show major overlapping of methine resonance of the PCU 'cage' thereby making it extremely difficult to assign the NMR ...

  8. Synthesis and characterization of nanostructured electrodes for solid state ionic devices (United States)

    Zhang, Yuelan

    Solid-state electrochemical energy conversion and storage technologies such as fuel cells and lithium ion batteries will influence the way we use energy and the environment we live in. The demands for advanced power sources with high energy efficiency, minimum environmental impact, and low cost have been the impetus for the development of a new generation of batteries and fuel cells. Currently, lithium ion battery technology's greatest disadvantages are long-term cycling stability and high charge/discharge rate capabilities. On the other hand, fuel cell technology's greatest disadvantage is cost. It is found that these problems could be attenuated by the incorporation of nano-structured materials. But, we are still far away from possessing a solid scientific understanding of what goes on at the nanoscale inside these solid state ionic devices, and what is the relationship between nano-structures and their electrochemical properties, especially between the microstructure and electrode polarization and degradation. Electrode polarization represents a voltage loss in an electrochemical energy conversion process. Such understanding is critical for further progress in solid state ionic devices. This thesis focused on the design, fabrication, and characterization of nanostructured porous electrodes with desired composition and microstructure to minimize electrode polarization losses in the application of fuel cells and lithium ion batteries. Various chemical methods such as sol-gel, hydrothermal, surfactant, colloidal and polymer template-assisted processes have been applied in this work. And various characterization techniques have been used to explore the understanding of the microscopic features with electrochemical interfacial properties of the electrodes. Solid-state diffusion often limits the utilization and rate capability of electrode materials in a lithium-ion battery, especially at high charge/discharge rates. When the fluxes of Li+ insertion or extraction

  9. The high-temperature modification of ScRuSi - Structure, 29Si and 45Sc solid state NMR spectroscopy (United States)

    Hoffmann, Rolf-Dieter; Rodewald, Ute Ch.; Haverkamp, Sandra; Benndorf, Christopher; Eckert, Hellmut; Heying, Birgit; Pöttgen, Rainer


    A polycrystalline sample of the TiNiSi type low-temperature (LT) modification of ScRuSi was synthesized by arc-melting. Longer annealing in a sealed silica tube (6 weeks at 1270 K) followed by quenching led to the high-temperature (HT) phase. HT-ScRuSi adopts the ZrNiAl structure type: P 6 bar 2 m , a = 688.27(9), c = 336.72(5) pm, wR2 = 0.0861, 260 F2 values, 14 variables. The striking structural building units are regular, tricapped trigonal prisms Si1@Ru3Sc6 and Si2@Ru6Sc3. Both polymorphs have been characterized by 29Si and 45Sc MAS-NMR spectroscopy. The local scandium environments in the two polymorphs are easily distinguished by their electric field gradient tensor values, in agreement with theoretically calculated values.

  10. Mechanism of Phenol Alkylation in Zeolite H-BEA Using In Situ Solid-State NMR Spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Zhao, Zhenchao [Institute; Shi, Hui [Institute; Wan, Chuan [Institute; Hu, Mary Y. [Institute; Liu, Yuanshuai [Department; Mei, Donghai [Institute; Camaioni, Donald M. [Institute; Hu, Jian Zhi [Institute; Lercher, Johannes A. [Institute; Department


    Alkylation of phenolic compounds in the liquid phase is of fundamental and practical importance to the conversion of biomass-derived feedstocks into fuels and chemicals. In this work, the reaction mechanism for phenol alkylation with cyclohexanol and cyclohexene has been investigated on a commercial HBEA zeolite by in situ 13C MAS NMR, using decalin as the solvent. From the variable temperature 13C MAS NMR measurements of phenol and cyclohexanol adsorption on HBEA from decalin solutions, it is shown that the two molecules have similar adsorption strength in the HBEA pore. Phenol alkylation with cyclohexanol, however, becomes significantly measurable only after cyclohexanol is largely converted to cyclohexene via dehydration. This is in contrast to the initially rapid alkylation of phenol when using cyclohexene as the co-reactant. 13C isotope scrambling results demonstrate that the electrophile, presumably cyclohexyl carbenium ion, is directly formed in a protonation step when cyclohexene is the co-reactant, but requires re-adsorption of the alcohol dehydration product, cyclohexene, when cyclohexanol dimer is the dominant surface species (e.g., at 0.5 M cyclohexanol concentration) that is unable to generate carbenium ion. At the initial reaction stage of phenol-cyclohexanol alkylation on HBEA, the presence of the cyclohexanol dimer species hinders the adsorption of cyclohexene at the Brønsted acid site and the subsequent activation of the more potent electrophile (carbenium ion). Isotope scrambling data also show that intramolecular rearrangement of cyclohexyl phenyl ether, the O-alkylation product, does not significantly contribute to the formation of C-alkylation products.

  11. Synthesis, photophysics of two new perylene bisimides and their photovoltaic performances in quasi solid state dye sensitized solar cells

    Energy Technology Data Exchange (ETDEWEB)

    Mikroyannidis, John A.; Stylianakis, Minas M. [Chemical Technology Laboratory, Department of Chemistry, University of Patras, GR-26500 Patras (Greece); Roy, M.S. [Defence Laboratory, Jodhpur 342011 (Raj.) (India); Suresh, P.; Sharma, G.D. [Physics Department, Molecular Electronic and Optoelectronic Device Laboratory, JNV University, Jodhpur 342005 (Raj.) (India)


    Two new symmetrical compounds A and P based on perylene-anthracene and perylene-pyrene, respectively, were synthesized and characterized by FT-IR, {sup 1}H NMR, TGA and TMA. These compounds contained tert-butyl groups which enhanced their solubility, decomposed above 400 C and gave char yields of 46-65% at 800 C in N{sub 2}. Compound A showed significantly higher glass transition temperature (124 C) than P (75 C). Their absorption spectra were broad with longer wavelength absorption at 467-525 nm and optical band gap of 2.05 eV. The solutions of the compounds emitted green-yellow light with maximum at 555 nm, while their films were not photoluminescent. The compound A shows better photovoltaic response than compound P. Quasi solid state dye sensitized solar cells (DSSCs) have been fabricated employing compound A as sensitizer and polymer sol gel as electrolyte and characterized through the current-voltage characteristics in dark as well as under illumination and electrochemical impedance spectra. We found that the Al{sub 2}O{sub 3} modification of TiO{sub 2} layer significantly improves the dye absorption resulting in enhancement of power conversion efficiency (PCE) (from 1.15 to 2.13%) which is attributed to the increase in electron lifetime and reduction in back transfer of electrons. Finally, the TiO{sub 2} has been incorporated into the polymer electrolyte gel to improve the power conversion efficiency (3.42%) of the quasi solid state DSSC. The faster electron diffusion in the device, the high ionic conductivity and the low activation energy of the polymer electrolyte are also responsible for enhanced PCE, when TiO{sub 2} nano-particles are incorporated in the polymer electrolyte. (author)

  12. (15)N and (1)H Solid-State NMR Investigation of a Canonical Low-Barrier Hydrogen-Bond Compound: 1,8-Bis(dimethylamino)naphthalene. (United States)

    White, Paul B; Hong, Mei


    Strong or low-barrier hydrogen bonds have often been proposed in proteins to explain enzyme catalysis and proton-transfer reactions. So far (1)H chemical shifts and scalar couplings have been used as the main NMR spectroscopic signatures for strong H-bonds. In this work, we report simultaneous measurements of (15)N and (1)H chemical shifts and N-H bond lengths by solid-state NMR in (15)N-labeled 1,8-bis(dimethylamino)naphthalene (DMAN), which contains a well-known strong NHN H-bond. We complexed DMAN with three different counteranions to examine the effects of the chemical environment on the H-bond lengths and chemical shifts. All three DMAN compounds exhibit significantly elongated N-H distances compared to the covalent bond length, and the (1)H(N) chemical shifts are larger than ∼17 ppm, consistent with strong NHN H-bonds in the DMAN cation. However, the (15)N and (1)H chemical shifts and the precise N-H distances differ among the three compounds, and the (15)N chemical shifts show opposite dependences on the proton localization from the general trend in organic compounds, indicating the significant effects of the counteranions on the electronic structure of the H-bond. These data provide useful NMR benchmarks for strong H-bonds and caution against the sole reliance on chemical shifts for identifying strong H-bonds in proteins since neighboring side chains can exert influences on chemical shifts similar to those of the bulky organic anions in DMAN. Instead, N-H bond lengths should be measured, in conjunction with chemical shifts, as a more fundamental parameter of H-bond strength.

  13. Conformational Plasticity of the Cell-Penetrating Peptide SAP As Revealed by Solid-State (19)F-NMR and Circular Dichroism Spectroscopies. (United States)

    Afonin, Sergii; Kubyshkin, Vladimir; Mykhailiuk, Pavel K; Komarov, Igor V; Ulrich, Anne S


    The cell-penetrating peptide SAP, which was designed as an amphipathic poly-l-proline helix II (PPII), was suggested to self-assemble into regular fibrils that are relevant for its internalization. Herein we have analyzed the structure of SAP in the membrane-bound state by solid-state (19)F-NMR, which revealed other structural states, in addition to the expected surface-aligned PPII. Trifluoromethyl-bicyclopentyl-glycine (CF3-Bpg) and two rigid isomers of trifluoromethyl-4,5-methanoprolines (CF3-MePro) were used as labels for (19)F-NMR analysis. The equilibria between different conformations of SAP were studied and were found to be shifted by the substituents at Pro-11. Synchrotron-CD results suggested that substituting Pro-11 by CF3-MePro governed the coil-to-PPII equilibrium in solution and in the presence of a lipid bilayer. Using CD and (19)F-NMR, we examined the slow kinetics of the association of SAP with membranes and the dependence of the SAP conformational dynamics on the lipid composition. The peptide did not bind to lipids in the solid ordered phase and aggregated only in the liquid ordered "raft"-like bilayers. Self-association could not be detected in solution or in the presence of liquid disordered membranes. Surface-bound amphipathic SAP in a nonaggregated state was structured as a mixture of nonideal extended conformations reflecting the equilibrium already present in solution, i.e., before binding to the membrane.

  14. A study of transition-metal organometallic complexes combining 35Cl solid-state NMR spectroscopy and 35Cl NQR spectroscopy and first-principles DFT calculations. (United States)

    Johnston, Karen E; O'Keefe, Christopher A; Gauvin, Régis M; Trébosc, Julien; Delevoye, Laurent; Amoureux, Jean-Paul; Popoff, Nicolas; Taoufik, Mostafa; Oudatchin, Konstantin; Schurko, Robert W


    A series of transition-metal organometallic complexes with commonly occurring metal-chlorine bonding motifs were characterized using (35)Cl solid-state NMR (SSNMR) spectroscopy, (35)Cl nuclear quadrupole resonance (NQR) spectroscopy, and first-principles density functional theory (DFT) calculations of NMR interaction tensors. Static (35)Cl ultra-wideline NMR spectra were acquired in a piecewise manner at standard (9.4 T) and high (21.1 T) magnetic field strengths using the WURST-QCPMG pulse sequence. The (35)Cl electric field gradient (EFG) and chemical shielding (CS) tensor parameters were readily extracted from analytical simulations of the spectra; in particular, the quadrupolar parameters are shown to be very sensitive to structural differences, and can easily differentiate between chlorine atoms in bridging and terminal bonding environments. (35)Cl NQR spectra were acquired for many of the complexes, which aided in resolving structurally similar, yet crystallographically distinct and magnetically inequivalent chlorine sites, and with the interpretation and assignment of (35)Cl SSNMR spectra. (35)Cl EFG tensors obtained from first-principles DFT calculations are consistently in good agreement with experiment, highlighting the importance of using a combined approach of theoretical and experimental methods for structural characterization. Finally, a preliminary example of a (35)Cl SSNMR spectrum of a transition-metal species (TiCl4) diluted and supported on non-porous silica is presented. The combination of (35)Cl SSNMR and (35)Cl NQR spectroscopy and DFT calculations is shown to be a promising and simple methodology for the characterization of all manner of chlorine-containing transition-metal complexes, in pure, impure bulk and supported forms. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Room Temperature Solid State Synthesis, Characterization, and Application of a Zinc Complex with Pyromellitic Acid

    Directory of Open Access Journals (Sweden)

    Rong-Gui Yang


    Full Text Available The complex [Zn2(btca(H2O4] was synthesized with 1,2,4,5-benzenetetracarboxylic acid (H4btca and zinc acetate as materials via a room-temperature solid state reaction. The composition and structure of the complex were characterized by elemental analyses (EA, Fourier transform infrared spectroscopy (FTIR, X-ray powder diffraction (XRD, and thermogravimetric (TG analysis. The index results of X-ray powder diffraction data showed that the crystal structure of the complex belonged to monoclinic system with cell parameters a = 9.882 Å, b = 21.311 Å, c = 15.746 Å, and β = 100.69°. In order to expand the application of the complex, the nanometer zinc oxide was prepared by using the complex as a precursor, and the effect of the thermal decomposition temperature on the preparation of the nanometer zinc oxide was studied. The results showed that the grain size of zinc oxide gradually grew with the increase of the pyrolysis temperature, the obtained nanometer zinc oxide was spherical, and the diameter of the particles was about 25 nm.

  16. Synthesis and characterization of polyimide thin films obtained by thermal evaporation and solid state reaction

    Directory of Open Access Journals (Sweden)

    Al-Ajaj Ikram Atta


    Full Text Available In this research polyimide films were prepared by physical vapor deposition (PVD, using solid state reaction of pyromellitic dianhydride (PMDA and p-phenylene diamine (PDA to form poly(amic acid (PAA films. The resultant films were converted to polyimide by thermal treatment, usually below 300 °C. For this study, a FT-IR spectrometer has been used to measure the effect of imidization temperature on the chemical structure of the vapor-deposited thin films of aromatic PI. When temperature increased, an increase in all absorption peaks was observed. This suggests that residual PAA monomers continued to be converted into PI. The surface topology of the PI films obtained at imidization temperatures of 150, 200, 250 °C for 1 hour was further examined by using AFM atomic force microscopy. It can be clearly seen that the surface became rougher with increasing imidization temperature. The thermal stability of polyimide was also studied by using thermogravimetric analysis (TGA.

  17. Determination of the torsion angles of alanine and glycine residues of model compounds of spider silk (AGG){sub 10} using solid-state NMR methods

    Energy Technology Data Exchange (ETDEWEB)

    Ashida, Jun; Ohgo, Kosuke; Komatsu, Kohei; Kubota, Ayumi; Asakura, Tetsuo [Tokyo University of Agriculture and Technology, Department of Biotechnology (Japan)], E-mail:


    Spiders synthesize several kinds of silk fibers. In the primary structure of spider silk, one of the major ampullate (dragline, frame) silks, spidroin 1, and flagelliform silk (core fibers of adhesive spiral), there are common repeated X-Gly-Gly (X = Ala, Leu, Pro, Tyr, Glu, and Arg) sequences, which are considered to be related to the elastic character of these fibers. In this paper, two dimensional spin diffusion solid-state NMR under off magic angle spinning (OMAS), {sup 13}C chemical shift contour plots, and Rotational Echo DOuble Resonance (REDOR) were applied to determine the torsion angles of one Ala and two kinds of Gly residues in the Ala-Gly-Gly sequence of {sup 13}C=O isotope-labeled (Ala-Gly-Gly){sub 10}. The torsion angles were determined to be ({phi}, {psi}) = (-90 deg., 150 deg.) within an experimental error of {+-}10 deg. for each residue. This conformation is characterized as 3{sub 1} helix which is in agreement with the structure proposed from the X-ray powder diffraction pattern of poly(Ala-Gly-Gly). The 3{sub 1} helix of (Ala-Gly-Gly){sub 10} does not change by formic acid treatment although (Ala-Gly){sub 15} easily changes from the silk I conformation (the structure of Bombyx mori silk fibroin before spinning in the solid state) to silk II conformation (the structure of the silk fiber after spinning) by such treatment. Thus, the 3{sub 1} helix conformation of (Ala-Gly-Gly){sub 10} is considered very stable. Furthermore, the torsion angles of the 16th Leu residue of (Leu-Gly-Gly){sub 10} were also determined as ({phi}, {psi}) = (-90 deg., 150 deg.) and this peptide is also considered to take 3{sub 1} helix conformation.

  18. Effect of the addition of poly-saccharide in rejected (vinyl - ethylene - acetate) copolymer studied by solid state NMR; Efeito da adicao de polissacarideo em copolimero (etileno-acetato de vinila) rejeito por RMN no estado solido

    Energy Technology Data Exchange (ETDEWEB)

    Mothe, Cheila G. [Universidade Federal, Rio de Janeiro, RJ (Brazil). Escola de Quimica; Tavares, Maria Ines B. [Universidade Federal, Rio de Janeiro, RJ (Brazil). Inst. de Macromoleculas


    The solid state NMR study of vinyl-ethylene-acetate with and without starch has as main objective to obtain biodegradable materials. The biodegradation is affected by environmental conditions, but mainly by the type of polymer. In order to obtain more information concerning this process, several instrumental techniques were used. Results are presented 6 refs., 1 fig., 1 tab.

  19. Solid-state C-13 and Co-59 NMR spectroscopy of C-13-methylcobalt(III) complexes with amine ligands

    DEFF Research Database (Denmark)

    Ooms, Kristopher J.; Bernard, Guy M.; Kadziola, Anders


    spectroscopy, which also established the negative sign of C-Q(Co-59). Cobalt-59 NMR spectroscopy was used to characterize the cobalt magnetic shielding tensor, to verify the magnitudes of C-Q(Co-59) and to establish the value of eta(Q), which is difficult to determine indirectly. The measurements show...... that the EFG tensors are either axially symmetric or close to being so but there is a wide range of C-Q values, from -40 MHz for the complex with X = H2O to -105 MHz with X = CN-. The Co chemical shift tensors are approximately axially symmetric with the spans. delta(11) - delta(33), ranging from 3700 to 5600...... ppm for X = H2O and CN-, respectively. The latter measurements also established the relative orientations of the Co EFG and chemical shift tensors. Density functional theory calculations of the Co-59 EFG and magnetic shielding tensors as well as of (1)J(Co-59, C-13) for the NO2- and N-3(-) complexes...

  20. Investigating sorption on iron-oxyhydroxide soil minerals by solid-state NMR spectroscopy: a 6Li MAS NMR study of adsorption and absorption on goethite

    DEFF Research Database (Denmark)

    Nielsen, Ulla Gro; Paik, Younkee; Julmis, Keinia


    H, the system representing an ideal model system for NMR studies. 6Li resonances with large hyperfine shifts (approximately 145 ppm) were observed above the goethite point of zero charge, providing clear evidence for the presence of Li-O-Fe connectivities, and thus the formation of an inner sphere Li+ complex...

  1. Structure and Membrane Interactions of the Antibiotic Peptide Dermadistinctin K by Multidimensional Solution and Oriented 15N and 31P Solid-State NMR Spectroscopy


    Verly, Rodrigo M.; Moraes, Cléria Mendonça; Resende, Jarbas M.; Aisenbrey, Christopher; Bemquerer, Marcelo Porto; Piló-Veloso, Dorila; Valente, Ana Paula; Almeida, Fábio C.L.; Bechinger, Burkhard


    DD K, a peptide first isolated from the skin secretion of the Phyllomedusa distincta frog, has been prepared by solid-phase chemical peptide synthesis and its conformation was studied in trifluoroethanol/water as well as in the presence of sodium dodecyl sulfate and dodecylphosphocholine micelles or small unilamellar vesicles. Multidimensional solution NMR spectroscopy indicates an α-helical conformation in membrane environments starting at residue 7 and extending to the C-terminal carboxyami...

  2. Medium-Range Structural Organization of Phosphorus-Bearing Borosilicate Glasses Revealed by Advanced Solid-State NMR Experiments and MD Simulations: Consequences of B/Si Substitutions. (United States)

    Yu, Yang; Stevensson, Baltzar; Edén, Mattias


    The short and intermediate range structures of a large series of bioactive borophosphosilicate (BPS) glasses were probed by solid-state nuclear magnetic resonance (NMR) spectroscopy and atomistic molecular dynamics (MD) simulations. Two BPS glass series were designed by gradually substituting SiO2 by B2O3 in the respective phosphosilicate base compositions 24.1Na2O-23.3CaO-48.6SiO2-4.0P2O5 ("S49") and 24.6Na2O-26.7CaO-46.1SiO2-2.6P2O5 ("S46"), the latter constituting the "45S5 Bioglass" utilized for bone grafting applications. The BPS glass networks are built by interconnected SiO4, BO4, and BO3 moieties, whereas P exists mainly as orthophosphate anions, except for a minor network-associated portion involving P-O-Si and P-O-B([4]) motifs, whose populations were estimated by heteronuclear (31)P{(11)B} NMR experimentation. The high Na(+)/Ca(2+) contents give fragmented glass networks with large amounts of nonbridging oxygen (NBO) anions. The MD-generated glass models reveal an increasing propensity for NBO accommodation among the network units according to BO4 B NMR experiments, which evidenced the presence of all three BO3-BO3, BO3-BO4, and BO4-BO4 connectivities, with B([3])-O-B([4]) bridges dominating. Notwithstanding that B([4])-O-B([4]) linkages are disfavored, both NMR spectroscopy and MD simulations established their presence in these modifier-rich BPS glasses, along with non-negligible B([4])-NBO contacts, at odds with the conventional structural view of borosilicate glasses. We discuss the relative propensities for intermixing of the Si/B/P network formers. Despite the absence of pronounced preferences for Si-O-Si bond formation, the glass models manifest subtle subnanometer-sized structural inhomogeneities, where SiO4 tetrahedra tend to self-associate into small chain/ring motifs embedded in BO3/BO4-dominated domains.

  3. Solid-state synthesis of monocrystalline iron oxide nanoparticle based ferrofluid suitable for magnetic resonance imaging contrast application (United States)

    Lu, Jun; Yang, Shihe; Ng, Ka Ming; Su, Chia-Hao; Yeh, Chen-Sheng; Wu, Ya-Na; Shieh, Dar-Bin


    A new γ-Fe2O3 MION ferrofluid has been developed with a salt-assisted solid-state reaction. Characterizations show that the ferrofluid is composed of maghemite nanoparticles with a mean diameter of 2.7 nm. Though the nanoparticles are ultrafine, they are well crystallized, with a saturation magnetization value of 34.7 emu g-1, making them suitable for MRI applications. In spite of the absence of any surfactant, the ferrofluid can be stable for more than 6 months. An in vitro cytotoxicity test revealed good biocompatibility of the maghemite nanoparticles, suggesting that they may be further explored for biomedical applications. NMR measurements revealed significantly reduced water proton relaxation times T1 and T2. The MR images of the nanoparticles in aqueous dispersion were investigated using a 3 T clinical MR imager. These preliminary experiments have demonstrated the potential of the as-synthesized ultrafine, cap-free maghemite MIONs in functional molecular imaging for biomedical research and clinical diagnosis.

  4. Protonation equilibria and pore-opening structure of the dual-histidine influenza B virus M2 transmembrane proton channel from solid-state NMR. (United States)

    Williams, Jonathan K; Shcherbakov, Alexander A; Wang, Jun; Hong, Mei


    The influenza A and B viruses are the primary cause of seasonal flu epidemics. Common to both viruses is the M2 protein, a homotetrameric transmembrane proton channel that acidifies the virion after endocytosis. Although influenza A M2 (AM2) and B M2 (BM2) are functional analogs, they have little sequence homology, except for a conserved HXXXW motif, which is responsible for proton selectivity and channel gating. Importantly, BM2 contains a second titratable histidine, His-27, in the tetrameric transmembrane domain that forms a reverse WXXXH motif with the gating tryptophan. To understand how His-27 affects the proton conduction property of BM2, we have used solid-state NMR to characterize the pH-dependent structure and dynamics of His-27. In cholesterol-containing lipid membranes mimicking the virus envelope, 15N NMR spectra show that the His-27 tetrad protonates with higher pKa values than His-19, indicating that the solvent-accessible His-27 facilitates proton conduction of the channel by increasing the proton dissociation rates of His-19. AM2 is inhibited by the amantadine class of antiviral drugs, whereas BM2 has no known inhibitors. We measured the N-terminal interhelical separation of the BM2 channel using fluorinated Phe-5. The interhelical 19F-19F distances show a bimodal distribution of a short distance of 7 Å and a long distance of 15-20 Å, indicating that the phenylene rings do not block small-molecule entry into the channel pore. These results give insights into the lack of amantadine inhibition of BM2 and reveal structural diversities in this family of viral proton channels. © 2017 by The American Society for Biochemistry and Molecular Biology, Inc.

  5. Orientation-dependent (19)F dipolar couplings within a trifluoromethyl group are revealed by static multipulse NMR in the solid state. (United States)

    Grage, S L; Ulrich, A S


    The homonuclear dipolar coupling between the three equivalent (19)F-spins of a trifluoromethyl group, rotating about its threefold symmetry axis, was studied by multipulse solid-state NMR. A modified CPMG sequence was used first to resolve the dipolar splitting of a powder sample, and then to follow its orientation-dependence in uniaxially aligned samples. Our aim is to employ the CF(3)-group as a highly sensitive reporter to describe the mobility and spacial alignment of (19)F-labeled molecules in biomembranes. As an example, the fluorinated anti-inflammatory drug, flufenamic acid, was embedded as a guest compound in lipid bilayers. Undistorted (19)F dipolar spectra of its CF(3)-group were obtained without (1)H-decoupling, revealing a sharp triplet lineshape. When an oriented membrane sample was tilted in the magnetic field, the change in dipolar splittings confirmed that the guest molecule is motionally averaged about the membrane normal, as expected. A different behavior of flufenamic acid, however, was observed under conditions of low bilayer hydration. From this set of orientation-dependent lineshapes we conclude that the axis of motional averaging becomes aligned perpendicular to the sample normal. It thus appears that flufenamic acid induces a hexagonal phase in the membrane at low hydration. Finally, the dipolar (19)F NMR experiments were extended to frozen samples, where no molecular diffusion occurs besides the fast rotation about the CF(3)-axis. Also under these conditions, the CPMG experiment with composite pulses could successfully resolve the dipolar coupling between the three (19)F-nuclei. Copyright 2000 Academic Press.

  6. Transport-Relevant Protein Conformational Dynamics and Water Dynamics on Multiple Timescales in an Archetypal Proton Channel - Insights from Solid-State NMR. (United States)

    Mandala, Venkata; Gelenter, Martin D; Hong, Mei


    The influenza M2 protein forms a tetrameric proton channel that conducts protons from the acidic endosome into the virion by shuttling protons between water and a transmembrane histidine. Previous NMR studies have shown that this histidine protonates and deprotonates on the microsecond timescale. However, M2's proton conduction rate is 10 - 1000 s-1, more than two orders of magnitude slower than the histidine-water proton-exchange rate. M2 is also known to be conformationally plastic. To address the disparity between the functional timescale and the timescales of protein conformational dynamics and water dynamics, we have now investigated a W41F mutant of the M2 transmembrane domain using solid-state NMR. 13C chemical shifts of the membrane-bound peptide indicate the presence of two distinct tetramer conformations, whose concentrations depend exclusively on pH and hence the charge-state distribution of the tetramers. High-temperature 2D correlation spectra indicate that these two conformations interconvert at a rate of ~400 s-1 when the +2 and +3 charge states dominate, which gives the first experimental evidence of protein conformational motion on the transport timescale. Protein 13C-detected water 1H T2 relaxation measurements show that channel water relaxes an order of magnitude faster than bulk water and membrane-associated water, indicating that channel water undergoes nanosecond motion in a pH-independent fashion. These results connect motions on three timescales to explain M2's proton-conduction mechanism: picosecond-to-nanosecond motions of water molecules facilitate proton Grotthuss hopping, microsecond motions of the histidine sidechain allow water-histidine proton transfer, while millisecond motions of the entire four-helix bundle constitute the rate-limiting step, dictating the number of protons released into the virion.

  7. Spying on the boron-boron triple bond using spin-spin coupling measured from 11B solid-state NMR spectroscopy. (United States)

    Perras, Frédéric A; Ewing, William C; Dellermann, Theresa; Böhnke, Julian; Ullrich, Stefan; Schäfer, Thomas; Braunschweig, Holger; Bryce, David L


    There is currently tremendous interest in the previously documented example of a stable species exhibiting a boron-boron triple bond (Science, 2012, 336, 1420). Notably, it has recently been stated using arguments based on force constants that this diboryne may not, in reality, feature a boron-boron triple bond. Here, we use advanced solid-state NMR and computational methodology in order to directly probe the orbitals involved in multiple boron-boron bonds experimentally via analysis of 11B-11B spin-spin (J) coupling constants. Computationally, the mechanism responsible for the boron-boron spin-spin coupling in these species is found to be analogous to that for the case of multiply-bonded carbon atoms. The trend in reduced J coupling constants for diborenes and a diboryne, measured experimentally, is in agreement with that known for alkenes and alkynes. This experimental probe of the electronic structure of the boron-boron multiple bond provides strong evidence supporting the originally proposed nature of the bonds in the diboryne and diborenes, and demonstrates that the orbitals involved in boron-boron bonding are equivalent to those well known to construct the multiple bonds between other second-row elements such as carbon and nitrogen.

  8. Tungsten(VI) Carbyne/Bis(carbene) Tautomerization Enabled by N-Donor SBA15 Surface Ligands: A Solid-State NMR and DFT Study

    KAUST Repository

    Bendjeriou-Sedjerari, Anissa


    Designing supported well-defined bis(carbene) complexes remains a key challenge in heterogeneous catalysis. The reaction of W(CtBu)(CH(2)tBu)(3) with amine-modified mesoporous SBA15 silica, which has vicinal silanol/silylamine pairs [(SiOH)(SiNH2)], leads to [(SiNH2-)(SiO-)W(CHtBu)(CH(2)tBu)(2)] and [(SiNH2-)(SiO-)W(=CHtBu)(2)(CH(2)tBu). Variable temperature, H-1-H-1 2D double-quantum, H-1-C-13 HETCOR, and HETCOR with spin diffusion solid-state NMR spectroscopy demonstrate tautomerization between the alkyl alkylidyne and the bis(alkylidene) on the SBA15 surface. Such equilibrium is possible through the coordination of W to the surface [(Si-OH)(Si-NH2)] groups, which act as a [N,O] pincer ligand. DFT calculations provide a rationalization for the surface-complex tautomerization and support the experimental results. This direct observation of such a process shows the strong similarity between molecular mechanisms in homogeneous and heterogeneous catalysis. In propane metathesis (at 150 degrees C), the tungsten bis(carbene) tautomer is favorable, with a turnover number (TON) of 262. It is the highest TON among all the tungsten alkyl-supported catalysts.

  9. Early diagenesis of mangrove leaves in a tropical estuary: Bulk chemical characterization using solid-state 13C NMR and elemental analyses (United States)

    Benner, R.; Hatcher, P.G.; Hedges, J.I.


    Changes in the chemical composition of mangrove (Rhizophora mangle) leaves during decomposition in tropical estuarine waters were characterized using solid-state 13C nuclear magnetic resonance (NMR) and elemental (CHNO) analysis. Carbohydrates were the most abundant components of the leaves accounting for about 50 wt% of senescent tissues. Tannins were estimated to account for about 20 wt% of leaf tissues, and lipid components, cutin, and possibly other aliphatic biopolymers in leaf cuticles accounted for about 15 wt%. Carbohydrates were generally less resistant to decomposition than the other constituents and decreased in relative concentration during decomposition. Tannins were of intermediate resistance to decomposition and remained in fairly constant proportion during decomposition. Paraffinic components were very resistant to decomposition and increased in relative concentration as decomposition progressed. Lignin was a minor component of all leaf tissues. Standard methods for the colorimetric determination of tannins (Folin-Dennis reagent) and the gravimetric determination of lignin (Klason lignin) were highly inaccurate when applied to mangrove leaves. The N content of the leaves was particularly dynamic with values ranging from 1.27 wt% in green leaves to 0.65 wt% in senescent yellow leaves attached to trees. During decomposition in the water the N content initially decreased to 0.51 wt% due to leaching, but values steadily increased thereafter to 1.07 wt% in the most degraded leaf samples. The absolute mass of N in the leaves increased during decomposition indicating that N immobilization was occurring as decomposition progressed. ?? 1990.

  10. Understanding API-polymer proximities in amorphous stabilized composite drug products using fluorine-carbon 2D HETCOR solid-state NMR. (United States)

    Abraham, Anuji; Crull, George


    A simple and robust method for obtaining fluorine-carbon proximities was established using a (19)F-(13)C heteronuclear correlation (HETCOR) two-dimensional (2D) solid-state nuclear magnetic resonance (ssNMR) experiment under magic-angle spinning (MAS). The method was applied to study a crystalline active pharmaceutical ingredient (API), avagacestat, containing two types of fluorine atoms and its API-polymer composite drug product. These results provide insight into the molecular structure, aid with assigning the carbon resonances, and probe API-polymer proximities in amorphous spray dried dispersions (SDD). This method has an advantage over the commonly used (1)H-(13)C HETCOR because of the large chemical shift dispersion in the fluorine dimension. In the present study, fluorine-carbon distances up to 8 Å were probed, giving insight into the API structure, crystal packing, and assignments. Most importantly, the study demonstrates a method for probing an intimate molecular level contact between an amorphous API and a polymer in an SDD, giving insights into molecular association and understanding of the role of the polymer in API stability (such as recrystallization, degradation, etc.) in such novel composite drug products.

  11. Capturing Guest Dynamics in Metal-Organic Framework CPO-27-M (M = Mg, Zn) by (2)H Solid-State NMR Spectroscopy. (United States)

    Xu, Jun; Sinelnikov, Regina; Huang, Yining


    Metal-organic frameworks (MOFs) are promising porous materials for gas separation and storage as well as sensing. In particular, a series of isostructural MOFs with coordinately unsaturated metal centers, namely, CPO-27-M or M-MOF-74 (M = Mg, Zn, Mn, Fe, Ni, Co, Cu), have shown exceptional adsorption capacity and selectivity compared to those of classical MOFs that contain only fully coordinated metal sites. Although it is widely accepted that the interaction between guest molecules and exposed metal centers is responsible for good selectivity and large maximum uptake, the investigation of such guest-metal interaction is very challenging because adsorbed molecules are usually disordered in the pores and undergo rapid thermal motions. (2)H solid-state NMR (SSNMR) spectroscopy is one of the most extensively used techniques for capturing guest dynamics in porous materials. In this work, variable-temperature (2)H wide-line SSNMR experiments were performed on CPO-27-M (M = Mg, Zn) loaded with four prototypical guest molecules: D2O, CD3CN, acetone-d6, and C6D6. The results indicate that different guest molecules possess distinct dynamic behaviors inside the channel of CPO-27-M. For a given guest molecule, its dynamic behavior also depends on the nature of the metal centers. The binding strength of guest molecules is discussed on the basis of the (2)H SSNMR data.

  12. Assignment of solid-state 13C and 1H NMR spectra of paramagnetic Ni(II) acetylacetonate complexes aided by first-principles computations

    DEFF Research Database (Denmark)

    Rouf, Syed Awais; Jakobsen, Vibe Boel; Mareš, Jiří


    Recent advances in computational methodology allowed for first-principles calculations of the nuclear shielding tensor for a series of paramagnetic nickel(II) acetylacetonate complexes, [Ni(acac)2L2] with L = H2O, D2O, NH3, ND3, and PMe2Ph have provided detailed insight into the origin of the par......Recent advances in computational methodology allowed for first-principles calculations of the nuclear shielding tensor for a series of paramagnetic nickel(II) acetylacetonate complexes, [Ni(acac)2L2] with L = H2O, D2O, NH3, ND3, and PMe2Ph have provided detailed insight into the origin...... of the paramagnetic contributions to the total shift tensor. This was employed for the assignment of the solid-state 1,2H and 13C MAS NMR spectra of these compounds. The two major contributions to the isotropic shifts are by orbital (diamagnetic-like) and contact mechanism. The orbital shielding, contact, as well...... as dipolar terms all contribute to the anisotropic component. The calculations suggest reassignment of the 13C methyl and carbonyl resonances in the acac ligand [Inorg. Chem. 53, 2014, 399] leading to isotropic paramagnetic shifts of δ(13C) ≈ 800–1100 ppm and ≈180–300 ppm for 13C for the methyl and carbonyl...

  13. Tracking Sodium-Antimonide Phase Transformations in Sodium-Ion Anodes: Insights from Operando Pair Distribution Function Analysis and Solid-State NMR Spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Allan, Phoebe K. [University of Cambridge, University Chemical Laboratory, Lensfield Road, Cambridge, CB2 1EW, U.K.; Gonville and Caius College, Trinity; Griffin, John M. [University of Cambridge, University Chemical Laboratory, Lensfield Road, Cambridge, CB2 1EW, U.K.; Darwiche, Ali [Institut; Réseau sur le Stockage Electrochimique de l’Energie (RS2E), FR CNRS 3459, 80039 Amiens Cedex, France; Borkiewicz, Olaf J. [X-ray; Wiaderek, Kamila M. [X-ray; Chapman, Karena W. [X-ray; Morris, Andrew J. [Theory of; Chupas, Peter J. [X-ray; Monconduit, Laure [Institut; Réseau sur le Stockage Electrochimique de l’Energie (RS2E), FR CNRS 3459, 80039 Amiens Cedex, France; Grey, Clare P. [University of Cambridge, University Chemical Laboratory, Lensfield Road, Cambridge, CB2 1EW, U.K.


    Operando pair distribution function (PDF) analysis and ex situ Na-23 magic-angle spinning solid-state nuclear magnetic resonance (MAS ssNMR) spectroscopy are used to gain insight into the alloying mechanism of high-capacity antimony anodes for sodium-ion batteries. Subtraction of the PDF of crystalline NaxSb phases from the total PDF, an approach constrained by chemical phase information gained from Na-23 ssNMR in reference to relevant model compounds, identifies two previously uncharacterized intermediate species formed electro-chemically; a-Na3-xSb (x approximate to 0.4-0.5), a structure locally similar to crystalline Na3Sb (c-Na3Sb) but with significant numbers of sodium vacancies and a limited correlation length, and a-Na1.7Sb, a highly amorphous structure featuring some Sb-Sb bonding. The first sodiation breaks down the crystalline antimony to form first a-Na3-xSb and, finally, crystalline Na3Sb. Desodiation results in the formation of an electrode formed of a composite of crystalline and amorphous antimony networks. We link the different reactivity of these networks to a series of sequential sodiation reactions manifesting as a cascade of processes observed in the electrochemical profile of subsequent cycles. The amorphofis network reacts at higher voltages reforming a-Na1.7Sb, then a-Na3-xSb, whereas lower potentials are required for the sodiation of crystalline antimony, which reacts to form a-Na3-xSb without the formation of a-Na3-xSb. a-Na3-xSb is converted to crystalline Na3Sb at the end of the second discharge. We find no evidence of formation of NaSb. Variable temperature Na-23 NMR experiments reveal significant sodium mobility within c-Na3Sb; this is a possible contributing factor to the excellent rate performance of Sb anodes.

  14. Tracking the evolution and differences between guest-induced phases of Ga-MIL-53 via ultra-wideline (69/71)Ga solid-state NMR spectroscopy. (United States)

    Zhang, Yue; Lucier, Bryan E G; Terskikh, Victor V; Zheng, Renlong; Huang, Yining

    Ga-MIL-53 is a metal-organic framework (MOF) that exhibits a "breathing effect," in which the pore size and overall MOF topology can be influenced by temperature, pressure, and host-guest interactions. The phase control afforded by this flexible framework renders Ga-MIL-53 a promising material for guest storage and sensing applications. In this work, the structure and behavior of four Ga-MIL-53 phases (as, ht, enp and lt), along with CO2 adsorbed within Ga-MIL-53 at various loading levels, has been investigated using (69/71)Ga solid-state NMR (SSNMR) experiments at 21.1T and 9.4T. (69/71)Ga SSNMR spectra are observed to be very sensitive to distortions in the octahedral GaO6 secondary building units within Ga-MIL-53; by extension, Ga NMR parameters are indicative of the particular crystallographic phase of Ga-MIL-53. The evolution of Ga NMR parameters with CO2 loading levels in Ga-MIL-53 reveals that the specific CO2 loading level offers a profound degree of control over the MOF phase, and the data also suggests that a re-entrant phase transition is present. Adsorption of various organic compounds within Ga-MIL-53 has been investigated using a combination of thermal gravimetric analysis (TGA), powder X-ray diffraction (pXRD) and (69/71)Ga SSNMR experiments. Notably, pXRD experiments reveal that guest adsorption and host-guest interactions trigger unambiguous changes in the long-range structure of Ga-MIL-53, while (69/71)Ga SSNMR parameters yield valuable information regarding the effect of the organic adsorbates on the local GaO6 environments. This approach shows promise for the ultra-wideline investigation of other quadrupolar metal nuclei in MIL-53 (e.g., In-MIL-53) and MOFs in general, particularly in regards to adsorption-related applications. Copyright © 2017 Elsevier Inc. All rights reserved.

  15. High throughput methodology for synthesis, screening, and optimization of solid state lithium ion electrolytes. (United States)

    Beal, Mark S; Hayden, Brian E; Le Gall, Thierry; Lee, Christopher E; Lu, Xiaojuan; Mirsaneh, Mehdi; Mormiche, Claire; Pasero, Denis; Smith, Duncan C A; Weld, Andrew; Yada, Chihiro; Yokoishi, Shoji


    A study of the lithium ion conductor Li(3x)La(2/3-x)TiO(3) solid solution and the surrounding composition space was carried out using a high throughput physical vapor deposition system. An optimum total ionic conductivity value of 5.45 × 10(-4) S cm(-1) was obtained for the composition Li(0.17)La(0.29)Ti(0.54) (Li(3x)La(2/3-x)TiO(3)x = 0.11). This optimum value was calculated using an artificial neural network model based on the empirical data. Due to the large scale of the data set produced and the complexity of synthesis, informatics tools were required to analyze the data. Partition analysis was carried out to determine the synthetic parameters of importance and their threshold values. Multivariate curve resolution and principal component analysis were applied to the diffraction data set. This analysis enabled the construction of phase distribution diagrams, illustrating both the phases obtained and the compositional zones in which they occur. The synthetic technique presented has significant advantages over other thin film and bulk methodologies, in terms of both the compositional range covered and the nature of the materials produced.

  16. Effect of precursors on the solid-state synthesis of semiconducting PbS nanostructures

    Directory of Open Access Journals (Sweden)

    Sujata Kasabe


    Full Text Available In this communication, we report facile and economical in-situ preparation of lead sulphide (PbS nanorods and nanocubes within the Polyphenylene sulphide (PPS matrix. PPS plays a dual role in the synthesis of the resultant nanostructures as - (i a chalcogen source and (ii a stabilizing matrix. We studied the effect of change of lead precursor from lead nitrate to acetate on the morphological properties of the resultant nanostructures. The effect of molar ratios of the reactants (1:1, 1:5, 1:10, 1:15 and 1:20 on the morphology of the products was also studied. The resultant nanocomposites were characterized by various physico-chemical techniques like X-ray Diffractometry (XRD, SEM equipped with EDAX, TEM and UV-Visible spectroscopy. The prima-facie observations suggest effective formation and subsequent entrapment of lead sulphide nanorods and nanocubes, respectively, when lead acetate and lead nitrate precursors were used. Additionally, simultaneous occurrence of nanocrystalline cubic lead as an impurity phase is noticed in case of heated admixtures for both the precursors.

  17. Inhibitory Kinetics of Azachalcones and their Oximes on Mushroom Tyrosinase: A Facile Solid-state Synthesis. (United States)

    Radhakrishnan, Sini K; Shimmon, Ronald G; Conn, Costa; Baker, Anthony T


    A solid-state-based mechanochemical process was used to synthesize novel azachalcones and their oximes as tyrosinase inhibitors. Their inhibitory activities on mushroom tyrosinase using l-3,4-dihydroxyphenylalanine as a substrate were investigated. Two of the novel oxime derivatives synthesized were seen to be more potent than the positive control, kojic acid. Both the compounds 1b and 2b inhibited the diphenolase activity of tyrosinase in a dose-dependent manner with their IC50 values of 15.3 and 12.7 μm, respectively. The kinetic analysis showed that their inhibition mechanism was reversible. Both the novel oxime compounds displayed competitive inhibition with their Ki values of 5.1 and 2.5 μm, respectively. This method minimizes waste disposal problems and provides a simple, efficient, and benign method for the synthesis of novel tyrosinase inhibitors for use as skin-whitening agents or as anti-browning food additives. © 2016 Verlag Helvetica Chimica Acta AG, Zürich.

  18. A risk-based statistical investigation of the quantification of polymorphic purity of a pharmaceutical candidate by solid-state 19F NMR. (United States)

    Barry, Samantha J; Pham, Tran N; Borman, Phil J; Edwards, Andrew J; Watson, Simon A


    The DMAIC (Define, Measure, Analyse, Improve and Control) framework and associated statistical tools have been applied to both identify and reduce variability observed in a quantitative (19)F solid-state NMR (SSNMR) analytical method. The method had been developed to quantify levels of an additional polymorph (Form 3) in batches of an active pharmaceutical ingredient (API), where Form 1 is the predominant polymorph. In order to validate analyses of the polymorphic form, a single batch of API was used as a standard each time the method was used. The level of Form 3 in this standard was observed to gradually increase over time, the effect not being immediately apparent due to method variability. In order to determine the cause of this unexpected increase and to reduce method variability, a risk-based statistical investigation was performed to identify potential factors which could be responsible for these effects. Factors identified by the risk assessment were investigated using a series of designed experiments to gain a greater understanding of the method. The increase of the level of Form 3 in the standard was primarily found to correlate with the number of repeat analyses, an effect not previously reported in SSNMR literature. Differences in data processing (phasing and linewidth) were found to be responsible for the variability in the method. After implementing corrective actions the variability was reduced such that the level of Form 3 was within an acceptable range of ±1% ww(-1) in fresh samples of API. Copyright © 2011. Published by Elsevier B.V.

  19. Solid-state NMR spectroscopy of a membrane protein in biphenyl phospholipid bicelles with the bilayer normal parallel to the magnetic field (United States)

    Park, Sang Ho; Loudet, Cécile; Marassi, Francesca M.; Dufourc, Erick J.; Opella, Stanley J.


    Bicelles composed of the long-chain biphenyl phospholipid TBBPC (1-tetradecanoyl-2-(4-(4-biphenyl)butanoyl)-sn-glycero-3-PC) and the short-chain phospholipid DHPC align with their bilayer normals parallel to the direction of the magnetic field. In contrast, in typical bicelles the long-chain phospholipid is DMPC or DPPC, and the bilayers align with their normals perpendicular to the field. Samples of the membrane-bound form of the major coat protein of Pf1 bacteriophage in TBBPC bicelles are stable for several months, align magnetically over a wide range of temperatures, and yield well-resolved solid-state NMR spectra similar to those obtained from samples aligned mechanically on glass plates or in DMPC bicelle samples "flipped" with lanthanide ions so that their bilayer normals are parallel to the field. The order parameter of the TBBPC bicelle sample decreases from approximately 0.9 to 0.8 upon increasing the temperature from 20 °C to 60 °C. Since the frequency spans of the chemical shift and dipolar coupling interactions are twice as large as those obtained from proteins in DMPC bicelles without lanthanide ions, TBBPC bicelles provide an opportunity for structural studies with higher spectral resolution of the metal-binding membrane proteins without the risk of chemical or spectroscopic interference from the added lanthanide ions. In addition, the large temperature range of these samples is advantageous for the studies of membrane proteins that are unstable at elevated temperatures and for experiments requiring measurements as a function of temperature.

  20. Structural changes of a light-activated G protein-coupled receptor determined by solid-state NMR: Channeling light energy into the visual pigment rhodopsin (United States)

    Crocker, Evan Daniel

    Absorption of light by the visual pigment rhodopsin triggers an 11- cis to all-trans isomerization of the retinal chromophore within the interior of this G protein-coupled receptor. Two-dimensional solid-state NMR of rhodopsin and the active metarhodopsin II intermediate is used to determine the trajectory of the retinal and the effects of retinal isomerization on the structure of the protein. Structural constraints obtained in this study indicate that helices H5, H6 and H7 undergo changes in orientation relative to the H1--H4 core of the receptor upon retinal isomerization. The position of the retinal beta-ionone ring in metarhodopsin II was found to translate toward and interact with H5. Changes observed in the H4--H5 interface are consistent with a small counter clockwise rotation of H5, as observed from the extracellular side of the protein. Retinal isomerization also alters the structure and position of H6. The position of Trp265 relative to H3 and the retinal in metarhodopsin II indicates that the extracellular end of H6 moves inward and rotates upon activation. Together with previous EPR measurements of the relative positions of the intracellular ends of H3 and H6 in metarhodopsin II, the NMR constraints define how Trp265 serves as a lever for the motion of H6. Retinal translation also leads to an inward motion of the extracellular end of H7, suggesting that H6 and H7 move in concert upon receptor activation. A function of the highly conserved NPxxY sequence on the intracellular end of H7 is proposed. Based on the observations described above and indications that helices H1 through H4 form a stable core that serves as a platform for the motion of H5, H6 and H7, a model for the structure of the active state of rhodopsin is presented. Aspects of this model are put into the context of the proposed activation mechanisms of other members of the GPCR superfamily.

  1. Structural Characterization of Febuxostat/l-Pyroglutamic Acid Cocrystal Using Solid-State 13C-NMR and Investigational Study of Its Water Solubility

    Directory of Open Access Journals (Sweden)

    Ji-Hun An


    Full Text Available Febuxostat (FB is a poorly water-soluble drug that belongs to BCS class II. The drug is employed for the treatment of inflammatory disease arthritis urica (gout, and the free base, FB form-A, is most preferred for drug formulation. In order to achieve a goal of improving the water solubility of FB form-A, this study was carried out using the cocrystallization technique called the liquid-assisted grinding method to produce FB cocrystals. Here, five amino acids containing amine (NH, oxygen (O, and hydroxyl (OH functional groups, and possessing difference of pKa less than 3 with FB, were selected as coformers. Then, solvents including methanol, ethanol, isopropyl alcohol, n-hexane, dichloromethane, and acetone were used for the cocrystal screening. As a result, a cocrystal was obtained when acetone and l-pyroglutamic acid (PG of 0.5 eq. were employed as solvent and coformer, respectively. The ratio of 2:1, which is the ratio of FB to PG within FB-PG cocrystal, was predicted by means of solid-state CP/MAS 13C-NMR, solution-state NMR (1H, 13C, and 2D and FT-IR. Moreover, Powder X-ray Diffraction (PXRD, Differential Scanning Calorimetry (DSC, and Thermogravimetric Analysis (TGA were used to investigate the characteristics of FB-PG cocrystal. In addition, comparative solubility tests between FB-PG cocrystal and FB form-A were conducted in deionized water and under simulated gastrointestinal pH (1.2, 4, and 6.8 conditions. The result revealed that FB-PG cocrystal has a solubility of four-fold higher than FB form-A in deionized water and two-fold and five-fold greater than FB form-A at simulated gastrointestinal pH 1.2 and pH 4, respectively. Besides, solubilities of FB-PG cocrystal and FB form-A at pH 6.8 were similar to the results measured in deionized water. Therefore, it is postulated that FB-PG cocrystal has a potential overcoming the limitations related to the low aqueous solubility of FB form-A. Accordingly, FB-PG cocrystal is suggested as an

  2. Alpha-tricalcium phosphate (α-TCP): solid state synthesis from different calcium precursors and the hydraulic reactivity. (United States)

    Cicek, Gulcin; Aksoy, Eda Ayse; Durucan, Caner; Hasirci, Nesrin


    The effects of solid state synthesis process parameters and primary calcium precursor on the cement-type hydration efficiency (at 37 °C) of α-tricalcium phosphate (Ca(3)(PO(4))(2) or α-TCP) into hydroxyapatite (Ca(10-x)HPO(4)(PO(4))(6-x)(OH)(2-x) x = 0-1, or HAp) have been investigated. α-TCP was synthesized by firing of stoichiometric amount of calcium carbonate (CaCO(3)) and monetite (CaHPO(4)) at 1150-1350 °C for 2 h. Three commercial grade CaCO(3) powders of different purity were used as the starting material and the resultant α-TCP products for all synthesis routes were compared in terms of the material properties and the reactivity. The reactant CaHPO(4) was also custom synthesized from the respective CaCO(3) source. A low firing temperature in the range of 1150-1350°C promoted formation of β-polymorph as a second phase in the resultant TCP. Meanwhile, higher firing temperatures resulted in phase pure α-TCP with poor hydraulic reactivity. The extension of firing operation also led to a decrease in the reactivity. It was found that identical synthesis history, morphology, particle size and crystallinity match between the α-TCPs produced from different CaCO(3) sources do not essentially culminate in products exhibiting similar hydraulic reactivity. The changes in reactivity are arising from differences in the trace amount of impurities found in the CaCO(3) precursors. In this regard, a correlation between the observed hydraulic reactivities and the impurity content of the CaCO(3) powders--as determined by inductively coupled plasma mass spectrometry--has been established. A high level of magnesium impurity in the CaCO(3) almost completely hampers the hydration of α-TCP. This impurity also favors formation of β- instead of α-polymorph in the product of TCP upon firing.

  3. Solid-State Form Characterization of Riparin I

    Directory of Open Access Journals (Sweden)

    Elisana Afonso de Moura


    Full Text Available Riparin I is an alkamide with potential anxiolytic activity in preclinical studies. The characterization and understanding of solid-state properties play an importance role in drug development. For this work, the solid state of five riparin I batches (RIP-1, RIP-2, RIP-3, RIP-4, and RIP-5, obtained by the same synthesis process, were characterized by Scanning Electron Microscopy (SEM, Differential Scanning Calorimetry (DSC, DSC-photovisual, Thermogravimetry (TG, Fourier Transform Infrared (FTIR, Pyrolysis (Pyr-GC/MS, X-ray Powder Diffraction (PXRD, and Solid-State Nuclear Magnetic Resonance (ssNMR techniques. Batches of riparin I with different crystal habits resulting in crystallization impurities were observed, which can be attributed to the presence of triethylamine. The main differences were observed by DSC, PXRD, and ssNMR analysis. DSC curves of RIP-2 and RIP-3 presented endothermic peaks at different temperatures of fusion, which can be attributed to the mixture of different crystalline forms. PXRD and ssNMR results confirmed crystallinity differences. The results offer evidence of the importance of controlling the reproducibility of the synthesis in order to obtain the adequate morphology for therapeutic efficacy and avoiding future problems in quality control of riparin I products.

  4. Solid state synthesis of Bi 0 . 4 Sr 0 . 6 FeO 3 - δ powder for SOFC applications (United States)

    Rico, M.; Rodriguez, R.; Zapata, V. H.; Medina-Barreto, M. H.; Cruz-Mu noz, B.; Tabares, J. A.; Benitez-Castro, A. M.; Giraldo-Betancur, A. L.; Muñoz-Saldaña, J.


    We report on the synthesis of Bi0.4Sr0.6FeO3 powder with cubic structure by solid state reaction (mechanical milling and calcination) from Bi2O3, SrCO3 and Fe2O3 stoichiometric ratios. Milled powder mixtures were heat treated between 775∘C and 825∘C for 30 and 60 min in oxygen atmosphere and characterized by X-ray diffraction (XRD), impedance as well as Mössbauer spectroscopy. The cubic phase of Bi0.4Sr0.6FeO3 was successfully obtained in samples milled for only 2 h and a subsequent calcination at 800∘C. Irrespective of milling time, heat treatments at lower temperatures (775∘C) still show spurious phases such as Sr0.23Bi0.76O1.1 (30 min) and Sr0.53Bi1.72O3 (60 min). Impedance spectroscopy show high values (105-109) Ω indicating strong structural bond between the atoms of the system and activation energies for the strontium ion around 04 eV. These results show a single dynamic behavior in a range from 1 to 2*105 Hz enabling data adjustment and analysis to a RC circuit. Conductivity results normally show a behavior that obeys the universal law of Jonscher's relaxation ( σ = σ Dc + α ω n) with values for the exponent n (0.8 Fe2O3. While the result of isomer shift corresponds to a Fe+3 oxidation state irrespective of the heat treatment.

  5. Combustion Synthesis of UHTC Composites from Ti–B4C Solid State Reaction with Addition of VIb Transition Metals

    Directory of Open Access Journals (Sweden)

    Chun-Liang Yeh


    Full Text Available UHTC composites were prepared by self-propagating high-temperature synthesis (SHS from the Ti–B4C reaction system with addition of Cr, Mo, and W. The starting sample composition was formulated as (3−xTi + B4C + xMe with x = 0.1–1.0 and Me = Cr, Mo, or W. For all samples conducted in this study, self-sustaining combustion was well established and propagated with a distinct reaction front. With no addition of Cr, Mo, or W, solid state combustion of the 3Ti + B4C sample featuring a combustion front temperature (Tc of 1766 °C and a combustion wave velocity (Vf of 16.5 mm/s was highly exothermic and produced an in situ composite of 2TiB2 + TiC. When Cr, Mo, or W was adopted to replace a portion of Ti, the reaction exothermicity was lowered, and hence, a significant decrease in Tc (from 1720 to 1390 °C and Vf (from 16.1 to 3.9 mm/s was observed. With addition of Cr, Mo, and W, the final products were CrB-, MoB-, and WB-added TiB2–TiC composites. The absence of CrB2, MoB2, and WB2 was attributed partly to the loss of boron from thermal decomposition of B4C and partly to lack of sufficient reaction time inherent to the SHS process.

  6. Solid state chemistry and its applications

    CERN Document Server

    West, Anthony R


    Solid State Chemistry and its Applications, 2nd Edition: Student Edition is an extensive update and sequel to the bestselling textbook Basic Solid State Chemistry, the classic text for undergraduate teaching in solid state chemistry worldwide. Solid state chemistry lies at the heart of many significant scientific advances from recent decades, including the discovery of high-temperature superconductors, new forms of carbon and countless other developments in the synthesis, characterisation and applications of inorganic materials. Looking forward, solid state chemistry will be crucial for the

  7. Amplitudes and time scales of picosecond-to-microsecond motion in proteins studied by solid-state NMR: a critical evaluation of experimental approaches and application to crystalline ubiquitin

    Energy Technology Data Exchange (ETDEWEB)

    Haller, Jens D.; Schanda, Paul, E-mail: [Univ. Grenoble Alpes, Institut de Biologie Structurale (IBS) (France)


    Solid-state NMR provides insight into protein motion over time scales ranging from picoseconds to seconds. While in solution state the methodology to measure protein dynamics is well established, there is currently no such consensus protocol for measuring dynamics in solids. In this article, we perform a detailed investigation of measurement protocols for fast motions, i.e. motions ranging from picoseconds to a few microseconds, which is the range covered by dipolar coupling and relaxation experiments. We perform a detailed theoretical investigation how dipolar couplings and relaxation data can provide information about amplitudes and time scales of local motion. We show that the measurement of dipolar couplings is crucial for obtaining accurate motional parameters, while systematic errors are found when only relaxation data are used. Based on this realization, we investigate how the REDOR experiment can provide such data in a very accurate manner. We identify that with accurate rf calibration, and explicit consideration of rf field inhomogeneities, one can obtain highly accurate absolute order parameters. We then perform joint model-free analyses of 6 relaxation data sets and dipolar couplings, based on previously existing, as well as new data sets on microcrystalline ubiquitin. We show that nanosecond motion can be detected primarily in loop regions, and compare solid-state data to solution-state relaxation and RDC analyses. The protocols investigated here will serve as a useful basis towards the establishment of a routine protocol for the characterization of ps–μs motions in proteins by solid-state NMR.

  8. Synthesis and photoluminescence properties of LiSrPO{sub 4}:Eu{sup 2+} phosphor for solid state lighting

    Energy Technology Data Exchange (ETDEWEB)

    Game, D. N., E-mail: [Deccan Education Society’s Technical Institute, Fergusson College Campus, Pune (India); Taide, S. T.; Khan, Z. S.; Omanwar, S. K. [Department of Physics, Sant Gadge Baba, Aravati University, Amravati (India); Ingale, N. B. [Prof. Ram Meghe Institute of Technology and Research, Badnera, Amravati (India)


    A novel method to prepare orthophosphate LiSrPO{sub 4}: Eu{sup 2+} phosphor for white light-emitting diodes (w-LEDs) is given in this paper. Phosphor was successfully synthesized by Pechini (citrate gel) method which is efficient than conventional high temperature solid state reaction. X-ray powder diffraction (XRD) analysis confirmed the single phase formation of LiSrPO{sub 4}:Eu{sup 2+} with monoclinic crystal structure. Luminescence results showed that the phosphor could be efficiently excited by near UV and exhibited bright blue emission at λ{sub em} = 420 nm corresponding to 5d– 4f transition of Eu{sup 2+}. The phosphor exhibits blue emission bands under 350 nm excitation. This mercury-free excitation is useful for solid state lighting and light-emitting diode (LED). Hence it could be useful for solid state lighting and light-emitting diode (LED) application.

  9. Hydrogen Atomic Positions of O-H···O Hydrogen Bonds in Solution and in the Solid State: The Synergy of Quantum Chemical Calculations with ¹H-NMR Chemical Shifts and X-ray Diffraction Methods. (United States)

    Siskos, Michael G; Choudhary, M Iqbal; Gerothanassis, Ioannis P


    The exact knowledge of hydrogen atomic positions of O-H···O hydrogen bonds in solution and in the solid state has been a major challenge in structural and physical organic chemistry. The objective of this review article is to summarize recent developments in the refinement of labile hydrogen positions with the use of: (i) density functional theory (DFT) calculations after a structure has been determined by X-ray from single crystals or from powders; (ii) ¹H-NMR chemical shifts as constraints in DFT calculations, and (iii) use of root-mean-square deviation between experimentally determined and DFT calculated ¹H-NMR chemical shifts considering the great sensitivity of ¹H-NMR shielding to hydrogen bonding properties.

  10. Hydrogen Atomic Positions of O–H···O Hydrogen Bonds in Solution and in the Solid State: The Synergy of Quantum Chemical Calculations with 1H-NMR Chemical Shifts and X-ray Diffraction Methods

    Directory of Open Access Journals (Sweden)

    Michael G. Siskos


    Full Text Available The exact knowledge of hydrogen atomic positions of O–H···O hydrogen bonds in solution and in the solid state has been a major challenge in structural and physical organic chemistry. The objective of this review article is to summarize recent developments in the refinement of labile hydrogen positions with the use of: (i density functional theory (DFT calculations after a structure has been determined by X-ray from single crystals or from powders; (ii 1H-NMR chemical shifts as constraints in DFT calculations, and (iii use of root-mean-square deviation between experimentally determined and DFT calculated 1H-NMR chemical shifts considering the great sensitivity of 1H-NMR shielding to hydrogen bonding properties.

  11. A Modular Implementation for the Simulation of 1D and 2D Solid-State NMR Spectra of Quadrupolar Nuclei in the Virtual Multifrequency Spectrometer-Draw Graphical Interface. (United States)

    Presti, Davide; Pedone, Alfonso; Licari, Daniele; Barone, Vincenzo


    We present the implementation of the solid state (SoS)NMR module for the simulation of several 1D and 2D NMR spectra of all the elements in the periodic table in the virtual multifrequency spectrometer (VMS). This module is fully integrated with the graphical user interface of VMS (VMS-Draw) [Licari et al., J. Comput. Chem. 36, 2015, 321-334], a freeware tool which allows a user-friendly handling of structures and analyses of advanced spectroscopical properties of chemical compounds-from model systems to real-world applications. Besides the numerous modules already available in VMS for the study of electronic, optical, vibrational, vibronic, and EPR properties, here the simulation of NMR spectra is presented with a particular emphasis on those techniques usually employed to investigate solid state systems. The SoSNMR module benefits from its ability to work under both periodic and nonperiodic conditions, such that small molecules/molecular clusters can be treated, as well as extended three-dimensional systems enforcing (or not) translational periodicity. These features allow VMS to simulate spectra resulting from NMR calculations by some popular quantum chemistry codes, namely Gaussian09/16, Castep, and Quantum Espresso. The effectiveness of the SoSNMR module of VMS is examined throughout the manuscript, and applied to simulate 1D static, MAS, and VAS NMR spectra as well as 2D correlation (90°, MAS) and MQMAS spectra of active NMR nuclei embedded in different amorphous and crystalline systems of actual interest in chemistry and material science. Finally, the program is able to simulate the spectra of both the total ensemble of spin-active nuclei present in the system and of subensembles differentiated depending on the chemical environment of the first and second coordination sphere in a very general way applicable to any kind of systems.

  12. Solid-state synthesis and characterization of LiCoO2 and LiNiyCo1 ...

    Indian Academy of Sciences (India)


    Heider U, Oesten R, Heider L, Niemann M, Amann A and Lotz. N 1998 15th Int. sem. and exhibition on primary and secon- dary batteries (Florida). Julien C, Michael S S and Ziolkiewicz S 1999 Int. J. Inorg. Mater. 1 29. Kanno R, Kubo H, Kawamoto Y, Kamiyama T, Izumi F,. Takeda Y and Takano M 1994 J. Solid State Chem.

  13. Solid-state (185/187)Re NMR and GIPAW DFT study of perrhenates and Re2(CO)10: chemical shift anisotropy, NMR crystallography, and a metal-metal bond. (United States)

    Widdifield, Cory M; Perras, Frédéric A; Bryce, David L


    Advances in solid-state nuclear magnetic resonance (SSNMR) methods, such as dynamic nuclear polarization (DNP), intricate pulse sequences, and increased applied magnetic fields, allow for the study of systems which even very recently would be impractical. However, SSNMR methods using certain quadrupolar probe nuclei (i.e., I > 1/2), such as (185/187)Re remain far from fully developed due to the exceedingly strong interaction between the quadrupole moment of these nuclei and local electric field gradients (EFGs). We present a detailed high-field (B0 = 21.1 T) experimental SSNMR study on several perrhenates (KReO4, AgReO4, Ca(ReO4)2·2H2O), as well as ReO3 and Re2(CO)10. We propose solid ReO3 as a new rhenium SSNMR chemical shift standard due to its reproducible and sharp (185/187)Re NMR resonances. We show that for KReO4, previously poorly understood high-order quadrupole-induced effects (HOQIE) on the satellite transitions can be used to measure the EFG tensor asymmetry (i.e., ηQ) to nearly an order-of-magnitude greater precision than competing SSNMR and nuclear quadrupole resonance (NQR) approaches. Samples of AgReO4 and Ca(ReO4)2·2H2O enable us to comment on the effects of counter-ions and hydration upon Re(vii) chemical shifts. Calcium-43 and (185/187)Re NMR tensor parameters allow us to conclude that two proposed crystal structures for Ca(ReO4)2·2H2O, which would be considered as distinct, are in fact the same structure. Study of Re2(CO)10 provides insights into the effects of Re-Re bonding on the rhenium NMR tensor parameters and rhenium oxidation state on the Re chemical shift value. As overtone NQR experiments allowed us to precisely measure the (185/187)Re EFG tensor of Re2(CO)10, we were able to measure rhenium chemical shift anisotropy (CSA) for the first time in a powdered sample. Experimental observations are supported by gauge-including projector augmented-wave (GIPAW) density functional theory (DFT) calculations, with NMR tensor calculations also

  14. Determination of the Tautomeric Equilibria of Pyridoyl Benzoyl -Diketones in the Liquid and Solid State through the use of Deuterium Isotope Effects on 1H and 13C NMR Chemical Shifts and Spin Coupling Constants

    DEFF Research Database (Denmark)

    Hansen, Poul Erik; Borisov, Eugeny V.; Lindon, John C.


    , in the solution state the 2-bond and 3-bond J(1H–13C) coupling constants have been used to confirm the equilibrium positions. The isotope effects due to deuteriation at the OH position are shown to be superior to chemical shift in determination of equilibrium positions of these almost symmetrical -pyridoyl......-benzoyl methanes. The assignments of the NMR spectra are supported by calculations of the chemical shifts at the DFT level. The equilibrium positions are shown to be different in the liquid and the solid state. In the liquid state the 4-pyridoyl derivative is at the B-form (C-1 is OH), whereas the 2-and 3-pyridoyl...

  15. Distinguishing tautomerism in the crystal structure of (Z)-N-(5-ethyl-2,3-dihydro-1,3,4-thiadiazol-2-ylidene)-4-methylbenzenesulfonamide using DFT-D calculations and (13)C solid-state NMR

    DEFF Research Database (Denmark)

    Li, Xiaozhou; Bond, Andrew D; Johansson, Kristoffer E


    The crystal structure of the title compound, C11H13N3O2S2, has been determined previously on the basis of refinement against laboratory powder X-ray diffraction (PXRD) data, supported by comparison of measured and calculated (13)C solid-state NMR spectra [Hangan et al. (2010). Acta Cryst. B66, 615...... in this way. However, the correct tautomer can be distinguished from the incorrect one by previously reported quantitative criteria based on the extent of structural distortion on optimization of the crystal structure using dispersion-corrected density functional theory (DFT-D) calculations. Calculation...

  16. Synthesis and luminescence properties of Ca5(PO43Cl:Eu2+ phosphor for solid state lighting

    Directory of Open Access Journals (Sweden)

    Deorao N. Game


    Full Text Available A novel method to prepare Eu2+ doped chlorapatite phosphor Ca5(PO43Cl useful for solid state lighting has been given in this paper. The phosphor was synthesized by the Pechini (citrate gel method which turned out to be more efficient than the conventional high temperature solid state reaction. The results of the photoluminescence (PL investigation revealed that it was possible to efficiently excite the phosphor by a UV–visible light from 220 to 430nm; the phosphor exhibited a bright blue emission at the wavelength λem=456nm for the excitation wavelength λex=350nm of near-ultraviolet light. The developed phosphor emits in blue and, hence, could provide one of the three (RGB primary color components in a phosphor-converted LED-producing white light.

  17. Vapour-induced solid-state C-H bond activation for the clean synthesis of an organopalladium biothiol sensor. (United States)

    Monas, Andrea; Užarević, Krunoslav; Halasz, Ivan; Kulcsár, Marina Juribašić; Ćurić, Manda


    Room-temperature accelerated aging in the solid state has been applied for atom- and energy-efficient activation of either one or two C-H bonds of azobenzene and methyl orange by palladium(ii) acetate. Organopalladium complexes are prepared in quantitative reactions without potentially harmful side products. Dicyclopalladated methyl orange is water-soluble and is a selective chromogenic biothiol sensor at physiologically-relevant micromolar concentrations in buffered aqueous media.

  18. Ring-shaped silafluorene derivatives as efficient solid-state UV-fluorophores: synthesis, characterization, and photoluminescent properties. (United States)

    Cai, Yuanjing; Samedov, Kerim; Dolinar, Brian S; Albright, Haley; Guzei, Ilia A; Hu, Rongrong; Zhang, Chaocan; West, Robert


    Four ring-shaped silafluorene-containing compounds (1-4) were synthesized and characterized as potentially promising monomers for fluorescent polymers. Their optical properties in solution and solid state (thin film and powder) were studied. These compounds have low quantum yields in solution (Φ(fl)=0.13-0.15) with fluorescence maxima at about 355 nm, but high quantum yields in the solid state (powder, Φ(fl)=0.35-0.54) with fluorescence maxima at about 377 and 488 nm. Influence of the substituents and the number of silafluorene units in 1-4 on their optical properties was investigated. Extensive study of the X-ray crystal structures of 1-4 was undertaken to analyze and qualitatively estimate the role, extent, and influence of silafluorene moieties' interactions on solid-state fluorescent properties. Excited state UV/Vis and theoretical molecular orbital (MO) calculations were performed to explore possible fluorescence mechanisms and differences in quantum yields among these compounds. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. One-step synthesis of solid state luminescent carbon-based silica nanohybrids for imaging of latent fingerprints (United States)

    Li, Feng; Li, Hongren; Cui, Tianfang


    Fluorescent carbon-based nanomaterials(CNs) with tunable visible emission are biocompatible, environment friendly and most suitable for various biomedical applications. Despite the successes in preparing strongly fluorescent CNs, preserving the luminescence in solid materials is still challenging because of the serious emission quenching of CNs in solid state materials. In this work, fluorescent carbon and silica nanohybrids (SiCNHs) were synthesized via a simple one-step hydrothermal approach by carbonizing sodium citrate and (3-aminopropyl)triethoxysilane(APTES), and hydrolysis of tetraethyl orthosilicate(TEOS). The resultant SiCNs were characterized through X-ray diffraction (XRD), transmission electron microscopy (TEM), FT-IR, X-ray photoelectron spectroscopy (XPS), and photoluminescence (PL) spectroscopy. The SiCNs exhibited strong fluorescence in both aqueous and solid states. The luminescent solid state SiCNs power were successfully used as a fluorescent labeling material for enhanced imaging of latent fingerprints(LFPs) on single background colour and multi-coloured surfaces substrates in forensic science for individual identification.

  20. The stoichiometry of synthetic alunite as a function of hydrothermal aging investigated by solid-state NMR spectroscopy, powder X-ray diffraction and infrared spectroscopy

    DEFF Research Database (Denmark)

    Grube, Elisabeth; Nielsen, Ulla Gro


    angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy. The 1H MAS NMR spectra recorded at high magnetic field (21.1 T, 900 MHz) allowed for a clear separation of the different proton environments and for quantitative determination of the aluminum vacancy concentration as a function of time...

  1. Characterization of pitches by solid state nuclear magnetic resonance

    Energy Technology Data Exchange (ETDEWEB)

    Grint, A.; Proud, G.P.; Poplett, I.J.F.; Bartle, K.D.; Wallace, S.; Matthews, R.S. (The British Petroleum Company plc, Sunbury-on-Thames (UK). BP Research Centre)


    Solid petroleum, ethylene-cracker, and coal tar pitches were characterized by {sup 13}C cross-polarization-magic-angle-spinning nuclear magnetic resonance spectroscopy (CP/MAS n.m.r.) and by dipolar dephasing. The relative numbers of carbon atoms were determined by peak synthesis of the dipolar dephased (DD) spectrum and of the difference spectrum between the CP/MAS and DD spectra. Spectra and derived structural information obtained in this way were in good agreement with high-resolution n.m.r. spectra of pitch in solution. Solid state n.m.r. is shown to be an attractive alternative to the recording of spectra of pitches in reactive solvents. 11 refs., 3 figs., 3 tabs.

  2. Solid-state reaction synthesis for mixed-phase Eu3+-doped bismuth molybdate and its luminescence properties (United States)

    Liang, Danyang; Ding, Yu; Wang, Nan; Cai, Xiaomeng; Li, Jia; Han, Linyu; Wang, Shiqi; Han, Yuanyuan; Jia, Guang; Wang, Liyong


    A method for mixed-phase bismuth molybdate doped with Eu3+ ions was developed by solid-state reaction assisting with polyvinyl alcohol (PVA). The results of powder X-ray diffraction showed a mixed-phase structure and the microscopical characterization technology revealed the formation process with the addition of PVA. As a structure inducer, the PVA molecules played a vital role in the formation of phase structure. The as-obtained Eu3+-doped bismuth molybdates were also characterized by using different spectroscopic techniques including FTIR and photoluminescence (PL). The results show that doping concentration, PVA addition and calcination temperature affect photoluminescence properties remarkably.


    Directory of Open Access Journals (Sweden)

    Rigoberto Lopez-Juarez


    Full Text Available Lanthanum-doped sodium tantalate was synthesized by solid state method at low temperature and short calcination time. Pure phase powders were obtained after calcination at 950°C and 1000°C for 1h with average crystal size below 150 nm. The photocatalytic performance was increased with La concentration, reaching a maximum at 2 mol% La. Good activity was observed even without any loading cocatalyst. After further calcination, there was no evidence of improvement of the photocatalytic performance

  4. Enhanced efficiency of solid-state NMR investigations of energy materials using an external automatic tuning/matching (eATM) robot (United States)

    Pecher, Oliver; Halat, David M.; Lee, Jeongjae; Liu, Zigeng; Griffith, Kent J.; Braun, Marco; Grey, Clare P.


    We have developed and explored an external automatic tuning/matching (eATM) robot that can be attached to commercial and/or home-built magic angle spinning (MAS) or static nuclear magnetic resonance (NMR) probeheads. Complete synchronization and automation with Bruker and Tecmag spectrometers is ensured via transistor-transistor-logic (TTL) signals. The eATM robot enables an automated "on-the-fly" re-calibration of the radio frequency (rf) carrier frequency, which is beneficial whenever tuning/matching of the resonance circuit is required, e.g. variable temperature (VT) NMR, spin-echo mapping (variable offset cumulative spectroscopy, VOCS) and/or in situ NMR experiments of batteries. This allows a significant increase in efficiency for NMR experiments outside regular working hours (e.g. overnight) and, furthermore, enables measurements of quadrupolar nuclei which would not be possible in reasonable timeframes due to excessively large spectral widths. Additionally, different tuning/matching capacitor (and/or coil) settings for desired frequencies (e.g.7Li and 31P at 117 and 122 MHz, respectively, at 7.05 T) can be saved and made directly accessible before automatic tuning/matching, thus enabling automated measurements of multiple nuclei for one sample with no manual adjustment required by the user. We have applied this new eATM approach in static and MAS spin-echo mapping NMR experiments in different magnetic fields on four energy storage materials, namely: (1) paramagnetic 7Li and 31P MAS NMR (without manual recalibration) of the Li-ion battery cathode material LiFePO4; (2) paramagnetic 17O VT-NMR of the solid oxide fuel cell cathode material La2NiO4+δ; (3) broadband 93Nb static NMR of the Li-ion battery material BNb2O5; and (4) broadband static 127I NMR of a potential Li-air battery product LiIO3. In each case, insight into local atomic structure and dynamics arises primarily from the highly broadened (1-25 MHz) NMR lineshapes that the eATM robot is uniquely

  5. Solid state physics at ISOLDE

    CERN Document Server

    Deicher, M; Wichert, T


    Radioactive atoms have been used in solid state physics and in materials science for decades. Besides their classical applications as tracers for diffusion studies, nuclear techniques such as Mossbauer spectroscopy, perturbed gamma gamma angular correlation, beta -NMR, and emission channeling make use of nuclear properties (via hyperfine interactions or emitted alpha or beta particles) to gain microscopic information on structural and dynamical properties of solids. During the last decade, the availability of many different radioactive isotopes as clean ion beams at ISOL facilities like ISOLDE/CERN has triggered a new era involving methods sensitive to the optical and electronic properties of solids, especially in the field of semiconductor physics. This overview will browse through ongoing solid state physics experiments with radioactive ion beams at ISOLDE. A wide variety of problems is under study, involving bulk properties, surfaces and interfaces in many different systems like semiconductors, superconduc...

  6. Solid state video cameras

    CERN Document Server

    Cristol, Y


    Solid State Video Cameras reviews the state of the art in the field of solid-state television cameras as compiled from patent literature. Organized into 10 chapters, the book begins with the basic array types of solid-state imagers and appropriate read-out circuits and methods. Documents relating to improvement of picture quality, such as spurious signal suppression, uniformity correction, or resolution enhancement, are also cited. The last part considerssolid-state color cameras.

  7. Solid state physics

    CERN Document Server

    Burns, Gerald


    Solid State Physics, International Edition covers the fundamentals and the advanced concepts of solid state physics. The book is comprised of 18 chapters that tackle a specific aspect of solid state physics. Chapters 1 to 3 discuss the symmetry aspects of crystalline solids, while Chapter 4 covers the application of X-rays in solid state science. Chapter 5 deals with the anisotropic character of crystals. Chapters 6 to 8 talk about the five common types of bonding in solids, while Chapters 9 and 10 cover the free electron theory and band theory. Chapters 11 and 12 discuss the effects of moveme

  8. Solid state, thermal synthesis of site-specific protein-boron cluster conjugates and their physicochemical and biochemical properties. (United States)

    Goszczyński, Tomasz M; Kowalski, Konrad; Leśnikowski, Zbigniew J; Boratyński, Janusz


    Boron clusters represent a vast family of boron-rich compounds with extraordinary properties that provide the opportunity of exploitation in different areas of chemistry and biology. In addition, boron clusters are clinically used in boron neutron capture therapy (BNCT) of tumors. In this paper, a novel, in solid state (solvent free), thermal method for protein modification with boron clusters has been proposed. The method is based on a cyclic ether ring opening in oxonium adduct of cyclic ether and a boron cluster with nucleophilic centers of the protein. Lysozyme was used as the model protein, and the physicochemical and biological properties of the obtained conjugates were characterized. The main residues of modification were identified as arginine-128 and threonine-51. No significant changes in the secondary or tertiary structures of the protein after tethering of the boron cluster were found using mass spectrometry and circular dichroism measurements. However, some changes in the intermolecular interactions and hydrodynamic and catalytic properties were observed. To the best of our knowledge, we have described the first example of an application of cyclic ether ring opening in the oxonium adducts of a boron cluster for protein modification. In addition, a distinctive feature of the proposed approach is performing the reaction in solid state and at elevated temperature. The proposed methodology provides a new route to protein modification with boron clusters and extends the range of innovative molecules available for biological and medical testing. Copyright © 2014 Elsevier B.V. All rights reserved.

  9. Facile solid-state synthesis of Ni@C nanosheet-assembled hierarchical network for high-performance lithium storage (United States)

    Gu, Jinghe; Li, Qiyun; Zeng, Pan; Meng, Yulin; Zhang, Xiukui; Wu, Ping; Zhou, Yiming


    Micro/nano-architectured transition-metal@C hybrids possess unique structural and compositional features toward lithium storage, and are thus expected to manifest ideal anodic performances in advanced lithium-ion batteries (LIBs). Herein, we propose a facile and scalable solid-state coordination and subsequent pyrolysis route for the formation of a novel type of micro/nano-architectured transition-metal@C hybrid (i.e., Ni@C nanosheet-assembled hierarchical network, Ni@C network). Moreover, this coordination-pyrolysis route has also been applied for the construction of bare carbon network using zinc salts instead of nickel salts as precursors. When applied as potential anodic materials in LIBs, the Ni@C network exhibits Ni-content-dependent electrochemical performances, and the partially-etched Ni@C network manifests markedly enhanced Li-storage performances in terms of specific capacities, cycle life, and rate capability than the pristine Ni@C network and carbon network. The proposed solid-state coordination and pyrolysis strategy would open up new opportunities for constructing micro/nano-architectured transition-metal@C hybrids as advanced anode materials for LIBs.

  10. Confined Synthesis of Carbon Nitride in a Layered Host Matrix with Unprecedented Solid-State Quantum Yield and Stability. (United States)

    Liu, Wendi; Xu, Simin; Guan, Shanyue; Liang, Ruizheng; Wei, Min; Evans, David G; Duan, Xue


    Fluorescent carbon nanomaterials have drawn tremendous attention for their intriguing optical performances, but their employment in solid-state luminescent devices is rather limited as a result of aggregation-induced photoluminescence quenching. Herein, ultrathin carbon nitride (CN) is synthesized within the 2D confined region of layered double hydroxide (LDH) via triggering the interlayer condensation reaction of citric acid and urea. The resulting CN/LDH phosphor emits strong cyan light under UV-light irradiation with an absolute solid-state quantum yield (SSQY) of 95.9 ± 2.2%, which is, to the best of our knowledge, the highest value of carbon-based fluorescent materials ever reported. Furthermore, it exhibits a strong luminescence stability toward temperature, environmental pH, and photocorrosion. Both experimental studies and theoretical calculations reveal that the host-guest interactions between the rigid LDH matrix and interlayer carbon nitride give the predominant contribution to the unprecedented SSQY and stability. In addition, prospective applications of the CN/LDH material are demonstrated in both white light-emitting diodes and upconversion fluorescence imaging of cancer cells. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. The nature of oxygen exchange in ZrW2O8 revealed by two-dimensional solid-state 17O NMR. (United States)

    Hampson, Matthew R; Hodgkinson, Paul; Evans, John S O; Harris, Robin K; King, Ian J; Allen, Simon; Fayon, Franck


    17O magic angle spinning (MAS) NMR has been used to determine the nature of oxygen exchange in ZrW(2)O(8). A highly effective isotopic labelling technique has been developed and 1D NMR and 2D exchange spectroscopy (EXSY) experiments have revealed that mutual exchange occurs between all oxygen sites, even at temperatures considerably below the alpha to beta order-disorder phase transition.

  12. Synthesis of high-purity Li{sub 8}ZrO{sub 6} powder by solid state reaction under hydrogen atmosphere

    Energy Technology Data Exchange (ETDEWEB)

    Shin-mura, Kiyoto; Otani, Yu; Ogawa, Seiya [Course of Mechanical Engineering, Graduate School of Engineering, Tokai University, 4-1-1 Kitakaname, Hiratsuka, Kanagawa 259-1292 (Japan); Niwa, Eiki; Hashimoto, Takuya [Department of Physics, College of Humanities and Sciences, Nihon University, 3-8-1 Sakurajousui, Setagaya-ku, Tokyo 156-8550 (Japan); Hoshino, Tsuyoshi [Breeding Functional Materials Development Group, Department of Blanket Systems Research, Rokkasho Fusion Institute, Sector of Fusion Research and Development, Japan Atomic Energy Agency, 2-166 Obuchi, Omotedate, Rokkasho-mura, Kamikita-gun, Aomori 039-3212 (Japan); Sasaki, Kazuya, E-mail: [Course of Mechanical Engineering, Graduate School of Engineering, Tokai University, 4-1-1 Kitakaname, Hiratsuka, Kanagawa 259-1292 (Japan); Department of Prime Mover Engineering, School of Engineering, Tokai University, 4-1-1 Kitakaname, Hiratsuka, Kanagawa 259-1292 (Japan)


    Highlights: • A fine pure Li{sub 8}ZrO{sub 6} powder was synthesized by using Li{sub 2}CO{sub 3} and ZrO{sub 2} via a solid state reaction. • Influences on the purity of product powder, lattice defect, and crystal orientation were revealed. • The suitable synthesis conditions of the fine and high purity Li{sub 8}ZrO{sub 6} powder were found. • The reaction process of the synthesis of Li{sub 8}ZrO{sub 6} was estimated. - Abstract: Li{sub 8}ZrO{sub 6} contains a large amount of Li and has a significant potential as a tritium breeder. However, few syntheses of fine-grain, high-purity Li{sub 8}ZrO{sub 6} powder have been reported. In this study, a high-purity powder of Li{sub 8}ZrO{sub 6} was synthesized by solid state reaction under hydrogen atmosphere combined with an effective lithium source and a suitable initial Li:Zr molar ratio. Mixed powders of Li{sub 2}CO{sub 3} and ZrO{sub 2} were fired at around 630 °C in H{sub 2} for several hours and several firing cycles. The low firing temperature inhibited the vaporization of Li during the heating, so that excessive amounts of Li were not needed for the synthesis, and the Li:Zr ratio in the starting material was 10:1 (mol:mol). In this synthesis, Li{sub 2}O was generated via the decomposition of Li{sub 2}CO{sub 3} during firing in H{sub 2}, and reacted with ZrO{sub 2} to form Li{sub 6}Zr{sub 2}O{sub 7}, which reacted with itself to form Li{sub 8}ZrO{sub 6}.

  13. Probing the contacts of a low-affinity substrate with a membrane-embedded transport protein using 1H-13C cross-polarisation magic-angle spinning solid-state NMR. (United States)

    Patching, Simon G; Henderson, Peter J F; Sharples, David J; Middleton, David A


    Solid-state NMR combined with sample deuteration was used to probe the proximity of the low-affinity substrate D-glucose to its binding site within the Escherichia coli sugar transport protein GalP. Samples of E. coli inner membranes with amplified expression of GalP were incubated in D(2)O with D-[(13)C(6)]glucose and (13)C NMR signals from the substrate were assigned in two-dimensional dipolar-assisted rotational resonance (DARR) spectra. The signals were confirmed as representing D-glucose bound to GalP as the peaks were abolished after the substrate was displaced from the specific site with the inhibitor forskolin. The (13)C chemical shift values for D-[(13)C(6)]glucose in solution revealed some differences compared to those for ligand bound to GalP, the differences being most pronounced for positions C1 and C2, and especially for C1 in the α-anomer. (13)C cross-polarization build-up was measured for C1 and C2 of D-[(13)C(6)]glucose and D-[(2)H(7), (13)C(6)]glucose in GalP membranes suspended in D(2)O. The build-up curves for the deuterated substrate reflect intermolecular (1)H-(13)C interactions between the protein and the fully deuterated substrate; the signal build-up suggests that the α-anomer is situated closer to the protein binding site than is the β-anomer, consistent with its relatively high signal intensities and more pronounced chemical shift changes in the 2D-correlation spectra. These results demonstrate the utility of solid-state NMR combined with sample deuteration for mapping the binding interface of low affinity ligands with membrane proteins.

  14. Colloidal Sb2S3 Nanocrystals: Synthesis, Characterization and Fabrication of Solid-State Semiconductor Sensitized Solar Cell

    KAUST Repository

    Abulikemu, Mutalifu


    Inorganic nanocrystals composed of earth-abundant and non-toxic elements are crucial to fabricated sustainable photovoltaic devices in large scale. In this study, various-shaped and different phases of antimony sulfide nanocrystals, which is composed of non-scarce and non-toxic elements, are synthesized using hot-injection colloidal method. The effect of various synthetic parameters on the final morphology is explored. Also, foreign ion (Chlorine) effects on the morphology of Sb2S3 nanocrystals have been observed. Structural, optical and morphological properties of the nanocrystals were investigated, and Sb2S3 nanocrystal-based solid-state semiconductor-sensitized solar cells were fabricated using as-prepared nanocrystals. We achieved promising power conversion efficiencies of 1.48%.

  15. Rapidly synthesis of nanocrystalline MgIn 2O 4 spinel using combustion and solid state chemistry (United States)

    Surblé, Suzy; Gosset, Dominique; Dollé, Mickaël; Baldinozzi, Gianguido; Urvoy, Stéphane; Siméone, David


    Nanometric/submicronic powders of magnesium indate spinel MgIn 2O 4 were prepared with a two-steps process. First, nano-oxides of In 2O 3 and MgO were obtained by combustion of aqueous solutions of metal nitrates (as an oxidizer) and different fuels (glycine/urea/citric acid). Then, the as-prepared combustion ashes were converted into pure spinels after calcinations at elevated temperature. The as-prepared powders spinels have nanometric or submicronic grain size. This process allows preparing the MgIn 2O 4 spinel compound in 1 day whilst 10 days were necessary when the classical solid state chemistry is used. In this paper, we compare these two ways and study the effect of different reaction parameters, such as the nature of fuels or the fuel/oxidiser ratio. Crystallites sizes of the synthesized compounds were investigated by powder X-ray diffraction and Scanning Electron Microscopy.

  16. Solid-State Synthesis, Characterization, and Biological Activity of the Bioinorganic Complex of Aspartic Acid and Arsenic Triiodide

    Directory of Open Access Journals (Sweden)

    Guo-Qing Zhong


    Full Text Available The bioinorganic complex of aspartic acid and arsenic triiodide was synthesized by a solid-state reaction at room temperature. The formula of the complex is AsI3[HOOCCH2CH(NH2COOH]2.5. The crystal structure of the complex belongs to monoclinic system with lattice parameters: a=1.0019 nm, b=1.5118 nm, c=2.1971 nm, and β=100.28°. The infrared spectra can demonstrate the complex formation between the arsenic ion and aspartic acid, and the complex may be a dimer with bridge structure. The result of primary biological test indicates that the complex possesses better biological activity for the HL-60 cells of the leukemia than arsenic triiodide.

  17. NMR reaction monitoring in flow synthesis

    Directory of Open Access Journals (Sweden)

    M. Victoria Gomez


    Full Text Available Recent advances in the use of flow chemistry with in-line and on-line analysis by NMR are presented. The use of macro- and microreactors, coupled with standard and custom made NMR probes involving microcoils, incorporated into high resolution and benchtop NMR instruments is reviewed. Some recent selected applications have been collected, including synthetic applications, the determination of the kinetic and thermodynamic parameters and reaction optimization, even in single experiments and on the μL scale. Finally, software that allows automatic reaction monitoring and optimization is discussed.

  18. Synthesis, spectroscopic characterization, solid state d.c. electrical conductivity and biological studies of some lanthanide(III chloride complexes with a heterocyclic Schiff base ligand

    Directory of Open Access Journals (Sweden)

    K. Mohanan


    Full Text Available Condensation of 2-hydroxy-1-naphthaldehyde with 2-amino-3-carboxyethyl-4,5-dimethylthiophene in 1:1 molar ratio, yielded a potentially tridentate Schiff base viz. 2-[N-(2′-hydroxy-1-naphthylideneamino]-3-carboxyethyl-4,5-dimethylthiophene (HNAT. This ligand formed complexes with lanthanum(III, cerium(III, praseodymium(III, neodymium(III, samarium(III, europium(III and gadolinium(III chloride under well defined conditions. These complexes were characterized through elemental analysis, molar conductance, magnetic moment measurements, IR, UV–Vis, FAB mass and 1H NMR spectral studies. Analytical data showed that all the metal complexes exhibited 1:1 metal–ligand ratio. Molar conductance values adequately confirmed the non-electrolytic nature of the metal complexes. The proton NMR spectral observations supplement the IR spectral assignments. The spectral data revealed that the ligand acted as neutral tridentate, coordinating to the metal ion through azomethine nitrogen, ester carbonyl and naphtholate oxygen without deprotonation. The ligand and its lanthanum(III chloride complex were subjected to XRD studies. The lanthanum(III chloride complex has undergone a facile transesterification reaction. The solid state d.c. electrical conductivity of some selected complexes were measured as a function of temperature, indicating the semiconducting nature of the metal complexes. The antimicrobial activities were examined by disk diffusion method against some pathogenic bacterial and fungal species.

  19. Study and characterization of crystalline hydrate/polymorph forms of 5,11-dihydro-11-ethyl-5-methyl-8-(2-(1-oxido-4-quinolinyl)ethyl-6H-dipyrido(3,2-B:2',3'-E)(1,4)diazepin-6-one by solid-state NMR and solution NMR. (United States)

    Gonnella, N C; Smoliga, John A; Campbell, Scot; Busacca, Carl A; Cerreta, Michael; Varsolona, Richard; Norwood, Daniel L


    A novel inhibitor of reverse transcriptase was studied by solid-state NMR. Three phases of the compound were examined which included the dihydrate and two anhydrous polymorphs (Form I and Form III). By correlating (1)H and (13)C solution NMR with the solid-state (13)C NMR CP/MAS and CPPI spectral editing experiments, comparative (13)C assignments were made for each phase. Polymorphs of Form I and Form III and the dihydrate were easily distinguished based upon chemical shift patterns of the carbon resonances. The (1)H spin-lattice relaxation times were also measured for each phase which provided information on the mobility and relative crystallinity. The (13)C ssNMR spectrum of Form I showed the presence of a minor component identified as the dihydrate. Weight/percent quantitation of major and minor components in Form I was obtained from integrated intensities of a 50:50 mixture containing weighed amounts of Form I and the pure dihydrate. Comparison of the ssNMR and X-ray powder diffraction techniques is discussed. Copyright 2009 Elsevier B.V. All rights reserved.

  20. Multinuclear solid-state high-resolution and C-13 -{Al-27} double-resonance magic-angle spinning NMR studies on aluminum alkoxides

    NARCIS (Netherlands)

    Abraham, A.; Prins, R.; Bokhoven, J.A. van; Eck, E.R.H. van; Kentgens, A.P.M.


    A combination of Al-27 magic-angle spinning (MAS)/multiple quantum (MQ)-MAS, C-13-H-1 CPMAS, and C-13-{Al-27} transfer of population in double-resonance (TRAPDOR) nuclear magnetic resonance (NMR) were used for the structural elucidation of the aluminum alkoxides aluminum ethoxide, aluminum

  1. Vanadium phosphates on mesoporous supports: model catalysts for solid-state NMR studies of the selective oxidation of n-butane. (United States)

    Frey, Jörg; Sang Ooi, Yean; Thomas, Bejoy; Reddy Marthala, V R; Bressel, Arne; Schölkopf, Thomas; Schleid, Thomas; Hunger, Michael


    SBA-15 was utilized as mesoporous support for the dispersion of vanadium phosphate (VPO) compounds. Loading of SBA-15 with VPO compounds was found to be accompanied by decreasing (29)Si MAS NMR signals of Q(2) (Si(2Si,2OH)) and Q(3) (Si(3Si,1OH)) silicon species, which indicates coverage of the mesoporous support by the guest compounds. The (51)V MAS NNR spectra of the activated VPO/SBA-15 catalysts consist of patterns typical for the alpha(II)- and beta-phases of vanadyl orthophosphate. In the (31)P MAS NMR spectra of the activated VPO/SBA-15 catalysts, signals of beta-, delta-, and alpha(II)-VOPO(4) phases could be identified. Upon conversion of n-butane-(13)C(4), a strong decrease of the (31)P MAS NMR signals characteristic for the delta-VOPO(4) phase occurred, while by (13)C MAS NMR spectroscopy the formation of maleic anhydride, carbon monoxide, and carbon dioxide was observed. This finding supports the active role of the delta-VOPO(4) phase in the selective oxidation of n-butane on VPO/SBA-15 catalysts.

  2. Solid State NMR Structure Analysis of the Antimicrobial Peptide Gramicidin S in Lipid Membranes: Concentration-Dependent Re-alignment and Self-Assembly as a β-Barrel (United States)

    Afonin, Sergii; Dürr, Ulrich H. N.; Wadhwani, Parvesh; Salgado, Jesus; Ulrich, Anne S.

    Antimicrobial peptides can kill bacteria by permeabilizing their cell membrane, as these amphiphilic molecules interact favourably with lipid bilayers. This mechanism of action is attributed either to the formation of a peptide “carpet” on the membrane surface, or to a transmembrane pore. However, the structure of such a pore has not yet been resolved under relevant conditions. Gramicidin S is a symmetrical cyclic β-sheet decapeptide, which has been previously shown by solid state NMR to lie flat on the membrane surface at low peptide:lipid ratios (≤ 1:80). Using highly sensitive 19F-NMR, supported by 15N-labelling, we found that gramicidin S can flip into an upright transmembrane alignment at high peptide:lipid ratios (≥ 1:40). Orientational NMR constraints suggest that the peptide may self-assemble as an oligomeric β-barrel pore, which is stabilized by intermolecular hydrogen bonds. Comparison of different model membranes shows that the observed re-alignment is favoured in thin bilayers with short-chain lipids, especially near the chain melting temperature, whereas long-chain lipids suppress pore formation. Based on the oligomeric structural model and the conditions of pore formation, guidelines may now be derived for rationally designing peptide analogues as antibiotics with improved selectivity and reduced side effects.

  3. Nature and structure of aluminum surface sites grafted on silica from a combination of high-field aluminum-27 solid-state NMR spectroscopy and first-principles calculations

    KAUST Repository

    Kerber, Rachel Nathaniel


    The determination of the nature and structure of surface sites after chemical modification of large surface area oxides such as silica is a key point for many applications and challenging from a spectroscopic point of view. This has been, for instance, a long-standing problem for silica reacted with alkylaluminum compounds, a system typically studied as a model for a supported methylaluminoxane and aluminum cocatalyst. While 27Al solid-state NMR spectroscopy would be a method of choice, it has been difficult to apply this technique because of large quadrupolar broadenings. Here, from a combined use of the highest stable field NMR instruments (17.6, 20.0, and 23.5 T) and ultrafast magic angle spinning (>60 kHz), high-quality spectra were obtained, allowing isotropic chemical shifts, quadrupolar couplings, and asymmetric parameters to be extracted. Combined with first-principles calculations, these NMR signatures were then assigned to actual structures of surface aluminum sites. For silica (here SBA-15) reacted with triethylaluminum, the surface sites are in fact mainly dinuclear Al species, grafted on the silica surface via either two terminal or two bridging siloxy ligands. Tetrahedral sites, resulting from the incorporation of Al inside the silica matrix, are also seen as minor species. No evidence for putative tri-coordinated Al atoms has been found. © 2012 American Chemical Society.

  4. Insight into the local environment of magnesium and calcium in low-coordination-number organo-complexes using (25)Mg and (43)Ca solid-state NMR: a DFT study. (United States)

    Gervais, Christel; Jones, Cameron; Bonhomme, Christian; Laurencin, Danielle


    With the increasing number of organocalcium and organomagnesium complexes under development, there is a real need to be able to characterize in detail their local environment in order to fully rationalize their reactivity. For crystalline structures, in cases when diffraction techniques are insufficient, additional local spectroscopies like (25)Mg and (43)Ca solid-state NMR may provide valuable information to help fully establish the local environment of the metal ions. In this current work, a prospective DFT investigation on crystalline magnesium and calcium complexes involving low-coordination numbers and N-bearing organic ligands was carried out, in which the (25)Mg and (43)Ca NMR parameters [isotropic chemical shift, chemical shift anisotropy (CSA) and quadrupolar parameters] were calculated for each structure. The analysis of the calculated parameters in relation to the local environment of the metal ions revealed that they are highly sensitive to very small changes in geometry/distances, and hence that they could be used to assist in the refinement of crystal structures. Moreover, such calculations provide a guideline as to how the NMR measurements will need to be performed, revealing that these will be very challenging.

  5. Solid state synthesis, characterization and optical properties of Tb doped SrSnO{sub 3} phosphor

    Energy Technology Data Exchange (ETDEWEB)

    Kotan, Z. [Ege University, Institute of Nuclear Sciences, 35100 Bornova-İzmir (Turkey); Ayvacikli, M.; Karabulut, Y. [Celal Bayar University, Faculty of Arts and Sciences, Department of Physics, 45010 Muradiye-Manisa (Turkey); Garcia-Guinea, J.; Tormo, L. [Museo Nacional Ciencias Naturales, Jose Gutierrez Abascal 2, Madrid 28006 (Spain); Canimoglu, A. [Niğde University, Faculty of Arts and Sciences, Department of Physics, Niğde (Turkey); Karali, T. [Ege University, Institute of Nuclear Sciences, 35100 Bornova-İzmir (Turkey); Can, N., E-mail: [Celal Bayar University, Faculty of Arts and Sciences, Department of Physics, 45010 Muradiye-Manisa (Turkey)


    Highlights: •A new stannate phosphor, SrSnO{sub 3}:Tb{sup 3+} was synthesized by solid state reaction method. •The role of Tb{sup 3+} doped into SrSnO{sub 3} was discussed. •A structural phase transition in SrSnO{sub 3}:Tb{sup 3+} at ∼270 K was suggested. -- Abstract: In the present study, the structural and optical properties of SrSnO{sub 3} doped with Tb ions are reported. Novel SrSnO{sub 3}:Tb{sup 3+} phosphors were conventionally synthesized using a solid state reaction process under a mildly reduced atmosphere (5%H{sub 2} and 95%N{sub 2}). The crystal structures, morphologies and optical properties of the resultant materials have been characterised by experimental techniques such as X-ray Diffraction (XRD), Raman spectroscopy (RS), Photoluminescence (PL), Radioluminescence (RL) and Cathodoluminescence coupled to an ESEM (ESEM-CL). The new phosphor material has good crystallization without any impurity phases, which matches with the standard JCPDS files (No. 22-1442) from XRD analysis. The PL, RL and CL measurements taken at room temperature showed that the transitions of {sup 5}D{sub 4} to {sup 7}F{sub J} (j = 6, 5, 4, 3) corresponding to the typical 4f → 4f dipole forbidden intra-configurational transitions of Tb{sup 3+} are largely independent of the host material. The green emissions of the {sup 5}D{sub 4} → {sup 7}F{sub 5} magnetic dipole transition at ∼540 nm are predominant for three types of luminescence. PL emission spectra recorded in the temperature range from 10 K to 300 K were influenced by temperature. We report anomalies in the PL spectra of SrSnO{sub 3}:Tb{sup 3+} compatible with a structural phase transition at 260 K while simultaneously exciting and cooling the sample. This work clearly confirms the existence of a phase transition discovered by Singh et al. in SrSnO{sub 3} at 270 K.

  6. Thin films of PtAl{sub 2} and AuAl{sub 2} by solid-state reactive synthesis

    Energy Technology Data Exchange (ETDEWEB)

    Supansomboon, S.; Dowd, A.; Gentle, A. [Institute for Nanoscale Technology, University of Technology Sydney, PO Box 123, Broadway, NSW 2007 (Australia); Lingen, E. van der [Department of Engineering and Technology Management, University of Pretoria, Lynnwood Road, Hatfield, Pretoria (South Africa); Cortie, M.B., E-mail: [Institute for Nanoscale Technology, University of Technology Sydney, PO Box 123, Broadway, NSW 2007 (Australia)


    The intermetallic compounds AuAl{sub 2} and PtAl{sub 2} are colored purple and yellow respectively. In the past they have been prepared by bulk melting techniques or by co-deposition in a magnetron sputterer. Here, however, we investigate films of AuAl{sub 2}, PtAl{sub 2} and (Au,Pt)Al{sub 2} prepared by sequential physical vapor deposition of the elements, followed by in situ solid-state reaction. The microstructure, dielectric functions, optical properties and thermal stability of the resulting films are characterized and compared to those prepared by bulk melting or co-deposition. The (Au,Pt)Al{sub 2} films show a color gamut that stretches from purple to brassy yellow depending on composition and microstructure. High temperature synchrotron X-ray diffraction experiments show that the (Au,Pt)Al{sub 2} phase is metastable, decomposing when heated above 420 °C. In contrast, the pure AuAl{sub 2} or PtAl{sub 2} phases are stable to about 580 °C before they oxidize or decompose. The alternative possibility of producing the purple-to-yellow color gamut by depositing optical stacks of very thin films of AuAl{sub 2} and PtAl{sub 2} is also assessed. Either scheme will provide a range of colors lying between those of the binary compound endpoints. Calculations predict that deposition of AuAl{sub 2} onto PtAl{sub 2} will produce more intense colors than vice versa, an unexpected finding that is worth further investigation. - Highlights: • AuAl{sub 2}, PtAl{sub 2} and (Au,Pt)Al{sub 2} synthesized by solid-state reaction • (Au,Pt)Al{sub 2} is metastable and decomposes at elevated temperature. • Optical properties of the compounds and their layered structures measured. • The color of alloys or mixtures can be tuned between purple and yellow. • Bilayer optical stacks of AuAl{sub 2}/PtAl{sub 2} can reproduce colors of (Au,Pt)Al{sub 2}.

  7. Understanding solid state physics

    CERN Document Server

    Holgate, Sharon Ann


    Where Sharon Ann Holgate has succeeded in this book is in packing it with examples of the application of solid state physics to technology. … All the basic elements of solid state physics are covered … . The range of materials is good, including as it does polymers and glasses as well as crystalline solids. In general, the style makes for easy reading. … Overall this book succeeds in showing the relevance of solid state physics to the modern world … .-Contemporary Physics, Vol. 52, No. 2, 2011I was indeed amused and inspired by the wonderful images throughout the book, carefully selected by th

  8. Theoretical solid state physics

    CERN Document Server

    Haug, Albert


    Theoretical Solid State Physics, Volume 1 focuses on the study of solid state physics. The volume first takes a look at the basic concepts and structures of solid state physics, including potential energies of solids, concept and classification of solids, and crystal structure. The book then explains single-electron approximation wherein the methods for calculating energy bands; electron in the field of crystal atoms; laws of motion of the electrons in solids; and electron statistics are discussed. The text describes general forms of solutions and relationships, including collective electron i

  9. The solid state maser

    CERN Document Server

    Orton, J W; Walling, J C; Ter Haar, D


    The Solid State Maser presents readings related to solid state maser amplifier from the first tentative theoretical proposals that appeared in the early 1950s to the successful realization of practical devices and their application to satellite communications and radio astronomy almost exactly 10 years later. The book discusses a historical account of the early developments (including that of the ammonia maser) of solid state maser; the properties of paramagnetic ions in crystals; the development of practical low noise amplifiers; and the characteristics of maser devices designed for communica

  10. Synthesis, characterization and thermal behaviour of solid-state compounds of benzoates with some bivalent transition metal ions

    Directory of Open Access Journals (Sweden)

    Adriano B. Siqueira


    Full Text Available Solid-state MBz compounds, where M stands for bivalent Mn, Fe, Co, Ni, Cu and Zn and Bz is benzoate, have been synthesized. Simultaneous thermogravimetry and differential thermal analysis (TG-DTA, differential scanning calorimetry (DSC, infrared spectroscopy and complexometry were used to characterize and to study the thermal behaviour of these compounds. The procedure used in the preparation of the compounds via reaction of basic carbonates with benzoic acid is not efficient in eliminating excess acid. However the TG-DTA curves permitted to verify that the binary compounds can be obtained by thermosynthesis, because the benzoic acid can be eliminated before the thermal decomposition of these compounds. The results led to information about the composition, dehydration, thermal stability, thermal decomposition and structure of the isolated compounds. On heating, these compounds decompose in two (Mn, Co, Ni, Zn or three (Fe, Cu steps with formation of the respective oxide (Mn3O4, Fe2O3, Co3O4, NiO, CuO and ZnO as final residue. The theoretical and experimental spectroscopic studies suggest a covalent bidentate bond between ligand and metallic center.

  11. Scalable Synthesis of Freestanding Sandwich-structured Graphene/Polyaniline/Graphene Nanocomposite Paper for Flexible All-Solid-State Supercapacitor (United States)

    Xiao, Fei; Yang, Shengxiong; Zhang, Zheye; Liu, Hongfang; Xiao, Junwu; Wan, Lian; Luo, Jun; Wang, Shuai; Liu, Yunqi


    We reported a scalable and modular method to prepare a new type of sandwich-structured graphene-based nanohybrid paper and explore its practical application as high-performance electrode in flexible supercapacitor. The freestanding and flexible graphene paper was firstly fabricated by highly reproducible printing technique and bubbling delamination method, by which the area and thickness of the graphene paper can be freely adjusted in a wide range. The as-prepared graphene paper possesses a collection of unique properties of highly electrical conductivity (340 S cm-1), light weight (1 mg cm-2) and excellent mechanical properties. In order to improve its supercapacitive properties, we have prepared a unique sandwich-structured graphene/polyaniline/graphene paper by in situ electropolymerization of porous polyaniline nanomaterials on graphene paper, followed by wrapping an ultrathin graphene layer on its surface. This unique design strategy not only circumvents the low energy storage capacity resulting from the double-layer capacitor of graphene paper, but also enhances the rate performance and cycling stability of porous polyaniline. The as-obtained all-solid-state symmetric supercapacitor exhibits high energy density, high power density, excellent cycling stability and exceptional mechanical flexibility, demonstrative of its extensive potential applications for flexible energy-related devices and wearable electronics.

  12. Observation of immobile regions in natural rubber at ambient temperature by solid-state C-13 CP/MAS NMR spectroscopy

    DEFF Research Database (Denmark)

    Larsen, F.H.; Rasmussen, T.; Pedersen, Walther Batsberg


    Employing C-13 CP/MAS NMR spectroscopy, the existence of immobile regions in natural rubber (cis-1,4-polyisoprene) corresponding to a few percent of the monomer units has been detected at ambient temperature. For synthetic rubbers no immobile regions have been detected at all. Applying different ...... physical and chemical treatments to natural rubber it is shown that mastication, gamma-irradiation, and increasing the temperature, slightly above the ambient, reduce the amount of immobile regions. (C) 1999 Elsevier Science Ltd. All rights reserved.......Employing C-13 CP/MAS NMR spectroscopy, the existence of immobile regions in natural rubber (cis-1,4-polyisoprene) corresponding to a few percent of the monomer units has been detected at ambient temperature. For synthetic rubbers no immobile regions have been detected at all. Applying different...

  13. Residue specific hydration of primary cell wall potato pectin identified by solid-state 13C single-pulse MAS and CP/MAS NMR spectroscopy

    DEFF Research Database (Denmark)

    Larsen, Flemming Hofmann; Chrestensen, Inge Byg; Damager, Iben


    Hydration of rhamnogalacturonan-I (RG-I) derived from potato cell wall was analyzed by 13C single-pulse (SP) magic-angle-spinning (MAS) and 13C cross-polarization (CP) MAS nuclear magnetic resonance (NMR) and supported by 2H SP/MAS NMR experiments. The study shows that the arabinan side chains...... hydrate more readily than the galactan side chains and suggests that the overall hydration properties can be controlled by modifying the ratio of these side chains. Enzymatic modification of native (NA) RG-I provided samples with reduced content of arabinan (sample DA), galactan (sample DG), or both side...... chains (sample DB). Results of these samples suggested that hydration properties were determined by the length and character of the side chains. NA and DA exhibited similar hydration characteristics, whereas DG and DB were difficult to hydrate because of the less hydrophilic properties of the rhamnose...

  14. Quantitative comparison of structure and dynamics of elastin following three isolation schemes by 13C solid state NMR and MALDI mass spectrometry


    Papaioannou, A.; Louis, M.; Dhital, B.; Ho, H. P.; Chang, E. J.; Boutis, G. S.


    Methods for isolating elastin from fat, collagen, and muscle, commonly used in the design of artificial elastin based biomaterials, rely on exposing tissue to harsh pH levels and temperatures that usually denature many proteins. At present, a quantitative measurement of the modifications to elastin following isolation from other extracellular matrix constituents has not been reported. Using magic angle spinning 13C NMR spectroscopy and relaxation methodologies, we have measured the modificati...

  15. 13C and 14N Solid State NMR Characterization of Aramid-Containing Nylon-6 Polymers Synthesized by In Situ Polymerization of Caprolactam with Benzoyl Caprolactam Derivatives. (United States)


    Charmcterizjtic;a 0 polyamides by solution 1N NMR is, however, hampered by the limited solubility of many polyamides, especially homo- and copolymers...261.3 show equivalent areas consistant with tiie alternating copolymer structure. Comparison with the model acetanilide (-241.5) indicates the...T.; Fujito, T.; Deguchi. 1\\.; Ando, 1. Macromolecules. 1987, 2?0, 2441. 4 TABLE I CP MNAS ,_’ii N-methyl benzamide -2-o3.3 -226. Acetanilide -241.9

  16. Synthesis, characterization and quantitative analysis of porous metal microstructures: Application to microporous copper produced by solid state foaming

    Directory of Open Access Journals (Sweden)

    Mark A. Atwater


    Full Text Available Porous metals can be created through a wide variety of processing techniques, and the pore morphology resulting from these processes is equally diverse. The structural and functional properties of metal foams are directly dependent on the size, shape, interconnectedness and volume fraction of pores, so accurately quantifying the pore characteristics is of great importance. Methods for analyzing porous materials are presented here and applied to a copper-based metallic foam generated through solid state foaming via oxide reduction and expansion. This process results in large voids (10s of microns between sintered particles and small pores (10 microns to less than 50 nm within particles. Optical and electron microscopy were used to image the porosity over this wide range, and the pore characteristics were quantified using image segmentation and statistical analysis. Two-dimensional pore analysis was performed using the Chan-Vese method, and two-point correlation and lineal path functions were used to assess three-dimensional reconstructions from FIB tomography. Two-dimensional analysis reveals distinct size and morphological differences in porosity between particles and within them. Three-dimensional analysis adds further information on the high level interconnectedness of the porosity and irregular shape it takes, forming tortuous pathways rather than spherical cells. Mechanical polishing and optical microscopy allow large areas to be created and analyzed quickly, but methods such as focused ion beam (FIB sectioning can provide additional insight about microstructural features. In particular, after FIB milling is used to create a flat surface, that surface can be analyzed for structural and compositional information.

  17. sup 13 C NMR study of the C60 cluster in the solid state: Molecular motion and carbon chemical shift anisotropy

    Energy Technology Data Exchange (ETDEWEB)

    Yannoni, C.S.; Johnson, R.D.; Meijer, G.; Bethune, D.S.; Salem, J.R. (Almaden Research Center, San Jose, CA (USA))


    {sup 13}C NMR spectra of solid buckminsterfullerene, the soccerball-like cluster of 60 carbon atoms, have been obtained at temperatures down to 77 K. The ambient spectrum shows rapid isotropic rotational motion. The motion is sufficiently slow at 77 K that a measurement of the chemical shift tensor of the carbon nucleus can be made. The tensor components (220, 186, 40 ppm) have values that are typical for an aromatic carbon. Spectra at intermediate temperatures suggest the possibility of either growth of a low-temperature phase in which C60 rotation is inhibited or a distribution of rotational correlation times.

  18. Elaboration of hybrid organic-inorganic materials for ammonium ions retention: Electron microscopy bipolarized observations and {sup 129}Xe solid-state NMR

    Energy Technology Data Exchange (ETDEWEB)

    Barthelemy, A.; Duchamp, C.; Uttaro, J.-P. [Universite de Lyon, Lyon, F-69003 (France); Universite Lyon 1, Villeurbanne, F-69622 (France); CNRS, UMR 5246, ICBMS, equipe CSAp, Villeurbanne, F-69622 (France); Rousseau, C. [Universite de Lyon, Lyon, F-69003 (France); Universite Lyon 1, Villeurbanne F-69622, France, IBCP, UMR 5086, Lyon, F-69367 (France); Fenet, B. [Universite de Lyon, Lyon, F-69003 (France); Universite Lyon 1, Villeurbanne, F-69622 (France); Centre Commun de RMN, Villeurbanne, F-69622 (France); Ananchenko, G.; Lang, S. [Steacie Institute for Molecular Sciences, NRC, 100 Sussex drive, Ottawa, Ontario, K1A 0R6 (Canada); Coleman, A.W. [Universite de Lyon, Lyon, F-69003 (France); Universite Lyon 1, Villeurbanne F-69622 (France); IBCP, UMR 5086, Lyon, F-69367 (France); Ripmeester, J. [Steacie Institute for Molecular Sciences, NRC, 100 Sussex drive, Ottawa, Ontario, K1A 0R6 (Canada); Guillard, C. [Universite de Lyon, Lyon, F-69003 (France); Universite Lyon 1, Villeurbanne F-69622 (France); IRCELyon, UMR 5256, Villeurbanne, F-69622 (France); Elsellami, L. [Universite de Lyon, Lyon, F-69003 (France); Universite Lyon 1, Villeurbanne, F-69622 (France); CNRS, UMR 5246, ICBMS, equipe CSAp, Villeurbanne, F-69622 (France); Universite de Lyon, Lyon, F-69003 (France); Universite Lyon 1, Villeurbanne F-69622 (France); IRCELyon, UMR 5256, Villeurbanne, F-69622 (France); Lamartine, R.; Felix, C. [Universite de Lyon, Lyon, F-69003 (France); Universite Lyon 1, Villeurbanne, F-69622 (France); CNRS, UMR 5246, ICBMS, equipe CSAp, Villeurbanne, F-69622 (France); Vocanson, F. [Universite de Lyon, Lyon, F-69003 (France); Universite Lyon 1, Villeurbanne, F-69622 (France); CNRS, UMR 5246, ICBMS, equipe CSAp, Villeurbanne, F-69622 (France)], E-mail:


    Translucent organic-inorganic hybrid porous silica materials have been prepared via the acid-catalysed hydrolysis and condensation of TEOS and various p-sulphonatocalix[n]arene derivatives. Xerogels and aerogels have been prepared. The morphology of the gels was characterized by electron microscopy (SEM and ESEM) and by hyperpolarized {sup 129}Xe NMR. The aerogels showed a porous structure not influenced by the size of the calixarene derivative incorporated in the gel. The efficiency of these new materials towards the retention of ammonium ions was discussed.

  19. Probing intermolecular interactions in a diethylcarbamazine citrate salt by fast MAS (1)H solid-state NMR spectroscopy and GIPAW calculations. (United States)

    Venâncio, Tiago; Oliveira, Lyege Magalhaes; Ellena, Javier; Boechat, Nubia; Brown, Steven P


    Fast magic-angle spinning (MAS) NMR is used to probe intermolecular interactions in a diethylcarbamazine salt, that is widely used as a treatment against adult worms of Wuchereria bancrofti which cause a common disease in tropical countries named filariasis. Specifically, a dihydrogen citrate salt that has improved thermal stability and solubility as compared to the free form is studied. One-dimensional (1)H, (13)C and (15)N and two-dimensional (1)H-(13)C and (14)N-(1)H heteronuclear correlation NMR experiments under moderate and fast MAS together with GIPAW (CASTEP) calculations enable the assignment of the (1)H, (13)C and (14)N/(15)N resonances. A two-dimensional (1)H-(1)H double-quantum (DQ) -single-quantum (SQ) MAS spectrum recorded with BaBa recoupling at 60kHz MAS identifies specific proton-proton proximities associated with citrate-citrate and citrate-diethylcarbamazine intermolecular interactions. Copyright © 2017 Elsevier Inc. All rights reserved.

  20. Relationship between water structure and properties of poly(methyl methacrylate-b-2-hydroxyethyl methacrylate) by solid-state NMR. (United States)

    Mochizuki, Akira; Miwa, Yuko; Miyoshi, Riko; Namiki, Takahiro

    We previously reported that the platelet compatibility of methyl methacrylate (MMA)-2-hydroxyethyl methacrylate (HEMA) diblock copolymers is related to the characteristic water structure in the copolymer, as the copolymer has an excess amount of nonfreezing water when compared with that estimated from the amounts of water in HEMA and MMA homopolymers. Thus, in this study, the relationship between water structure and polymer structure, including the heterogeneity and mobility of the copolymer, was investigated using differential scanning calorimetry (DSC) and nuclear magnetic resonance (NMR) spectroscopy. The prepared copolymers were classified into two groups: copolymers with a short, constant polyMMA segment length (Mn = ~2900) and copolymers with a constant polyHEMA segment length (Mn = ~9500), whereas the lengths of the counter segments varied. DSC analysis showed that when the polyMMA and polyHEMA segment lengths are similar, the amount of nonfreezing water increases, regardless of the total molecular weight of the copolymer. NMR analysis showed that heterogeneity of the copolymer is enhanced and the mobility of the copolymer decreases when the segment lengths are similar. These findings suggested that the excess amount of nonfreezing water is formed when the properties of water near the HEMA unit change from freezing to nonfreezing owing to interactions with the MMA unit. In addition, it is suggested that the heterogeneity of the copolymer structure or the mobility of the polymer are involved in the generation of excess nonfreezing water.

  1. Supporting Information Synthesis and NMR Elucidation of Novel ...

    African Journals Online (AJOL)


    1. Supporting Information. Synthesis and NMR Elucidation of Novel Octa-Amino Acid Resorcin[4]arenes derivatives. Iman Elidrisi,. [a]. Pralav V. Bhatt,. [b]. Thavendran Govender,. [b]. Hendrik G. Kruger,. [b] and. Glenn E. M. Maguire,. [a]. * a. School of Chemistry, University of KwaZulu--Natal, Westville Campus, Private Bag.

  2. Novel Dodecaarylporphyrins: Synthesis and Variable Temperature NMR Studies

    Energy Technology Data Exchange (ETDEWEB)

    Cancilla, Mark; Lebrilla, Carlito; Ma, Jian-Guo; Medforth, Craig J.; Muzzi, Cinzia M.; Shelnutt, John A.; Smith, Kevin M.; Voss, Lisa


    An investigation of the synthesis of novel dodecaarylporphyrins using the Suzuki coupling reaction of arylboronic acids with octabromotetraarylporphyrins is reported. Studies of the dynamic properties of these new porphyrins using variable temperature (VT) 1H NMR spectroscopy and molecular mechanics provide interesting insights into their dynamic properties, including the first determination of {beta} aryl rotation in a porphyrin system.

  3. synthesis and nmr elucidation of novel pentacycloundecane derived ...

    African Journals Online (AJOL)


    SYNTHESIS AND NMR ELUCIDATION OF NOVEL. PENTACYCLOUNDECANE DERIVED PEPTIDES. Rajshekhar Karpoormath, a. Oluseye K. Onajole, a. Thavendran Govender, b. Glenn E. M. Maguire, a and Hendrik G. Kruger a* a. School of Chemistry, University of KwaZulu-Natal, Durban 4001, South Africa b. School of ...

  4. Investigation of the Curvature Induction and Membrane Localization of the Influenza Virus M2 Protein Using Static and Off-Magic-Angle Spinning Solid-State NMR of Oriented Bicelles (United States)

    Wang, Tuo; Hong, Mei


    A wide variety of membrane proteins induce membrane curvature for function, thus it is important to develop new methods to simultaneously determine membrane curvature and protein binding sites in membranes with multiple curvatures. We introduce solid-state NMR methods based on magnetically oriented bicelles and off-magic-angle spinning (OMAS) to measure membrane curvature and the binding site of proteins in mixed-curvature membranes. We demonstrate these methods on the influenza virus M2 protein, which not only acts as a proton channel but also mediates virus assembly and membrane scission. An M2 peptide encompassing the transmembrane (TM) domain and an amphipathic helix, M2(21-61), was studied and compared with the TM peptide (M2TM). Static 31P NMR spectra of magnetically oriented DMPC/DHPC bicelles exhibit a temperature-independent isotropic chemical shift in the presence of M2(21-61) but not M2TM, indicating that the amphipathic helix confers the peptide with the ability to generate a high-curvature phase. 2D 31P spectra indicate that this high-curvature phase is associated with the DHPC bicelle edges, suggestive of the structure of budding viruses from the host cell. 31P- and 13C-detected 1H relaxation times of the lipids indicate that the majority of M2(21-61) is bound to the high-curvature phase. Using OMAS experiments, we resolved the 31P signals of lipids with identical headgroups based on their distinct chemical shift anisotropies. Based on this resolution, 2D 1H-31P correlation spectra show that the amide protons in M2(21-61) correlate with the DMPC but not the DHPC 31P signal of the bicelle, indicating that a small percentage of M2(21-61) partitions into the planar region of the bicelles. These results show that the M2 amphipathic helix induces high membrane curvature and localizes the protein to this phase, in excellent agreement with the membrane-scission function of the protein. These bicelle-based relaxation and OMAS solid-state NMR techniques are

  5. Effect of the addition of sugar cane bagasse fibers in the composite with the copolymer vinyl ethylene-acetate (EVA) by solid state NMR; Efeito da adicao de fibras do bagaco de cana-de-acucar no composito com o copolimero de etileno-acetato de vinila (EVA) por ressonancia magnetica nuclear no estado solido

    Energy Technology Data Exchange (ETDEWEB)

    Stael, Giovanni Chaves [Universidade Estadual Norte Fluminense, Campos dos Goytacazes, RJ (Brazil); D`Almeida, Jose Roberto Moraes [Pontificia Univ. Catolica do Rio de Janeiro, RJ (Brazil); Menezes, Sonia M.C. de [PETROBRAS, Rio de Janeiro, RJ (Brazil). Centro de Pesquisas; Tavares, Maria Ines Bruno [Universidade Federal, Rio de Janeiro, RJ (Brazil). Inst. de Macromoleculas


    Natural fibers composites obtained form sugar cane bagasse and ethylene-vinyl-acetate copolymer were prepared with different compositions and analysed by solid state Carbon-13 NMR aiming the observation of molecular mobility, compatibility, and chemical structure of the different obtained composites. One objective of this work was to enable the future commercial application of these materials 12 refs., 2 figs., 3 tabs.

  6. Measurement of -OH groups in coals of different rank using microwave methodology, and the development of quantitative solid state n.m.r. methods for in situ analysis

    Energy Technology Data Exchange (ETDEWEB)

    Monsef-Mirzai, P.; McWhinnie, W.R.; Perry, M.C.; Burchill, P. [Aston University, Birmingham (United Kingdom). Dept. of Chemical Engineering and Applied Chemistry


    Experiments with both model compounds (substituted phenols) and with 11 coals (nine British and two American) have established that microwave heating will greatly accelerate silylation reactions of the phenolic -OH groups, e.g. for Creswell coal complete silylation of -OH groups occurs in 35 min in the microwave oven, whereas 24 h is required using a bench reflux technique. Microwave reaction times for coals vary from 35 min to 3 h for more dense coals such as Cortonwood. The above observations have allowed the development of a `one pot` silylation of coal, followed by an in situ analysis of the added Me{sub 3}Si- groups by quantitative {sup 29}Si magic angle spinning nuclear magnetic resonance (MAS n.m.r.) spectroscopy. The development of a quantitative n.m.r. method required the determination of {sup 29}Si spin lattice relaxation times, T{sub 1}, e.g. for silylated coals T{sub 1} {approximately} 8s; for silylated phenols, T{sub 1} {approximately} 25s; for the synthetic smectite clay laponite, T{sub 1} {approximately} 25 s; and for Ph{sub 3}SiH, T{sub 1} {approximately} 64 s. Inert laponite was selected as the standard. The requirement to wait for five T{sub 1 max} between pulses, together with the relatively low natural abundance of {sup 29}Si (4.71%), results in rather long accumulation times to obtain spectra of analytical quality (8-48 h). However, in comparison with other methods, even in the most unfavourable case, the total time from commencement of analysis to result may be described as `rapid`. The results for O{sub OH}/O{sub total} obtained are compared with other literature data. Comparison with ketene data, for example, shows agreement to vary from excellent (Creswell) through satisfactory (Cortonwood) to poor (Pittsburgh). Even in cases where agreement with ketene data is less good, the silylation results may be close to estimates made via other acetylation methods. Possible reasons for the variations observed are discussed. 18 refs., 2 figs., 7 tabs.

  7. Solid-state circuits

    CERN Document Server

    Pridham, G J


    Solid-State Circuits provides an introduction to the theory and practice underlying solid-state circuits, laying particular emphasis on field effect transistors and integrated circuits. Topics range from construction and characteristics of semiconductor devices to rectification and power supplies, low-frequency amplifiers, sine- and square-wave oscillators, and high-frequency effects and circuits. Black-box equivalent circuits of bipolar transistors, physical equivalent circuits of bipolar transistors, and equivalent circuits of field effect transistors are also covered. This volume is divided

  8. Quantitative comparison of structure and dynamics of elastin following three isolation schemes by 13C solid state NMR and MALDI mass spectrometry. (United States)

    Papaioannou, A; Louis, M; Dhital, B; Ho, H P; Chang, E J; Boutis, G S


    Methods for isolating elastin from fat, collagen, and muscle, commonly used in the design of artificial elastin based biomaterials, rely on exposing tissue to harsh pH levels and temperatures that usually denature many proteins. At present, a quantitative measurement of the modifications to elastin following isolation from other extracellular matrix constituents has not been reported. Using magic angle spinning (13)C NMR spectroscopy and relaxation methodologies, we have measured the modification in structure and dynamics following three known purification protocols. Our experimental data reveal that the (13)C spectra of the hydrated samples appear remarkably similar across the various purification methods. Subtle differences in the half maximum widths were observed in the backbone carbonyl suggesting possible structural heterogeneity across the different methods of purification. Additionally, small differences in the relative signal intensities were observed between purified samples. Lyophilizing the samples results in a reduction of backbone motion and reveals additional differences across the purification methods studied. These differences were most notable in the alanine motifs indicating possible changes in cross-linking or structural rigidity. The measured correlation times of glycine and proline moieties are observed to also vary considerably across the different purification methods, which may be related to peptide bond cleavage. Lastly, the relative concentration of desmosine cross-links in the samples quantified by MALDI mass spectrometry is reported. Copyright © 2015 Elsevier B.V. All rights reserved.

  9. 45Sc Solid State NMR studies of the silicides Sc TSi ( T=Co, Ni, Cu, Ru, Rh, Pd, Ir, Pt) (United States)

    Harmening, Thomas; Eckert, Hellmut; Fehse, Constanze M.; Sebastian, C. Peter; Pöttgen, Rainer


    The silicides Sc TSi ( T=Fe, Co, Ni, Cu, Ru, Rh, Pd, Ir, Pt) were synthesized by arc-melting and characterized by X-ray powder diffraction. The structures of ScCoSi, ScRuSi, ScPdSi, and ScIrSi were refined from single crystal diffractometer data. These silicides crystallize with the TiNiSi type, space group Pnma. No systematic influences of the 45Sc isotropic magnetic shift and nuclear electric quadrupolar coupling parameters on various structural distortion parameters calculated from the crystal structure data can be detected. 45Sc MAS-NMR data suggest systematic trends in the local electronic structure probed by the scandium atoms: both the electric field gradients and the isotropic magnetic shifts relative to a 0.2 M aqueous Sc(NO 3) 3 solution decrease with increasing valence electron concentration and within each T group the isotropic magnetic shift decreases monotonically with increasing atomic number. The 45Sc nuclear electric quadrupolar coupling constants are generally well reproduced by quantum mechanical electric field gradient calculations using the WIEN2k code.

  10. Elucidation of functional chemical groups responsible of compost phytotoxicity using solid-state 13C NMR spectroscopy under different initial C/N ratios. (United States)

    Azim, Khalid; Faissal, Youssef; Soudi, Brahim; Perissol, Claude; Roussos, Sevastianos; Thami Alami, Imane


    More than 1 million tons of fresh organic wastes is produced in the Souss-Massa region in Morocco. Tomato organic residues represent more than 25% of the total organic wastes and are deposited in uncontrolled landfills. Thus, composting can represent a valuable and pertinent solution to this environmental problem. The objectives of this experiment are to identify the potential functional groups responsible for compost phytotoxicity and to determine the optimum initial carbon to nitrogen ratio (C/N) for maximum recovery of tomato residues. The experiment consisted of the variation of the initial C/N ratios (25, 30, 35, and 40) using mixtures of different raw materials (tomato residues, melon residues, olive mill pomace, and sheep manure). Physicochemical parameters (pH, electrical conductivity, C/N ratio, and humic acid/fulvic acid ratio) were determined and spectroscopic analyses (UV-vis and NMR-13C) were performed during the composting process along with quality parameters (germination and phytotoxicity tests) at the end. The results showed that the compost with the initial C/N ratio of 35 is the most humified with the least phytotoxic effect. The germination and phytotoxicity tests were negatively correlated with the methoxyl/N-alkyl-C ratio and O-alkyl-C. These two functional groups are probably the origin of phytotoxicity expression in compost quality tests. Thus, a simple and precise quality test could be performed to evaluate directly the phytotoxicity and maturity of compost.

  11. Handbook of Applied Solid State Spectroscopy

    CERN Document Server

    Vij, D. R


    Solid-State spectroscopy is a burgeoning field with applications in many branches of science, including physics, chemistry, biosciences, surface science, and materials science. Handbook of Applied Solid-State Spectroscopy brings together in one volume information about various spectroscopic techniques that is currently scattered in the literature of these disciplines. This concise yet comprehensive volume covers theory and applications of a broad range of spectroscopies, including NMR, NQR, EPR/ESR, ENDOR, scanning tunneling, acoustic resonance, FTIR, auger electron emission, x-ray photoelectron emission, luminescence, and optical polarization, and more. Emphasis is placed on fundamentals and current methods and procedures, together with the latest applications and developments in the field.

  12. Structure of Amantadine-Bound M2 Transmembrane Peptide of Influenza A in Lipid Bilayers from Magic-Angle-Spinning Solid-State NMR: the Role of Ser31 in Amantadine Binding (United States)

    Cady, Sarah D.; Mishanina, Tatiana V.; Hong, Mei


    The M2 proton channel of influenza A is the target of the antiviral drugs amantadine and rimantadine, whose effectiveness has been abolished by a single-site mutation of Ser31 to Asn in the transmembrane domain of the protein. Recent high-resolution structures of the M2 transmembrane domain obtained from detergent-solubilized protein in solution and crystal environments gave conflicting drug binding sites. We present magic-angle-spinning solid-state NMR results of Ser31 and a number of other residues in the M2 transmembrane peptide (M2TMP) bound to lipid bilayers. Comparison of the spectra of the membrane-bound apo and complexed M2TMP indicates that Ser31 is the site of the largest chemical shift perturbation by amantadine. The chemical shift constraints lead to a monomer structure with a small kink of the helical axis at Gly34. A tetramer model is then constructed using the helix tilt angle and several interhelical distances previously measured on unoriented bilayer samples. This tetramer model differs from the solution and crystal structures in terms of the openness of the N-terminus of the channel, the constriction at Ser31, and the sidechain conformations of Trp41, a residue important for channel gating. Moreover, the tetramer model suggests that Ser31 may interact with amantadine amine via hydrogen bonding. While the apo and drug-bound M2TMP have similar average structures, the complexed peptide has much narrower linewidths at physiological temperature, indicating drug-induced changes of the protein dynamics in the membrane. Further, at low temperature, several residues show narrower lines in the complexed peptide than the apo peptide, indicating that amantadine binding reduces the conformational heterogeneity of specific residues. The differences of the current solid-state NMR structure of the bilayer-bound M2TMP from the detergent-based M2 structures suggest that the M2 conformation is sensitive to the environment, and care must be taken when interpreting

  13. Solid-state NMR spectroscopic study of coordination compounds of XeF(2) with metal cations and the crystal structure of [Ba(XeF(2))(5)][AsF(6)](2). (United States)

    Gerken, Michael; Hazendonk, Paul; Iuga, Adriana; Nieboer, Jared; Tramsek, Melita; Goreshnik, Evgeny; Zemva, Boris; Zheng, Shaohui; Autschbach, Jochen


    The coordination compounds [Mg(XeF(2))(2)][AsF(6)](2), [Mg(XeF(2))(4)][AsF(6)](2), [Ca(XeF(2))(2.5)][AsF(6)](2), [Ba(XeF(2))(3)][AsF(6)](2), and [Ba(XeF(2))(5)][AsF(60](2) were characterized by solid-state (19)F and (129)Xe magic-angle spinning NMR spectroscopy. The (19)F and (129)Xe NMR data of [Mg(XeF(2))(2)][AsF(6)](2), [Mg(XeF(2)(4)][AsF(6)](2), and [Ca(XeF(2))(2.5)][AsF(6)](2) were correlated with the previously determined crystal structures. The isotropic (19)F chemical shifts and (1)J((129)Xe-(19)F) coupling constants were used to distinguish the terminal and bridging coordination modes of XeF(2). Chemical-shift and coupling-constant calculations for [Mg(XeF(2))(4)][AsF(6)](2) confirmed the assignment of terminal and bridging chemical-shift and coupling-constant ranges. The NMR spectroscopic data of [Ba(XeF(2))(3)][AsF(6)](2) and [Ba(XeF(2))(5)][AsF(6)](2) indicate the absence of any terminal XeF(2) ligands, which was verified for [Ba(XeF(2))(5)][AsF(6)](2) by its X-ray crystal structure. The adduct [Ba(XeF(2))(5)][AsF(6)](2) crystallizes in the space group Fmmm, with a = 11.6604(14) Angstrom, b = 13.658(2) Angstrom, c = 13.7802(17) Angstrom, V = 2194.5(5) Angstrom(3) at -73 degrees C, Z = 4, and R = 0.0350 and contains two crystallographically independent bridging XeF(2) molecules and one nonligating XeF(2) molecule. The AsF(6-) anions in [Mg(XeF(2))(4)][AsF(6)](2), [Ca(XeF(2))(2.5)][AsF(6)](2), [Ba(XeF(2))(3)][AsF(6)](2), and [Ba(XeF(2))(5)][AsF(6)](2) were shown to be fluxional with the fluorines-on-arsenic being equivalent on the NMR time scale, emulating perfectly octahedral anion symmetry.

  14. Synthesis of LiNixMn2-xO4 by low-temperature solid-state reaction and its microstructure (United States)

    Purwaningsih, D.; Roto, R.; Sutrisno, H.


    This study aims to synthesis the Ni-doped LiNixMn2-xO4 (x = 0; 0.02; 0.04; 0.06; 08; 0.1) by low temperature solid-state reaction. The microstructure of the product was evaluated based on the mole ratio of Ni/Mn of the precursors. The structural analysis of LiNixMn2-xO4 was analyzed by x-ray diffraction equipped with the Direct Method of win PLOTR package program and Diamond. It was found that doping with Ni could change the size, crystallinity and microstructure of LiNixMn2-xO4. The LiNixMn2-xO4 solids have a cubic structure with a space group of Fd3m. The increase in the doping content does not affect the structure. The particle size of the products is about 150-500 nm. The crystallinity of the solids tends to increase with the increase in Ni content. However, the increase of Ni content in the product causes the lattice parameters of the unit cell to decrease.

  15. Solid-State Synthesis of Polyaniline/Single-Walled Carbon Nanotubes: A Comparative Study with Polyaniline/Multi-Walled Carbon Nanotubes (United States)

    Abdiryim, Tursun; Ubul, Aminam; Jamal, Ruxangul; Rahman, Adalet


    The polyaniline/single-walled carbon nanotubes (PANI/SWNTs) composites with a content of SWNTs varying from 8 wt% to 32 wt% were synthesized using a solid-state synthesis method. The structure and morphology of the samples were characterized by fourier transform infrared (FTIR) spectra, ultraviolet-visible (UV-vis) absorption spectra, X-ray diffraction (XRD) and transmission electron microscopy (TEM). The electrochemical performances of the composites were investigated by galvanostatic charge–discharge and cycling stability measurements. The structure and properties of PANI/SWNTs were compared with those of PANI/multi-walled carbon nanotubes (PANI/MWNTs) prepared under the same polymerization conditions. The results from FTIR and UV-vis spectra showed that the composites with SWNTs displayed a higher oxidation and doping degree than pure PANI, which is similar to that of PANI/MWNTs. The morphological studies revealed that PANI/SWNTs did not display any rod-like and granular-like features, which appeared in PANI/MWNTs. The galvanostatic charge–discharge measurements indicated that the specific capacitance of PANI/SWNTs is not higher than that of PANI/MWNTs, but the PANI/SWNTs exhibited higher cycling stability and more stable electrochemical behavior in neutral and alkaline electrolytes than PANI/MWNTs.

  16. Positively charged polysilsesquioxane/iodide lonic liquid as a quasi solid-state redox electrolyte for dye-sensitized photo electrochemical cells: infrared, 29 Si NMR, and electrical studies

    Directory of Open Access Journals (Sweden)


    Full Text Available A new sol-gel precursor based on 1-methyl-3-[3-(trimethoxy- λ 4 -silylpropyl]-1 H -imidazolium iodide (MTMSPI + I − was synthesized and investigated as a potential novel quasi solid-state ionic liquid redox electrolyte for dye-synthesized photoelectrochemical (DSPEC cells of the Graetzel type. MTMSPI + I − was hydrolyzed with acidified water and the reaction products of the sol-gel condensation reactions assessed with the help of 29 Si NMR and infrared spectroscopic techniques. Results of the time-dependent spectra analyses showed the formation of positively charged polyhedral cube-like silsesquioxane species that still contained a small amount of silanol end groups, which were removed after heating at 200 ° C . After cooling, the resulting material formed is a tough, yellowish, and transparent solid, which could be reheated again and used for assembling DSPEC cells. The addition of iodine increased the specific conductivity of the hydrolyzed and nonhydrolyzed MTMSPI + I − , which we attributed to the formation of triiodide ions contributed to the conductivity via the Grotthus mechanism. DSPEC cells based on a titania-dye system with MTMSPI + I − electrolyte containing iodine (0.1 M reached an overall efficiency between 3.3–3.7%.

  17. Examination of the structure in solid state of amino analogs of 4,4‧-[1,5-pentanediylbis(oxy)]bisbenzonitrile by means of X-ray diffraction, 13C CP/MAS NMR, and theoretical calculations (United States)

    Maciejewska, Dorota; Wolska, Irena; Żabiński, Jerzy


    A single crystal of X-ray diffraction structures is presented for 4,4'-[1,5-(3-oxapentanediylbis(amino))]bisbenzonitrile 2 and 4,4'-[1,5-( N-methyl-3-azapentane-diylbis(oxy))]bisbenzonitrile 3. The molecular structures of these derivatives differ especially in conformations of the central linker: in 2 this linker adopts a trans/ gauche conformation, whereas in 3 - a fully extended conformation. The N atoms in various positions of the aliphatic linker change dramatically the molecular packing mode of both bisnitriles. But in both cases the nitrile groups take part in intermolecular hydrogen bonds: a type of N sbnd H···N in 2 and of C sbnd H···N in 3. Various conformations of both molecules were reflected in 13C CP/MAS NMR spectra in solid state as single and double resonance patterns for 2 and 3, respectively. A preliminary anticancer assay against 60 cell lines of 3 reveals strong growth inhibition of leukemia, melanoma, and renal cancer cells.

  18. Monoclinic β-Li2TiO3 nanocrystalline particles employing novel urea assisted solid state route: Synthesis, characterization and sintering behavior (United States)

    Tripathi, Biranchi M.; Mohanty, Trupti; Prakash, Deep; Tyagi, A. K.; Sinha, P. K.


    Pure phase monoclinic nano-crystalline Li2TiO3 powder was synthesized by a novel urea assisted solid state synthesis method using readily available and economical precursors. A single phase and well crystalline Li2TiO3 powder has been obtained at slightly lower temperature (600-700 °C) and shorter duration (2 h) as compared to the conventional solid state method. The proposed method has significant advantages in comparison to other viable methods mainly in terms of phase purity, powder properties and sinterability. Analysis of chemical composition using inductively coupled plasma atomic emission spectroscopy (ICP-AES) shows no loss of lithium from Li2TiO3 in the proposed method. The emergence of monoclinic Li2TiO3 phase was confirmed by X-ray diffraction (XRD) pattern of as-synthesized powder. The crystallite size of Li2TiO3 powder was calculated to be in the range of 15-80 nm, which varied as a function of urea composition and temperature. The morphology of as-prepared Li2TiO3 powders was examined by scanning electron microscope (SEM). The effect of urea composition on phase and morphology was investigated so as to delineate the role of urea. Upon sintering at < 1000 °C temperature, the Li2TiO3 powder compact attained about 98% of the theoretical density with fine grained (grain size: 2-3 μm) microstructure. It indicates excellent sinter-ability of Li2TiO3 powder synthesized by the proposed method. The fine grained structure is desirable for better tritium breeding performance of Li2TiO3. Electrochemical impedance spectroscopy at variable temperature showed good electrical properties of Li2TiO3. The proposed method is simple, anticipated to be cost effective and convenient to realise for large scale production of phase pure nanocrystalline and having significantly enhanced sinter-ability Li2TiO3 powder.

  19. Evaluation of poly(methyl methacrylate)/poly(vinylpyrrolidone)/poly(ethylene oxide) blends by solution and solid state NMR; Avaliacao da mistura fisica de poli(metacrilato de metila)/polivinilpirrolidona/poli(oxido de etileno) por ressonancia magnetica nuclear em solucao e solido

    Energy Technology Data Exchange (ETDEWEB)

    Diniz, Teresinha M.F.F. [Instituto Nacional da Propriedade Industrial (INPI), Rio de Janeiro, RJ (Brazil)]. E-mail:; Tavares, Maria Ines B. [Universidade Federal, Rio de Janeiro, RJ (Brazil). Inst. de Macromoleculas]. E-mail:


    Ternary blends formed by poly(methyl methacrylate) (PMMA)/poly(vinyl pyrrolidone) (PVP)/poly(ethylene oxide) (PEO) have been investigated applying solution and solid state nuclear magnetic resonance. From solution NMR it can be seen that no change in the chemical shift of the microstructure detected in the carbonyl and C quaternary carbons of PMMA was found. However a small change in the form of those signals was observed. This change was attributed to the plasticization effect. The solid state techniques showed that both PEO and PVP acts as a plasticizer in different ways, which depends on these proportions that derives from different dynamical behavior. (author)

  20. Model-free estimation of the effective correlation time for C–H bond reorientation in amphiphilic bilayers: {sup 1}H–{sup 13}C solid-state NMR and MD simulations

    Energy Technology Data Exchange (ETDEWEB)

    Ferreira, Tiago Mendes, E-mail: [Department Chemie, Universität Paderborn, Warburger Straße 100, 33098 Paderborn (Germany); Physical Chemistry, Lund University, P.O. Box 124, SE-221 00 Lund (Sweden); Ollila, O. H. Samuli [Physical Chemistry, Lund University, P.O. Box 124, SE-221 00 Lund (Sweden); Helsinki Biophysics and Biomembrane Group, Department of Biomedical Engineering and Computational Science, Aalto University, Espoo (Finland); Pigliapochi, Roberta [Physical Chemistry, Lund University, P.O. Box 124, SE-221 00 Lund (Sweden); Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge CB2 1EW (United Kingdom); Dabkowska, Aleksandra P.; Topgaard, Daniel [Physical Chemistry, Lund University, P.O. Box 124, SE-221 00 Lund (Sweden)


    Molecular dynamics (MD) simulations give atomically detailed information on structure and dynamics in amphiphilic bilayer systems on timescales up to about 1 μs. The reorientational dynamics of the C–H bonds is conventionally verified by measurements of {sup 13}C or {sup 2}H nuclear magnetic resonance (NMR) longitudinal relaxation rates R{sub 1}, which are more sensitive to motional processes with correlation times close to the inverse Larmor frequency, typically around 1-10 ns on standard NMR instrumentation, and are thus less sensitive to the 10-1000 ns timescale motion that can be observed in the MD simulations. We propose an experimental procedure for atomically resolved model-free estimation of the C–H bond effective reorientational correlation time τ{sub e}, which includes contributions from the entire range of all-atom MD timescales and that can be calculated directly from the MD trajectories. The approach is based on measurements of {sup 13}C R{sub 1} and R{sub 1ρ} relaxation rates, as well as {sup 1}H−{sup 13}C dipolar couplings, and is applicable to anisotropic liquid crystalline lipid or surfactant systems using a conventional solid-state NMR spectrometer and samples with natural isotopic composition. The procedure is demonstrated on a fully hydrated lamellar phase of 1-palmitoyl-2-oleoyl-phosphatidylcholine, yielding values of τ{sub e} from 0.1 ns for the methyl groups in the choline moiety and at the end of the acyl chains to 3 ns for the g{sub 1} methylene group of the glycerol backbone. MD simulations performed with a widely used united-atom force-field reproduce the τ{sub e}-profile of the major part of the acyl chains but underestimate the dynamics of the glycerol backbone and adjacent molecular segments. The measurement of experimental τ{sub e}-profiles can be used to study subtle effects on C–H bond reorientational motions in anisotropic liquid crystals, as well as to validate the C–H bond reorientation dynamics predicted in MD

  1. Mechanochemically assisted room temperature solid state ...

    Indian Academy of Sciences (India)

    This communication reports a novel mechanochemically assisted room temperature solid state metathesis reaction for the synthesis of submicron-size alkaline-earth molybdates crystallizing in a tetragonal Scheelite structure. The solids were characterized by powder XRD, FTIR, TGA, DTA, SEM, EDAX and TEM to ascertain ...

  2. by a solid-state metathesis approach

    Indian Academy of Sciences (India)


    Abstract. A solid-state metathesis approach initiated by microwave energy has been successfully applied for the synthesis of orthovanadates, M3V2O8 (M = Ca, Sr, and Ba). The structural, vibrational, thermal, optical and chemical properties of synthesized powders are determined by powder X-ray diffraction, scanning ...

  3. Heterometallic molecular precursors for a lithium-iron oxide material: synthesis, solid state structure, solution and gas-phase behaviour, and thermal decomposition. (United States)

    Han, Haixiang; Wei, Zheng; Barry, Matthew C; Filatov, Alexander S; Dikarev, Evgeny V


    Three heterometallic single-source precursors with a Li : Fe = 1 : 1 ratio for a LiFeO2 oxide material are reported. Heterometallic compounds LiFeL3 (L = tbaoac (1), ptac (2), and acac(3)) have been obtained on a large scale, in nearly quantitative yields by one-step reactions that employ readily available reagents. The heterometallic precursor LiFe(acac)3 (3) with small, symmetric substituents on the ligand (acac = pentane-2,4-dionate), maintains a 1D polymeric structure in the solid state that limits its volatility and prevents solubility in non-coordinating solvents. The application of the unsymmetrical ligands, tbaoac (tert-butyl acetoacetate) and ptac (1,1,1-trifluoro-5,5-dimethyl-2,4-hexanedionate), that exhibit different bridging properties at the two ends of the ligand, allowed us to change the connectivity pattern within the heterometallic assembly. The latter was demonstrated by structural characterization of heterometallic complexes LiFe(tbaoac)3 (1) and LiFe(ptac)3 (2) that consist of discrete heterocyclic tetranuclear molecules Li2Fe2L6. The compounds are highly volatile and exhibit a congruent sublimation character. DART mass spectrometric investigation revealed the presence of heterometallic molecules in the gas phase. The positive mode spectra are dominated by the presence of [M - L]+ peaks (M = Li2Fe2L6). In accord with their discrete molecular structure, complexes 1 and 2 are highly soluble in nearly all common solvents. In order to test the retention of the heterometallic structure in solution, the diamagnetic analog of 1, LiMg(tbaoac)3 (4), has been isolated. Its tetranuclear molecular structure was found to be isomorphous to that of the iron counterpart. 1H and 7Li NMR spectroscopy unambiguously confirmed the presence of heterometallic molecules in solutions of non-coordinating solvents. The heterometallic precursor 1 was shown to exhibit clean thermal decomposition in air that results in phase-pure α-modification of layered oxide Li

  4. Solid state physics

    CERN Document Server

    Grosso, Giuseppe


    Solid State Physics is a textbook for students of physics, material science, chemistry, and engineering. It is the state-of-the-art presentation of the theoretical foundations and application of the quantum structure of matter and materials. This second edition provides timely coverage of the most important scientific breakthroughs of the last decade (especially in low-dimensional systems and quantum transport). It helps build readers' understanding of the newest advances in condensed matter physics with rigorous yet clear mathematics. Examples are an integral part of the text, carefully de

  5. Solid state physics

    CERN Document Server

    Burns, Gerald


    The objective of Solid State Physics is to introduce college seniors and first-year graduate students in physics, electrical engineering, materials science, chemistry, and related areas to this diverse and fascinating field. I have attempted to present this complex subject matter in a coherent, integrated manner, emphasizing fundamental scientific ideas to give the student a strong understanding and ""feel"" for the physics and the orders of magnitude involved. The subject is varied, covering many important, sophisticated, and practical areas, which, at first, may appear unrelated but which ar

  6. Solid state optical microscope (United States)

    Young, Ian T.


    A solid state optical microscope wherein wide-field and high-resolution images of an object are produced at a rapid rate by utilizing conventional optics with a charge-coupled photodiode array. A galvanometer scanning mirror, for scanning in one of two orthogonal directions is provided, while the charge-coupled photodiode array scans in the other orthogonal direction. Illumination light from the object is incident upon the photodiodes, creating packets of electrons (signals) which are representative of the illuminated object. The signals are then processed, stored in a memory, and finally displayed as a video signal.

  7. Solid state phenomena

    CERN Document Server

    Lawrance, R


    Solid State Phenomena explores the fundamentals of the structure and their influence on the properties of solids. This book is composed of five chapters that focus on the electrical and thermal conductivities of crystalline solids. Chapter 1 describes the nature of solids, particularly metals and crystalline materials. This chapter also presents a model to evaluate crystal structure, the forces between atom pairs, and the mechanism of plastic and elastic deformation. Chapter 2 demonstrates random vibrations of atoms in a solid using a one-dimensional array, while Chapter 3 examines the resista

  8. Solid-State 55Mn NMR Spectroscopy of bis(μ-oxo)dimanganese(IV) [Mn2O2(salpn)2], a Model for the Oxygen Evolving Complex in Photosystem II

    Energy Technology Data Exchange (ETDEWEB)

    Ellis, Paul D.; Sears, Jesse A.; Yang, Ping; Dupuis, Michel; Boron, Ted; Pecoraro, Vince; Stich, Troy; Britt, R. David; Lipton, Andrew S.


    Given the obvious global energy needs, it has become imperative to develop a catalytic process for converting water to molecular oxygen and protons. Many have sought to understand the details of photosynthesis and in particular the water splitting reaction to help in the development of the appropriate catalysis.1-3 While the scientific community has made great strides towards this goal, it has fallen short at the critical stage of the determination of the structure associated with the oxygen evolving complex (OEC) within photosystem II (PSII).4,5 Despite the existence of x-ray structures of PSII,6-8 the best data we have for the structure of the OEC comes from models derived from EPR and EXAFS measurements.9-14 This experimental situation has led to collaborations with theoreticians to enable the development of models for the structure of the OEC where the experimental observables (EXAFS and magnetic resonance parameters) serve as constraints to the theoretical calculations. Of particular interest to this study is the observation of the S1 state of the Kok cycle15 where the core of the OEC can be described as a tetranuclear manganese cluster composed of Mn4OxCa. The simplest model for the OEC can be thought of as two Mn-pairs and a Ca2+ where each Mn-pair is antiferromagnetically coupled to its partner. We utilize the term "pair" to describe the Mn atoms within the OEC with the same oxidation state, which for the S1 state is (Mn2(III, III) and Mn2(IV, IV)).16 It is unclear as to the degree of interaction between the pairs as well as the role of the Ca2+. At cryogenic temperatures the S1 state of the OEC is diamagnetic and in principle amenable to solid-state NMR experiments.

  9. Nano-Mole Scale Side-Chain Signal Assignment by 1H-Detected Protein Solid-State NMR by Ultra-Fast Magic-Angle Spinning and Stereo-Array Isotope Labeling

    KAUST Repository

    Wang, Songlin


    We present a general approach in 1H-detected 13C solid-state NMR (SSNMR) for side-chain signal assignments of 10-50 nmol quantities of proteins using a combination of a high magnetic field, ultra-fast magic-angle spinning (MAS) at ~80 kHz, and stereo-array-isotope-labeled (SAIL) proteins [Kainosho M. et al., Nature 440, 52–57, 2006]. First, we demonstrate that 1H indirect detection improves the sensitivity and resolution of 13C SSNMR of SAIL proteins for side-chain assignments in the ultra-fast MAS condition. 1H-detected SSNMR was performed for micro-crystalline ubiquitin (~55 nmol or ~0.5mg) that was SAIL-labeled at seven isoleucine (Ile) residues. Sensitivity was dramatically improved by 1H-detected 2D 1H/13C SSNMR by factors of 5.4-9.7 and 2.1-5.0, respectively, over 13C-detected 2D 1H/13C SSNMR and 1D 13C CPMAS, demonstrating that 2D 1H-detected SSNMR offers not only additional resolution but also sensitivity advantage over 1D 13C detection for the first time. High 1H resolution for the SAIL-labeled side-chain residues offered reasonable resolution even in the 2D data. A 1H-detected 3D 13C/13C/1H experiment on SAIL-ubiquitin provided nearly complete 1H and 13C assignments for seven Ile residues only within ~2.5 h. The results demonstrate the feasibility of side-chain signal assignment in this approach for as little as 10 nmol of a protein sample within ~3 days. The approach is likely applicable to a variety of proteins of biological interest without any requirements of highly efficient protein expression systems.

  10. Gallium-containing Heusler phases ScRh{sub 2}Ga, ScPd{sub 2}Ga, TmRh{sub 2}Ga and LuRh{sub 2}Ga. Magnetic and solid state NMR-spectroscopic characterization

    Energy Technology Data Exchange (ETDEWEB)

    Heletta, Lukas; Seidel, Stefan; Poettgen, Rainer [Muenster Univ. (Germany). Inst. fuer Anorganische und Analytische Chemie; Benndorf, Christopher [Leipzig Univ. (Germany). Inst. fuer Mineralogie, Kristallographie und Materialwissenschaften; Eckert, Hellmut [Muenster Univ. (Germany). Inst. fuer Physikalische Chemie; Sao Paulo Univ., Sao Carlos (Brazil). Inst. of Physics


    The gallium-containing Heusler phases ScRh{sub 2}Ga, ScPd{sub 2}Ga, TmRh{sub 2}Ga and LuRh{sub 2}Ga have been synthesized by arc-melting of the elements followed by different annealing sequences to improve phase purity. The samples have been studied by powder X-ray diffraction. The structures of Lu{sub 0.97}Rh{sub 2}Ga{sub 1.03} (Fm3m, a=632.94(5) pm, wR2=0.0590, 46 F{sup 2} values, seven variables) and Sc{sub 0.88}Rh{sub 2}Ga{sub 1.12} (a=618.91(4) pm, wR2=0.0284, 44 F{sup 2} values, six variables) have been refined from single crystal X-ray diffractometer data. Both gallides show structural disorder through Lu/Ga and Sc/Ga mixing. Temperature dependent magnetic susceptibility measurements showed Pauli paramagnetism for ScRh{sub 2}Ga, ScPd{sub 2}Ga, and LuRh{sub 2}Ga and Curie-Weiss paramagnetism for TmRh{sub 2}Ga. {sup 45}Sc and {sup 71}Ga solid state MAS NMR spectroscopic investigations of the Sc containing compounds confirmed the site mixing effects typically observed for Heusler phases. The data indicate that the effect of mixed Sc/Ga occupancy is significantly stronger in ScRh{sub 2}Ga than in ScPd{sub 2}Ga.

  11. Solid state magnetism

    CERN Document Server

    Crangle, John


    Solid state magnetism is important and attempts to understand magnetic properties have led to an increasingly deep insight into the fundamental make up of solids. Both experimental and theoretical research into magnetism continue to be very active, yet there is still much ground to cover before there can be a full understanding. There is a strong interplay between the developments of materials science and of magnetism. Hundreds of new materials have been dis­ covered, often with previously unobserved and puzzling magnetic prop­ erties. A large and growing technology exists that is based on the magnetic properties of materials. Very many devices used in everyday life involve magnetism and new applications are being invented all the time. Under­ standing the fundamental background to the applications is vital to using and developing them. The aim of this book is to provide a simple, up-to-date introduction to the study of solid state magnetism, both intrinsic and technical. It is designed to meet the needs a...

  12. Structural variation in ethylenediamine and -diphosphine adducts of (2,6-Me2C6H3S)2Pb: a single crystal X-ray diffraction and 207Pb solid-state NMR spectroscopy study. (United States)

    Rossini, Aaron J; Macgregor, Alan W; Smith, Anita S; Schatte, Gabriele; Schurko, Robert W; Briand, Glen G


    Coordination complexes of (2,6-Me2C6H3S)2Pb (1) with flexible bidentate ligands have been prepared to explore new bonding environments for Pb(II) thiolates. The reaction of 1 with a series of ethylenediamine and ethylenediphosphine ligands resulted in isolation of the adducts [(2,6-Me2C6H3S)2Pb]2(tmeda) (9), [(2,6-Me2C6H3S)2Pb]3(dmpe) (10) and [(2,6-Me2C6H3S)2Pb]2(dppe) (11) [tmeda = N,N,N',N'-tetramethylethylenediamine; dmpe = bis(dimethylphosphino)ethane; dppe = bis(diphenylphosphino)ethane]. The X-ray crystal structure of 9 shows a dinuclear species in which tmeda is chelating a ψ-trigonal bipyramidal S2N2 Pb centre via axial and equatorial sites. The structure of 10 displays a trinuclear structural unit in which dmpe is chelating a ψ-trigonal bipyramidal S2P2 Pb centre via equatorial sites. Compounds 9 and 10 also contain a second unique metal centre with ψ-tetrahedral S3Pb bonding motifs. The structure of 11 shows the dppe ligand bridging two Pb ψ-tetrahedral S2P metal bonding environments. Static (207)Pb solid-state NMR (SSNMR) spectra of 9-11 and [Ph4As][(PhS)3Pb] (12) were acquired with cross polarization (CP)-CPMG and frequency swept pulse (WURST)-CPMG pulse sequences, and the efficiencies of these pulse sequences are compared. The (207)Pb SSNMR spectra reveal that the lead chemical shift anisotropies (CSA) vary greatly between the different Pb sites, and are generally large in magnitude. DFT calculations are utilized to relate the orientations of the (207)Pb nuclear magnetic shielding tensors to the molecular structures, and to aid in spectral assignment where multiple Pb centres are present. The combination of X-ray diffraction, (207)Pb SSNMR and DFT is shown to be invaluable for the structural characterization of these important structural motifs, and should find wide-ranging application to numerous lead coordination compounds.

  13. Luminescence and the solid state

    CERN Document Server

    Ropp, Richard C


    Since the discovery of the transistor in 1948, the study of the solid state has been burgeoning. Recently, cold fusion and the ceramic superconductor have given cause for excitement. There are two approaches possible to this area of science, namely, that of solid state physics and solid state chemistry, although both overlap extensively. The former is more concerned with electronic states in solids (including electromagnetics) whereas the latter is more concerned with interactions of atoms in solids. The area of solid state physics is well documented, however, there are very few texts which de

  14. Solid state chemistry an introduction

    CERN Document Server

    Smart, Lesley E


    ""Smart and Moore are engaging writers, providing clear explanations for concepts in solid-state chemistry from the atomic/molecular perspective. The fourth edition is a welcome addition to my bookshelves. … What I like most about Solid State Chemistry is that it gives simple clear descriptions for a large number of interesting materials and correspondingly clear explanations of their applications. Solid State Chemistry could be used for a solid state textbook at the third or fourth year undergraduate level, especially for chemistry programs. It is also a useful resource for beginning graduate

  15. Solid state laser (United States)

    Rines, Glen A. (Inventor); Moulton, Peter F. (Inventor); Harrison, James (Inventor)


    A wavelength-tunable, injection-seeded, dispersion-compensated, dispersively-pumped solid state laser includes a lasing medium; a highly reflective mirror; an output coupler; at least one isosceles Brewster prism oriented to the minimum deviation angle between the medium and the mirror for directing light of different wavelengths along different paths; means for varying the angle of the highly reflective mirror relative to the light from at least one Brewster angle for selecting a predetermined laser operating wavelength; a dispersion compensation apparatus associated with the lasing medium; a laser injection seeding port disposed between the dispersion compensation apparatus and one of the mirror and coupler and including a reflective surface at an acute non-Brewster angle to the laser beam for introducing a seed input; a dispersion compensation apparatus associated with the laser medium including opposite chirality optical elements; the lasing medium including a pump surface disposed at an acute angle to the laser beam to define a discrete path for the pumping laser beam separate from the pumped laser beam.

  16. Synthesis and crystallochromy of 1,4,7,10-tetraalkyltetracenes: tuning of solid-state optical properties of tetracenes by alkyl side-chain length. (United States)

    Kitamura, Chitoshi; Abe, Yasushi; Ohara, Takuya; Yoneda, Akio; Kawase, Takeshi; Kobayashi, Takashi; Naito, Hiroyoshi; Komatsu, Toshiki


    We synthesized a series of 1,4,7,10-tetraalkyltetracenes using a new 2,6-naphthodiyne precursor and 2,5-dialkylfurans as starting materials (alkyl=methyl to hexyl). Surprisingly, the solid-state color of the tetracenes ranges through yellow, orange, and red. Both yellow and red solids are obtained for the butyl derivative. Optical properties in solution show no marked differences; however, those in the solid state show characteristics that vary with alkyl side-chain length: methyl, propyl, and pentyl derivatives are orange; ethyl and butyl derivatives are yellow; and another butyl and hexyl derivative are red. X-ray analyses reveal that the molecular structures are planar, semi-chair, or chair forms; the chair form takes a herringbone-like arrangement and the other forms take slipped parallel arrangements. The mechanism of crystallochromy is discussed in terms of molecular structure, crystal packing, and calculations that take account of exciton coupling.

  17. Facile synthesis of PbTiO3 truncated octahedra via solid-state reaction and their application in low-temperature CO oxidation by loading Pt nanoparticles

    KAUST Repository

    Yin, Simin


    Perovskite PbTiO3 (PTO) nanocrystals with a truncated octahedral morphology have been prepared by a facile solid-state reaction. Pt nanoparticles preferentially nucleated on the {111} facet of PTO nanocrystals exhibit a remarkable low-temperature catalytic activity towards CO oxidation from a temperature as low as 30 °C and achieve 100% conversion at ∼50 °C. © 2014 the Partner Organisations.

  18. Phosphate Phosphors for Solid-State Lighting

    CERN Document Server

    Shinde, Kartik N; Swart, H C; Park, Kyeongsoon


    The idea for this book arose out of the realization that, although excellent surveys and a phosphor handbook are available, there is no single source covering the area of phosphate based phosphors especially for lamp industry. Moreover, as this field gets only limited attention in most general books on luminescence, there is a clear need for a book in which attention is specifically directed toward this rapidly growing field of solid state lighting and its many applications. This book is aimed at providing a sound introduction to the synthesis and optical characterization of phosphate phosphor for undergraduate and graduate students as well as teachers and researchers. The book provides guidance through the multidisciplinary field of solid state lighting specially phosphate phosphors for beginners, scientists and engineers from universities, research organizations, and especially industry. In order to make it useful for a wide audience, both fundamentals and applications are discussed, together.

  19. Solid state synthesis of layered sodium manganese oxide for sodium-ion battery by in-situ high energy X-ray diffraction and X-ray absorption near edge spectroscopy (United States)

    Ma, Tianyuan; Xu, Gui-Liang; Zeng, Xiaoqiao; Li, Yan; Ren, Yang; Sun, Chengjun; Heald, Steve M.; Jorne, Jacob; Amine, Khalil; Chen, Zonghai


    In situ high energy X-ray diffraction (HEXRD) and in situ X-ray absorption near edge spectroscopy (XANES) were carried out to understand the solid state synthesis of NaxMnO2, with particular interest on the synthesis of P2 type Na2/3MnO2. It was found that there were multi intermediate phases formed before NaMnO2 appeared at about 600 °C. And the final product after cooling process is a combination of O‧3 NaMnO2 with P2 Na2/3MnO2. A P2 type Na2/3MnO2 was synthesized at reduced temperature (600 °C). The influence of Na2CO3 impurity on the electrochemical performance of P2 Na2/3MnO2 was thoroughly investigated in our work. It was found that the content of Na2CO3 can be reduced by optimizing Na2CO3/MnCO3 ratio during the solid state reaction or other post treatment such as washing with water. We expected our results could provide a good guide for future development of high performance cathode materials for sodium-ion batteries.

  20. Handbook of solid state batteries & capacitors

    National Research Council Canada - National Science Library

    Munshi, M. Z. A


    ... is witnessing a metamorphosis in the area of solid state power sources. The genesis of solid state battery research commenced with the discovery of highly conductive silver solid state and copper solid state electrolytes in the sixties and seventies, and their subsequent use in solid state batteries. These discoveries were major breakthroughs for those ti...

  1. Solid-state laser engineering

    CERN Document Server

    Koechner, Walter


    Solid-State Laser Engineering, written from an industrial perspective, discusses in detail the characteristics, design, construction, and performance of solid-state lasers. Emphasis is placed on engineering and practical considerations; phenomenological aspects using models are preferred to abstract mathematical derivations. This new edition has extensively been updated to account for recent developments in the areas of diode-laser pumping, mode locking, ultrashort-pulse generation etc. Walter Koechner received a doctorate in Electrical Engineering from the University of Technology in Vienna, Austria, in 1965. He has published numerous papers in the fields of solid-state physics, optics, and lasers. Dr. Koechner is founder and president of Fibertek, Inc., a research firm specializing in the design, development, and production of advanced solid-state lasers, optical radars, and remote-sensing systems.

  2. Solid-state laser engineering

    CERN Document Server

    Koechner, Walter


    Solid-State Laser Engineering, written from an industrial perspective, discusses in detail the characteristics, design, construction, and performance of solid-state lasers. Emphasis is placed on engineering and practical considerations; phenomenological aspects using models are preferred to abstract mathematical derivations. This new edition has extensively been updated to account for recent developments in the areas of diode-laser pumping, laser materials, and nonlinear crystals. Walter Koechner received a doctorate in Electrical Engineering from the University of Technology in Vienna, Austria, in 1965. He has published numerous papers in the fields of solid-state physics, optics, and lasers. Dr. Koechner is founder and president of Fibertek, Inc., a research firm specializing in the design, development, and production of advanced solid-state lasers, optical radars, and remote-sensing systems.

  3. Stereoblock poly(lactic acid): synthesis via solid-state polycondensation of a stereocomplexed mixture of poly(L-lactic acid) and poly(D-lactic acid). (United States)

    Fukushima, Kazuki; Furuhashi, Yukiko; Sogo, Kazuaki; Miura, Shigenobu; Kimura, Yoshiharu


    Stereoblock poly(lactic acid) consisting of D- and L-lactate stereosequences can be successfully synthesized by solid-state polycondensation of a 1:1 mixture of poly(L-lactic acid) and poly(D-lactic acid). In the first step, melt-polycondensation of L- and D-lactic acids is conducted to synthesize poly(L-lactic acid) and poly(D-lactic acid) with a medium-molecular-weight, respectively. In the next step, these poly(L-lactic acid) and poly(D-lactic acid) are melt-blended in 1:1 ratio to allow formation of their stereocomplex. In the last step, this melt-blend is subjected to solid-state polycondensation at temperature where the dehydrative condensation is allowed to promote chain extension in the amorphous phase with the stereocomplex crystals preserved. Finally, stereoblock poly(lactic acid) having high-molecular-weight is obtained. The stereoblock poly(lactic acid) synthesized by this way shows a higher melting temperature in consequence of the controlled block lengths and the resulting higher-molecular-weight. The product characterization as well as the optimization of the polymerization conditions is described. Changes in M(w) of stereoblock poly(lactic acid) (sb-PLA) as a function of the reaction time.

  4. Cobalt terephthalate MOF-templated synthesis of porous nano-crystalline Co3O4 by the new indirect solid state thermolysis as cathode material of asymmetric supercapacitor (United States)

    Bigdeli, Hadise; Moradi, Morteza; Hajati, Shaaker; Kiani, Mohammad Ali; Toth, Jozsef


    In this work, two different types of Co3O4 nano-crystals were synthesized by (i) conventional direct solid state thermolysis of cobalt terephthalate metal-organic framework (MOF-71) and (ii) new indirect solid state thermolysis of Co(OH)2 derived by alkaline aqueous treatment of MOF-71. The products were then characterized by X-ray diffraction technique (XRD), Fourier transforms infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), Reflection electron energy loss spectroscopy (REELS), Brunauer, Emmett, and Teller (BET), scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDX) techniques. By REELS analysis the energy band gap of MOF-71 was determined to be 3.7 eV. Further, electrochemical performance of each Co3O4 nanostructure was studied by the cyclic voltammetry (CV), galvanostatic charge-discharge (GCD), and electrochemical impedance spectroscopy (EIS) in a three-electrode system in KOH electrolyte. An asymmetric supercapacitor was fabricated using indirect Co3O4 nanoparticles as cathode and electrochemically reduced graphene oxide as anode, and the electrochemical properties were studied and showed a high energy density of 13.51 Wh kg-1 along with a power density of 9775 W kg-1 and good cycling stability with capacitance retention rate of 85% after 2000 cycles.

  5. Facile synthesis of amorphous FeOOH/MnO2 composites as screen-printed electrode materials for all-printed solid-state flexible supercapacitors (United States)

    Lu, Qiang; Liu, Li; Yang, Shuanglei; Liu, Jun; Tian, Qingyong; Yao, Weijing; Xue, Qingwen; Li, Mengxiao; Wu, Wei


    More convenience and intelligence life lead by flexible/wearable electronics requires innovation and hommization of power sources. Here, amorphous FeOOH/MnO2 composite as screen-printed electrode materials for supercapacitors (SCs) is synthesized by a facile method, and solid-state flexible SCs with aesthetic design are fabricated by fully screen-printed process on different substrates, including PET, paper and textile. The amorphous FeOOH/MnO2 composite shows a high specific capacitance and a good rate capability (350.2 F g-1 at a current density of 0.5 A g-1 and 159.5 F g-1 at 20 A g-1). It also possesses 95.6% capacitance retention even after 10 000 cycles. Moreover, the all-printed solid-state flexible SC device exhibits a high area specific capacitance of 5.7 mF cm-2 and 80% capacitance retention even after 2000 cycles. It also shows high mechanical flexibility. Simultaneously, these printed SCs on different substrates in series are capable to light up a 1.9 V yellow light emitting diode (LED), even after bending and stretching.

  6. A simple one step solid state synthesis of nanocrystalline ferromagnetic α-Fe{sub 2}O{sub 3} with high surface area and catalytic activity

    Energy Technology Data Exchange (ETDEWEB)

    Shete, Madhavi D.; Fernandes, J.B., E-mail:


    α-Fe{sub 2}O{sub 3} is obtained by a simple route involving solvent free solid state decomposition of ferric nitrate in presence of urea. The samples were characterized by X-ray diffraction, infra-red and UV–Vis spectral studies, TEM, BET surface area measurements and TG–DTA analysis. Magnetic measurements were done from M–H hysteresis profiles. By changing the ratio of ferric nitrate and urea, α-phase was obtained in all the synthesized samples and was accompanied with increase in ferromagnetic behavior. The samples showed good photocatalytic activity for decomposition of H{sub 2}O{sub 2} and could be correlated with surface area values. The results were interpreted in terms of activity for the heterogeneous photo-Fenton reaction. - Highlights: • α-Fe{sub 2}O{sub 3} were synthesized by a solid state method. • These oxides showed large surface area and ferromagnetic behavior. • The catalysts showed good heterogeneous photo-Fenton activity.

  7. Solid-state laser engineering

    CERN Document Server

    Koechner, Walter


    Solid-State Laser Engineering is written from an industrial perspective and discusses in detail the characteristics, design, construction and practical problems of solid-state lasers. Emphasis is placed on engineering and practical considerations, with a phenomenological treatment using modelsbeing preferred to abstract mathematical derivations. This new edition has been updated and revised to include important developments, concepts and technologies that have emerged since the publication of the first edition.

  8. Solid State Photovoltaic Research Branch

    Energy Technology Data Exchange (ETDEWEB)


    This report summarizes the progress of the Solid State Photovoltaic Research Branch of the Solar Energy Research Institute (SERI) from October 1, 1988, through September 30,l 1989. Six technical sections of the report cover these main areas of SERIs in-house research: Semiconductor Crystal Growth, Amorphous Silicon Research, Polycrystalline Thin Films, III-V High-Efficiency Photovoltaic Cells, Solid-State Theory, and Laser Raman and Luminescence Spectroscopy. Sections have been indexed separately for inclusion on the data base.

  9. Pulse Design in Solid-State Nuclear Magnetic Resonance

    DEFF Research Database (Denmark)

    Palani, Ravi Shankar

    The work presented in this dissertation is centred on the theory of experimental methods in solid-state Nuclear Magnetic Resonance (NMR) spectroscopy, which deals with interaction of electromagnetic radiation with nuclei in a magnetic field and possessing a fundamental quantum mechanical property...

  10. Synthesis and characteristic of nanocrystalline La{sub 0.7}Sr{sub 0.3}MnO{sub 3} manganites by solid state reaction route

    Energy Technology Data Exchange (ETDEWEB)

    Astik, Nidhi, E-mail:; Jha, Prafulla K. [Department of physics, Faculty of Science, The M. S. University of Baroda, Vadodara (India); Patil, Swapnilkumar, E-mail: [Department of Physics, M. K. Bhavnagar University, Bhavnagar (India); Bhargava, Parag [Department of Metallurgical Engineering & Material Science, IIT-Bombay (India)


    Nanocrystalline stoichiometric La{sub 0.7}Sr{sub 0.3}MnO{sub 3} (x=0.3) manganites have been synthesized through solid-state reaction by ball milling mechanical method at two different sintering temperatures 1250°C and 1350°C. The synthesized samples were characterized using X-ray diffraction (XRD) and found to have rhombohedral crystal structure (R-3c). The calcined samples exhibited a pure single phase perovskite, had a crystallite size of about 47-51 nm. The morphology of the prepared nanocrystalline manganites were recorded by the field emission gun-scanning electron microscope (FEG-SEM) and EDAX.

  11. Production of Sporotrichum thermophile xylanase by solid state fermentation utilizing deoiled Jatropha curcas seed cake and its application in xylooligosachharide synthesis. (United States)

    Sadaf, Ayesha; Khare, S K


    De-oiled Jatropha curcas seed cake, a plentiful by-product of biodiesel industry was used as substrate for the production of a useful xylanase from Sporotrichum thermophile in solid state fermentation. Under the optimized conditions, 1025U xylanase/g (deoiled seed cake) was produced. The xylanase exhibited half life of 4h at 45°C and 71.44min at 50°C respectively. It was stable in a broad pH range of 7.0-11.0. Km and Vmax were 12.54mg/ml and 454.5U/ml/min respectively. S. thermophile xylanase is an endoxylanase free of exoxylanase activity, hence advantageous for xylan hydrolysis to produce xylooligosachharides. Hydrolysis of oat spelt xylan by S. thermophile xylanase yielded 73% xylotetraose, 15.4% xylotriose and 10% xylobiose. The S. thermophile endoxylanase thus seem potentially useful in the food industries. Copyright © 2013 Elsevier Ltd. All rights reserved.

  12. Complete doping in solid-state by silica-supported perchloric acid as dopant solid acid: Synthesis and characterization of the novel chiral composite of poly [(±)-2-(sec-butyl) aniline

    Energy Technology Data Exchange (ETDEWEB)

    Farrokhzadeh, Abdolkarim; Modarresi-Alam, Ali Reza, E-mail:


    Poly [(±)-2-(sec-butyl) aniline]/silica-supported perchloric acid composites were synthesized by combination of poly[(±)-2-sec-butylaniline] base (PSBA) and the silica-supported perchloric acid (SSPA) as dopant solid acid in solid-state. The X-ray photoelectron spectroscopy (XPS) and CHNS results confirm nigraniline oxidation state and complete doping for composites (about 75%) and non-complete for the PSBA·HCl salt (about 49%). The conductivity of samples was (≈0.07 S/cm) in agreement with the percent of doping obtained of the XPS analysis. Also, contact resistance was determined by circular-TLM measurement. The morphology of samples by the scanning electron microscopy (SEM) and their coating were investigated by XPS, SEM-map and energy-dispersive X-ray spectroscopy (EDX). The key benefits of this work are the preparation of conductive chiral composite with the delocalized polaron structure under green chemistry and solid-state condition, the improvement of the processability by inclusion of the 2-sec-butyl group and the use of dopant solid acid (SSPA) as dopant. - Highlights: • The solid-state synthesis of the novel chiral composites of poly[(±)-2-(sec-butyl)aniline] (PSBA) and silica-supported perchloric acid (SSPA). • It takes 120 h for complete deprotonation of PSBA.HCl salt. • Use of SSPA as dopant solid acid for the first time to attain the complete doping of PSBA. • The coating of silica surface with PSBA.

  13. Solid state electrolyte systems

    Energy Technology Data Exchange (ETDEWEB)

    Pederson, L.R.; Armstrong, B.L.; Armstrong, T.R. [Pacific Northwest Lab., Richland, WA (United States)] [and others


    Lanthanum gallates are a new family of solid electrolytes that exhibit high ionic conductivity and are stable to high temperatures. Compositions have been developed that are as much as a factor of two more conductive than yttria-stabilized zirconia at a given temperature, through partial replacement of lanthanum by calcium, strontium, and/or barium and through partial replacement of gallium by magnesium. Oxide powders were prepared using combustion synthesis techniques developed in this laboratory; these were sintered to >95% of theoretical density and consisted of a single crystalline phase. Electrical conductivities, electron and ion transference numbers, thermal expansion, and phase behavior were evaluated as a function of temperature and oxygen partial pressure. A key advantage of the use of lanthanum gallate electrolytes in solid oxide fuel cells is that the temperature of operation may be lowered to perhaps 800 C, yet provide approximately the same power density as zirconia-based cells operating at 1000 C. Ceramic electrolytes that conduct both oxygen ions and electrons are potentially useful to passively separate pure oxygen from an air source at low cost. In such materials, an oxygen ion flux in one direction is charge-compensated by an opposing electron flux. The authors have examined a wide range of mixed ion and electron conducting perovskite ceramics in the system La{sub 1{minus}x}M{sub x}Co{sub 1{minus}y{minus}z}Fe{sub y}N{sub z}O{sub 3{minus}{delta}}, where M = Sr, Ca, and Ba, and N = Pr, Mn, Ni, Cu, Ti, and Al, as well as mixed conducting brownmillerite ceramics, and have characterized oxygen permeation behavior, defect chemistry, structural and phase stability, and performance as cathodes.

  14. Phosphate phosphors for solid-state lighting

    Energy Technology Data Exchange (ETDEWEB)

    Shinde, Kartik N. [N.S. Science and Arts College, Bhadrawati (India). Dept. of Physics; Swart, H.C. [University of the Orange Free State, Bloemfontein (South Africa). Dept. of Physics; Dhoble, S.J. [R.T.M. Nagpur Univ. (India). Dept. of Physics; Park, Kyeongsoon [Sejong Univ., Seoul (Korea, Republic of). Faculty of Nanotechnology and Advanced Materials Engineering


    Essential information for students in researchers working towards new and more efficient solid-state lighting. Comprehensive survey based on the authors' long experience. Useful both for teaching and reference. The idea for this book arose out of the realization that, although excellent surveys and a phosphor handbook are available, there is no single source covering the area of phosphate based phosphors especially for lamp industry. Moreover, as this field gets only limited attention in most general books on luminescence, there is a clear need for a book in which attention is specifically directed toward this rapidly growing field of solid state lighting and its many applications. This book is aimed at providing a sound introduction to the synthesis and optical characterization of phosphate phosphor for undergraduate and graduate students as well as teachers and researchers. The book provides guidance through the multidisciplinary field of solid state lighting specially phosphate phosphors for beginners, scientists and engineers from universities, research organizations, and especially industry. In order to make it useful for a wide audience, both fundamentals and applications are discussed, together.

  15. Organic solid-state lasers

    CERN Document Server

    Forget, Sébastien


    Organic lasers are broadly tunable coherent sources, potentially compact, convenient and manufactured at low-costs. Appeared in the mid 60’s as solid-state alternatives for liquid dye lasers, they recently gained a new dimension after the demonstration of organic semiconductor lasers in the 90's. More recently, new perspectives appeared at the nanoscale, with organic polariton and surface plasmon lasers. After a brief reminder to laser physics, a first chapter exposes what makes organic solid-state organic lasers specific. The laser architectures used in organic lasers are then reviewed, with a state-of-the-art review of the performances of devices with regard to output power, threshold, lifetime, beam quality etc. A survey of the recent trends in the field is given, highlighting the latest developments with a special focus on the challenges remaining for achieving direct electrical pumping of organic semiconductor lasers. A last chapter covers the applications of organic solid-state lasers.

  16. Solid-State Laser Engineering

    CERN Document Server

    Koechner, Walter


    Written from an industrial perspective, Solid-State Laser Engineering discusses in detail the characteristics, design, construction, and performance of solid-state lasers. Emphasis is placed on engineering and practical considerations; phenomenological aspects using models are preferred to abstract mathematical derivations. Since its first edition almost 30 years ago this book has become the standard in the field of solid-state lasers for scientists,engineers and graduate students. This new edition has been extensively revised and updated to account for recent developments in the areas of diode-laser pumping, laser materials and nonlinear crystals. Completely new sections have been added dealing with frequency control, the theory of mode-locking, femto second lasers, high efficiency harmonic generation, passive and acousto-optic Q-switching, semiconductor saturable absorber mirrors (SESAM) and peridically poled nonlinear crystals.

  17. Synthesis and characterization of high quantum yield and oscillator strength 6-chloro-2-(4-cynophenyl)-4-phenyl quinoline (cl-CN-DPQ) organic phosphor for solid-state lighting. (United States)

    Ghate, Minakshi; Dahule, H K; Thejo Kalyani, N; Dhoble, S J


    A novel blue luminescent 6-chloro-2-(4-cynophenyl) substituted diphenyl quinoline (Cl-CN DPQ) organic phosphor has been synthesized by the acid-catalyzed Friedlander reaction and then characterized to confirm structural, optical and thermal properties. Structural properties of Cl-CN-DPQ were analyzed by Fourier transform infrared (FTIR), nuclear magnetic resonance (NMR) spectroscopy, X-ray diffraction technique (XRD) and scanning electron microscopy (SEM) and energy dispersive analysis of X-ray (EDAX) spectroscopy. FTIR spectra confirmed the presence of different functional groups and bond stretching. 1 H-NMR and 13 C-NMR confirmed the formation of an organic Cl-CN-DPQ compound. X-ray diffraction study provided its crystalline nature. The surface morphology of Cl-CN-DPQ was analyzed by SEM, while EDAX spectroscopy revealed the elemental analysis. Differential thermal analysis (TGA/DTA) disclosed its thermal stability up to 250°C. The optical properties of Cl-CN-DPQ were investigated by UV-vis absorption and photoluminescence (PL) measurements. Cl-CN-DPQ exhibits intense blue emission at 434 nm in a solid-state crystalline powder with CIE co-ordinates (0.157, 0.027), when excited at 373 nm. Cl-CN-DPQ shows remarkable Stokes shift in the range 14800-5100 cm-1 , which is the characteristic feature of intense light emission. A narrow full width at half-maximum (FWHM) value of PL spectra in the range 42-48 nm was observed. Oscillator strength, energy band gap, quantum yield, and fluorescence energy yield were also examined using UV-vis absorption and photoluminescence spectra. These results prove its applications towards developing organic luminescence devices and displays, organic phosphor-based solar cells and displays, organic lasers, chemical sensors and many more. Copyright © 2017 John Wiley & Sons, Ltd.

  18. Introduction to solid state electronics

    CERN Document Server

    Wang, FFY


    This textbook is specifically tailored for undergraduate engineering courses offered in the junior year, providing a thorough understanding of solid state electronics without relying on the prerequisites of quantum mechanics. In contrast to most solid state electronics texts currently available, with their generalized treatments of the same topics, this is the first text to focus exclusively and in meaningful detail on introductory material. The original text has already been in use for 10 years. In this new edition, additional problems have been added at the end of most chapters. These proble

  19. Solid state physics an introduction

    CERN Document Server

    Hofmann, Philip


    A must-have textbook for any undergraduate studying solid state physics. This successful brief course in solid state physics is now in its second edition. The clear and concise introduction not only describes all the basic phenomena and concepts, but also such advanced issues as magnetism and superconductivity. Each section starts with a gentle introduction, covering basic principles, progressing to a more advanced level in order to present a comprehensive overview of the subject. The book is providing qualitative discussions that help undergraduates understand concepts even if they can?t foll

  20. Solid state physics for metallurgists

    CERN Document Server

    Weiss, Richard J


    Metal Physics and Physical Metallurgy, Volume 6: Solid State Physics for Metallurgists provides an introduction to the basic understanding of the properties that make materials useful to mankind. This book discusses the electronic structure of matter, which is the domain of solid state physics.Organized into 12 chapters, this volume begins with an overview of the electronic structure of free atoms and the electronic structure of solids. This text then examines the basis of the Bloch theorem, which is the exact periodicity of the potential. Other chapters consider the fundamental assumption in

  1. Solid-state lithium battery (United States)

    Ihlefeld, Jon; Clem, Paul G; Edney, Cynthia; Ingersoll, David; Nagasubramanian, Ganesan; Fenton, Kyle Ross


    The present invention is directed to a higher power, thin film lithium-ion electrolyte on a metallic substrate, enabling mass-produced solid-state lithium batteries. High-temperature thermodynamic equilibrium processing enables co-firing of oxides and base metals, providing a means to integrate the crystalline, lithium-stable, fast lithium-ion conductor lanthanum lithium tantalate (La.sub.1/3-xLi.sub.3xTaO.sub.3) directly with a thin metal foil current collector appropriate for a lithium-free solid-state battery.

  2. Solid-state interactions between trimethoprim and parabens

    DEFF Research Database (Denmark)

    Pedersen, S.; Kristensen, H. G.; Cornett, Claus


    Solid-state interactions between trimethoprim and the esters of 4-hydroxybenzoic acid (parahydroxybenzoates or parabens) used for anti-microbial preservation are investigated. The formation of a crystalline 1/1 molecular compound between trimethoprim and methyl parahydroxybenzoate is demonstrated...... by differential scanning calorimetry, X-ray powder diffraction, Fourier transform infrared spectroscopy, and solid-state C-13-NMR. Interactions between trimethoprim and 4-hydroxybenzoic acid and its ethyl,propyl and butyl esters were not observed. The nature of the trimethoprim and methyl parahydroxybenzoate...

  3. Ionic self-assembled derivative of tetraphenylethylene: Synthesis, enhanced solid-state emission, liquid crystalline structure and Cu2+ detection ability. (United States)

    Ren, Xiang-Kui; Lu, Lin; Liu, Rui; Jiang, Xu-Qiang; Geng, Lai-Yao; Zheng, Jun-Feng; Feng, Yakai; Chen, Er-Qiang


    A novel tetraphenylethylene complex (ETTC-DOAB) with enhanced solid-state emission was designed and synthesized via ionic self-assembly (ISA) strategy. The aggregation-induced emission property, phase behavior, and supramolecular structure of the complex were characterized by a combination of variety experimental measurements. The experimental results reveal that the ISA complex could self-assemble into ordered helical supramolecular structure with enhanced luminescent property though the ETTC cores possess large conjugation and high rigidity. Due to the prolonged conjugation length, the fluorescence quantum yield of ETTC-DOAB is boosted to 66%. Moreover, it is demonstrated that the assemblies of the ISA complex could be an effective sensor for Cu2+. Owing to the disassembly modulation of ETTC-DOAB aggregations, the fluorescence emission of the assemblies can be selectively and sensitively quenched by Cu2+ with the detection limit as low as 12.6 nM. The enhanced emission efficiency, in combination with the liquid crystallinity and superior sensing performance to Cu2+, make the ETTC-DOAB complex a potential candidate for fabrication of luminescent device and chemosensor for Cu2+ detection. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Synthesis, structures of four coordination compounds constructed from o-methacrylamidobenzoic acid and their relationship between structure and solid state luminescence

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Hong-Xia; Ma, Yong; Zhou, Feng; Wu, Bing [Key Laboratory of Organic Synthesis of Jiangsu Province, School of Chemistry, Chemical Engineering and Materials Science, Soochow University(DuShuHu Campus), 199 Renai Road, Suzhou, 215123 (China); Key Laboratory of Energy-Saving And Environmental Protection Materials Test and Technical Service Center of Jiangsu Province, Soochow University (DuShuHu Campus), 199 Renai Road, Suzhou, 215123 (China); Xu, Qing-Feng, E-mail: [Key Laboratory of Organic Synthesis of Jiangsu Province, School of Chemistry, Chemical Engineering and Materials Science, Soochow University(DuShuHu Campus), 199 Renai Road, Suzhou, 215123 (China); Key Laboratory of Energy-Saving And Environmental Protection Materials Test and Technical Service Center of Jiangsu Province, Soochow University (DuShuHu Campus), 199 Renai Road, Suzhou, 215123 (China); Lu, Jian-Mei, E-mail: [Key Laboratory of Organic Synthesis of Jiangsu Province, School of Chemistry, Chemical Engineering and Materials Science, Soochow University(DuShuHu Campus), 199 Renai Road, Suzhou, 215123 (China); Key Laboratory of Energy-Saving And Environmental Protection Materials Test and Technical Service Center of Jiangsu Province, Soochow University (DuShuHu Campus), 199 Renai Road, Suzhou, 215123 (China); Ge, Jian-Feng [Key Laboratory of Organic Synthesis of Jiangsu Province, School of Chemistry, Chemical Engineering and Materials Science, Soochow University(DuShuHu Campus), 199 Renai Road, Suzhou, 215123 (China); Key Laboratory of Energy-Saving And Environmental Protection Materials Test and Technical Service Center of Jiangsu Province, Soochow University (DuShuHu Campus), 199 Renai Road, Suzhou, 215123 (China)


    Four new coordination compounds, namely, Zn(o-MAABA){sub 2}(Phen) (1), [Cd(o-MAABA){sub 2}·2H{sub 2}O]{sub 2} (2), ([Pb{sub 2}Cl{sub 2}(o-MAABA){sub 2}(Phen){sub 4}])·2H{sub 2}O (3·2H{sub 2}O), [Pb(NO{sub 3})(o-MAABA)(Phen)]{sub n} (4), where o-MAABA=o-methacrylamidobenzoic acid and phen=1, 10-phenanthroline, have been synthesized. All compounds were fully confirmed by FT-IR, elemental analysis and TGA analysis. Their structures were determined by single crystal X-ray diffraction, in which compound 1 shows a mononuclear structure, compounds 2 and 3 have binuclear structures and compound 4 shows an infinite chain. In 2 and 4, the adjacent chains are extended into a 3D supramolecular architecture via π–π interactions. Solid-state room temperature luminescence spectra revealed that emission bands of compound 1 were located at 524 nm (λ{sub ex}=352 nm) and compound 4 at 479 and 584 nm (λ{sub ex}=390 nm) assigned to the excimer formation. The emission at 454 nm (λ{sub ex}=340 nm) of compound 2 was mainly ascribed to the Ligand–Metal Charge Transfer (LMCT). - Graphical abstract: Four coordination compounds constructed by o-methacrylamidobenzoic, phenanthroline and metal ions are reported. The photoluminescent properties is studied, which is affected by the molecular stacking and LMCT.

  5. A novel double perovskite La2ZnTiO6:Eu3+ red phosphor for solid-state lighting: Synthesis and optimum luminescence (United States)

    Fu, Anjie; Guan, Anxiang; Gao, Fangfang; Zhang, Xiaoshan; Zhou, Liya; Meng, Yingbin; Pan, Haiman


    A novel red-emitting phosphor (La2ZnTiO6:Eu3+) was synthesized using a high-temperature solid-state method. Phase purity was examined by X-ray diffraction analysis. Results showed that the obtained La2ZnTiO6:Eu3+ phosphors crystallized in the monoclinic space group P121/n1(14). The photoluminescence spectrum under the excitation of 394 nm revealed two narrow bands at 594 and 616 nm, which correspond to the 5D0-7F1 and 5D0-7F2 transitions of Eu3+, respectively. The energy transfer mechanism among Eu3+ ions was identified as dipole-dipole interactions. The phosphor exhibited ideal chromaticity coordinate (0.66, 0.34), which is close to the standard red color coordinates (0.67, 0.33). The temperature-dependent PL spectra were analyzed, and the calculated activation energy Ea indicated the good thermal stability of the phosphor. The red-emitting light-emitting diodes (LED) fabricated by LZT:Eu3+ and 395 nm-emitting InGaN chip exhibited high brightness intensity. Hence, La2ZnTiO6:Eu3+ can be potentially applied to LEDs.

  6. Synthesis and Characterization of Far-Red/NIR-Fluorescent BODIPY Dyes, Solid-State Fluorescence, and Application as Fluorescent Tags Attached to Carbon Nano-onions. (United States)

    Bartelmess, Juergen; Baldrighi, Michele; Nardone, Valentina; Parisini, Emilio; Buck, David; Echegoyen, Luis; Giordani, Silvia


    A series of π-extended distyryl-substituted boron dipyrromethene (BODIPY) derivatives with intense far-red/near-infrared (NIR) fluorescence was synthesized and characterized, with a view to enhance the dye's performance for fluorescence labeling. An enhanced brightness was achieved by the introduction of two methyl substituents in the meso positions on the phenyl group of the BODIPY molecule; these substituents resulted in increased structural rigidity. Solid-state fluorescence was observed for one of the distyryl-substituted BODIPY derivatives. The introduction of a terminal bromo substituent allows for the subsequent immobilization of the BODIPY fluorophore on the surface of carbon nano-onions (CNOs), which leads to potential imaging agents for biological and biomedical applications. The far-red/NIR-fluorescent CNO nanoparticles were characterized by absorption, fluorescence, and Raman spectroscopies, as well as by thermogravimetric analysis, dynamic light scattering, high-resolution transmission electron microscopy, and confocal microscopy. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Solid state synthesis, structural, physicochemical and optical properties of an inter-molecular compound: 2-hydroxy-1, 2-diphenylethanone-4-nitro-o-phenylenediamine system (United States)

    Rai, U. S.; Singh, Manjeet; Rai, R. N.


    The phase diagram of 2-hydroxy-1, 2-diphenylethanone (HDPE)-4-nitro-o-phenylenediamine (NOPDA) system, determined by the thaw-melt method, gives two eutectics E1 (m p = 66.0 °C) and E2 (m p = 155.0 °C) with 0.30 and 0.55 mol fractions of NOPDA, respectively, and an 1:1 inter-molecular compound (IMC) (m p 162.0 °C). This IMC was synthesized by adopting the green synthetic method of solid state reaction. While its formation and structure were confirmed by the X-ray diffraction and spectroscopic methods, the ORTEP view gives mode of crystal packing, C‒H…O, C‒H…N, π-π stacking and the inter-molecular hydrogen bonding in the compound. The single crystal of the IMC shows 53% transmission and emits significantly higher dual fluorescence, and the band gap was computed to be 3.04 eV. The values of solubility of the IMC, measured in the temperature range 304-322 K, satisfy the mole fraction (X) and temperature equation: Xeq= 5.1324 × 10-7 e 0.01356T.

  8. Solid-state chemical synthesis of rod-like fluorine-doped β-Bi2O3 and their enhanced photocatalytic property under visible light (United States)

    Liang, Zhiting; Cao, Yali; Li, Yizhao; Xie, Jing; Guo, Nana; Jia, Dianzeng


    The pure β-Bi2O3 and fluorine-doped β-Bi2O3 rod-like microstructures were successfully prepared by a facile solid-state chemical reaction process. The composition, structure and morphology of the samples were determined by XRD, EDS, SEM, TEM, HRTEM, XPS and PL. Photocatalytic activities of all samples were investigated via the degradation of methyl orange (MO) under the irradiation of visible light. The fluorine-doped β-Bi2O3 rods exhibited higher photocatalytic activities than the pure β-Bi2O3 rod-like structures and commercial sample. The 82% MO can be degraded by the fluorine-doped β-Bi2O3 rods after irradiation for 2 h under visible light, which is 2-3 times higher than that of counterparts. The enhanced properties of the fluorine-doped samples attribute to their higher separation efficiency of electron-hole pairs and strong oxidation potential of valance band holes. The results show that the as-prepared rod-like fluorine-doped β-Bi2O3 materials are potential candidates for photocatalysts irradiated by visible light.

  9. Control of Solid-State Dye-Sensitized Solar Cell Performance by Block-Copolymer-Directed TiO2 Synthesis

    KAUST Repository

    Docampo, Pablo


    Hybrid dye-sensitized solar cells are typically composed of mesoporous titania (TiO2), light-harvesting dyes, and organic molecular hole-transporters. Correctly matching the electronic properties of the materials is critical to ensure efficient device operation. In this study, TiO 2 is synthesized in a welldefined morphological confinement that arises from the self-assembly of a diblock copolymer - poly(isoprene-b-ethylene oxide) (Pl-b-PEO). The crystallization environment, tuned by the inorganic (TiO2 mass) to organic (polymer) ratio, is shown to be a decisive factor in determining the distribution of sub-bandgap electronic states and the associated electronic function in solid-state dye-sensitized solar cells. Interestingly, the tuning of the sub-bandgap states does not appear to strongly influence the charge transport and recombination in the devices. However, increasing the depth and breadth of the density of sub-bandgap states correlates well with an increase in photocurrent generation, suggesting that a high density of these sub-bandgap states is critical for efficient photo-induced electron transfer and charge separation. © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Control of solid-state dye-sensitized solar cell performance by block-copolymer-directed TiO{sub 2} synthesis

    Energy Technology Data Exchange (ETDEWEB)

    Docampo, Pablo; Tiwana, Priti; Snaith, Henry J. [Department of Physics, Clarendon Laboratory, University of Oxford Oxford, OX1 3PU (United Kingdom); Guldin, Stefan; Huettner, Sven [Department of Physics, Cavendish Laboratories, University of Cambridge Cambridge, CB3 OHE (United Kingdom); Stefik, Morgan; Orilall, M.C.; Sai, Hiroaki; Wiesner, Ulrich [Department of Materials Science and Engineering, Cornell University Ithaca, NY 14853 (United States); Steiner, Ulrich [Department of Physics, Cavendish Laboratories, University of Cambridge Cambridge, CB3 OHE (United Kingdom); Freiburg Institute for Advanced Studies (FRIAS), Abert-Ludwigs-Universitaet Freiburg Albertstrasse 19, D-79104 Freiburg (Germany)


    Hybrid dye-sensitized solar cells are typically composed of mesoporous titania (TiO{sub 2}), light-harvesting dyes, and organic molecular hole-transporters. Correctly matching the electronic properties of the materials is critical to ensure efficient device operation. In this study, TiO{sub 2} is synthesized in a well-defined morphological confinement that arises from the self-assembly of a diblock copolymer - poly(isoprene-b-ethylene oxide) (PI-b-PEO). The crystallization environment, tuned by the inorganic (TiO{sub 2} mass) to organic (polymer) ratio, is shown to be a decisive factor in determining the distribution of sub-bandgap electronic states and the associated electronic function in solid-state dye-sensitized solar cells. Interestingly, the tuning of the sub-bandgap states does not appear to strongly influence the charge transport and recombination in the devices. However, increasing the depth and breadth of the density of sub-bandgap states correlates well with an increase in photocurrent generation, suggesting that a high density of these sub-bandgap states is critical for efficient photo-induced electron transfer and charge separation. (Abstract Copyright [2010], Wiley Periodicals, Inc.)

  11. Solid State Reaction Synthesis of Si-HA as Potential Biomedical Material: An Endeavor to Enhance the Added Value of Indonesian Mineral Resources (United States)

    Hartatiek; Yudyanto; Ratnasari, S. D.; Windari, R. Y.; Hidayat, N.


    In recent years, one of the most prominently investigated materials is hydroxyapatite (HA). It is because of its excellent properties for medical applications, essentially related to orthopedic. Also, the introduction of other materials to HA becomes another research focus of many leading scientists. In this present study, silicon with various concentrations was introduced, by means of solid state reaction route, to HA forming Si-HA. The crystal structure properties of the as-prepared samples were evaluated by X-ray diffractometer (XRD). Fourier Transform Infra Red (FTIR) spectroscopy data collection and analysis were done to investigate the functional groups within the samples. The microstructural characteristics as well as elemental mapping of the samples were captured by scanning electron microscopy and energy dispersive x-ray spectroscopy (SEM-EDX). Vickers hardness test was also conducted to investigate the hardness properties of the samples. Furthermore, in vitro characterization-based bio resorbability of the samples in a simulated body fluid were also described. This study revealed that Indonesian limestone can be utilized as the raw material for synthesizing HA. The silicon has been successfully incorporated into phosphate site of the HA crystal. Conclusively, the Si-HA reported in this study shows good bioresorbability characteristic.

  12. Synthesis and Characterization of Ce-Doped Y3Al5O12 (YAG:Ce Nanopowders Used for Solid-State Lighting

    Directory of Open Access Journals (Sweden)

    Do Ngoc Chung


    Full Text Available Nano-Ce-doped Y3Al5O12 (YAG:Ce powders were synthesized by using a sol-gel low temperature combustion method, followed by thermal annealing. The annealing temperature for enriching nanoparticles was optimized and found to be 1000°C. The process for enriching uniform nanoparticles of YAG:Ce powder was carried out by using the nanosteam technique (NST. The nanoparticles obtained from this NST treatment had a size in the range of 9–20 nm. Measurements of the photoluminescence spectra of the dispersed YAG:Ce nanoparticles solutions showed a blue shift in the photoemission with a value of ca. 10 nm in the green region. WLEDs made from the blue LED chip coated with the nano-YAG:Ce + MEH-PPV composite epoxy exhibit white light with a broad band luminescent spectrum and a high color rending index (CRI. The photoluminescence spectra of the YAG:Ce nanoparticles showed a potential application of the prepared nanostructured YAG:Ce phosphor not only in energy-efficient solid-state lighting, but also in optoelectronic devices, including organic composite solar cells. In addition, it is suggested that NST can be applied for the enrichment of uniform inorganic nanoparticles.

  13. Solid-state nuclear magnetic resonance (NMR) spectroscopy of human immunodeficiency virus gp41 protein that includes the fusion peptide: NMR detection of recombinant Fgp41 in inclusion bodies in whole bacterial cells and structural characterization of purified and membrane-associated Fgp41. (United States)

    Vogel, Erica P; Curtis-Fisk, Jaime; Young, Kaitlin M; Weliky, David P


    Human immunodeficiency virus (HIV) infection of a host cell begins with fusion of the HIV and host cell membranes and is mediated by the gp41 protein, a single-pass integral membrane protein of HIV. The 175 N-terminal residues make up the ectodomain that lies outside the virus. This work describes the production and characterization of an ectodomain construct containing the 154 N-terminal gp41 residues, including the fusion peptide (FP) that binds to target cell membranes. The Fgp41 sequence was derived from one of the African clade A strains of HIV-1 that have been less studied than European/North American clade B strains. Fgp41 expression at a level of ~100 mg/L of culture was evidenced by an approach that included amino acid type (13)CO and (15)N labeling of recombinant protein and solid-state NMR (SSNMR) spectroscopy of lyophilized whole cells. The approach did not require any protein solubilization or purification and may be a general approach for detection of recombinant protein. The purified Fgp41 yield was ~5 mg/L of culture. SSNMR spectra of membrane-associated Fgp41 showed high helicity for the residues C-terminal of the FP. This was consistent with a "six-helix bundle" (SHB) structure that is the final gp41 state during membrane fusion. This observation and negligible Fgp41-induced vesicle fusion supported a function for SHB gp41 of membrane stabilization and fusion arrest. SSNMR spectra of residues in the membrane-associated FP provided evidence of a mixture of molecular populations with either helical or β-sheet FP conformation. These and earlier SSNMR data strongly support the existence of these populations in the SHB state of membrane-associated gp41. © 2011 American Chemical Society

  14. Four Thermochromic o-Hydroxy Schiff Bases of α-Aminodiphenylmethane: Solution and Solid State Study

    Directory of Open Access Journals (Sweden)

    Marija Zbačnik


    Full Text Available More than a hundred years after the first studies of the photo- and thermochromism of o-hydroxy Schiff bases (imines, it is still an intriguing topic that fascinates several research groups around the world. The reasons for such behavior are still under investigation, and this work is a part of it. We report the solution-based and mechanochemical synthesis of four o-hydroxy imines derived from α-aminodiphenylmethane. The thermochromic properties were studied for the single crystal and polycrystalline samples of the imines. The supramolecular impact on the keto-enol tautomerism in the solid state was studied using SCXRD and NMR, while NMR spectroscopy was used for the solution state. All four imines are thermochromic, although the color changes of the single crystals are not as strong as of the polycrystalline samples. One of the imines shows negative thermochromism, and that one is in keto-amine tautomeric form, both in the solid state as in solution.

  15. Solid State and Materials Chemistry

    Indian Academy of Sciences (India)


    It gives us immense pleasure to present this Special Issue of the Proceedings of the Indian. Academy of Sciences (Chemical Sciences) to mark the Silver Jubilee of the Solid State and Structural Chemistry Unit (SSCU), Indian Institute of Science, Bangalore. This Unit was created by Professor C N R Rao, FRS, at the Institute ...

  16. Solid-State Method Synthesis of SnO2-Decorated g-C3N4 Nanocomposites with Enhanced Gas-Sensing Property to Ethanol (United States)

    Cao, Jianliang; Qin, Cong; Wang, Yan; Zhang, Huoli; Sun, Guang; Zhang, Zhanying


    SnO2/graphitic carbon nitride (g-C3N4) composites were synthesized via a facile solid-state method by using SnCl4·5H2O and urea as the precursor. The structure and morphology of the as-synthesized composites were characterized by the techniques of X-ray diffraction (XRD), field-emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), energy dispersive spectrometer (EDS), thermogravimetry-differential thermal analysis (TG-DTA), X-ray photoelectron spectroscopy (XPS), and N2 sorption. The results indicated that the composites possessed a two-dimensional (2-D) structure, and the SnO2 nanoparticles were highly dispersed on the surface of the g-C3N4 nanosheets. The gas-sensing performance of the samples to ethanol was tested, and the SnO2/g-C3N4 nanocomposite-based sensor exhibited admirable properties. The response value (Ra/Rg) of the SnO2/g-C3N4 nanocomposite with 10 wt % 2-D g-C3N4 content-based sensor to 500 ppm of ethanol was 550 at 300 °C. However, the response value of pure SnO2 was only 320. The high surface area of SnO2/g-C3N4-10 (140 m2·g−1) and the interaction between 2-D g-C3N4 and SnO2 could strongly affect the gas-sensing property. PMID:28772960

  17. Solid-state characterization of the HIV protease inhibitor

    CERN Document Server

    Kim, Y A


    The LB71350, (3S, 4R)-Epoxy-(5S)-[[N-(1-methylethoxy) carbonyl]-3-(methylsulfonyl)-L-valinyl]amin= o]-N-[2-methyl-(1R)-[(phenyl)carbonyl]propyl-6-phenylhexanamide, is a novel HIV protease inhibitor. Its equilibrium solubility at room temperature was less than 40 mu g/mL. It was speculated that the low aqueous solubility might be due to the high crystalline lattice energy resulting from intermolecular hydrogen bonds. The present study was carried out to learn the solid-state characteristics of LB71350 using analytical methods such as NMR, FT-IR and XRD. sup 1 sup 3 C Solid-state NMR, solution NMR, and FT-IR spectra of the various solid forms of LB71350 were used to identify the conformation and structure of the solid forms. The chemical shifts of sup 1 sup 3 C solid-state NMR spectra suggest that the crystalline form might have 3 intermolecular hydrogen bondings between monomers.

  18. Synthesis and structural stability of Cr-doped Li2MnSiO4/C cathode materials by solid-state method (United States)

    Cheng, Hong-Mei; Zhao, Shi-Xi; Wu, Xia; Zhao, Jian-Wei; Wei, Lei; Nan, Ce-Wen


    The crystal structure of the Li2MnSiO4 cathode material would collapse during the charge and discharge process because of that the Mn-O coordination polyhedron changed from [MnO4] into [MnO6] in the process of Mn+2 to Mn+4, but the Cr element could remain [CrO4] crystal ligand from Cr+2 to Cr+4, so Cr element substitution was used to improve the structural stability of the Li2MnSiO4 cathode material. In this work, Li2Mn1-xCrxSiO4/C nanocomposites were synthesized by solid-state method. XRD, SEM and TEM observations show that the as-prepared Li2Mn1-xCrxSiO4/C materials presents an orthorhombic crystal structure (S.G. Pmn21), the particle size of Li2Mn1-xCrxSiO4/C powder ranges from 50 to 100 nm. The XRD and XPS results indicate that Cr+2 is successfully doped into Li2MnSiO4 lattice and has well compatibility with Li2MnSiO4. The electrochemical results display that Li2Mn92.5%Cr7.5%SiO4/C exhibits significantly enhanced cycle stability and discharge capability. The initial discharge capacity of the Li2Mn92.5%Cr7.5%SiO4/C sample is 255 mAh g-1, and the discharge capacity was still about 60 mAh g-1 after 50 cycles. Furthermore, the XRD patterns, TEM images and Raman analysis reveal that the Cr doping enhances the structural stability of Li2Mn1-xCrxSiO4/C and improves the electrochemical activity of the cathode. Thus, the Li2Mn92.5%Cr7.5%SiO4/C have shown potential applications for lithium ion batteries.

  19. Advances in Solid State Physics

    CERN Document Server

    Haug, Rolf


    The present volume 46 of Advances in Solid State Physics contains the written versions of selected invited lectures from the spring meeting of the Arbeitskreis Festkörperphysik of the Deutsche Physikalische Gesellschaft which was held from 27 to 31 March 2006 in Dresden, Germany. Many topical talks given at the numerous symposia are included. Most of these were organized collaboratively by several of the divisions of the Arbeitskreis. The topis range from zero-dimensional physics in quantum dots, molecules and nanoparticles over one-dimensional physics in nanowires and 1d systems to more applied subjects like optoelectronics and materials science in thin films. The contributions span the whole width of solid-state physics from truly basic science to applications.

  20. Solid-state laser engineering

    CERN Document Server

    Koechner, Walter


    This book is written from an industrial perspective and provides a detailed discussion of solid-state lasers, their characteristics, design and construction. Emphasis is placed on engineering and practical considerations. The book is aimed mainly at the practicing scientist or engineer who is interested in the design or use of solid-state lasers, but the comprehensive treatment of the subject will make the work useful also to students of laser physics who seek to supplement their theoretical knowledge with engineering information. In order to present the subject as clearly as possible, phenomenological descriptions using models have been used rather than abstract mathematical descriptions. This results in a simplified presentation. The descriptions are enhanced by the inclusion of numerical and technical data, tables and graphs. This new edition has been updated and revised to take account of important new developments, concepts, and technologies that have emerged since the publication of the first and second...

  1. Solid-state membrane module (United States)

    Gordon, John Howard [Salt Lake City, UT; Taylor, Dale M [Murray, UT


    Solid-state membrane modules comprising at least one membrane unit, where the membrane unit has a dense mixed conducting oxide layer, and at least one conduit or manifold wherein the conduit or manifold comprises a dense layer and at least one of a porous layer and a slotted layer contiguous with the dense layer. The solid-state membrane modules may be used to carry out a variety of processes including the separating of any ionizable component from a feedstream wherein such ionizable component is capable of being transported through a dense mixed conducting oxide layer of the membrane units making up the membrane modules. For ease of construction, the membrane units may be planar.

  2. One-step synthesis of vertically aligned anatase thornbush-like TiO2 nanowire arrays on transparent conducting oxides for solid-state dye-sensitized solar cells. (United States)

    Roh, Dong Kyu; Chi, Won Seok; Ahn, Sung Hoon; Jeon, Harim; Kim, Jong Hak


    Herein, we report a facile synthesis of high-density anatase-phase vertically aligned thornbush-like TiO2 nanowires (TBWs) on transparent conducting oxide glasses. Morphologically controllable TBW arrays of 9 μm in length are generated through a one-step hydrothermal reaction at 200 °C over 11 h using potassium titanium oxide oxalate dehydrate, diethylene glycol (DEG), and water. The TBWs consist of a large number of nanoplates or nanorods, as confirmed by SEM and TEM imaging. The morphologies of TBWs are controllable by adjusting DEG/water ratios. TBW diameters gradually decrease from 600 (TBW600) to 400 (TBW400) to 200 nm (TBW200) and morphologies change from nanoplates to nanorods with an increase in DEG content. TBWs are utilized as photoanodes for quasi-solid-state dye-sensitized solar cells (qssDSSCs) and solid-state DSSCs (ssDSSCs). The energy-conversion efficiency of qssDSSCs is in the order: TBW200 (5.2%)>TBW400 (4.5%)>TBW600 (3.4%). These results can be attributed to the different surface areas, light-scattering effects, and charge transport rates, as confirmed by dye-loading measurements, reflectance spectroscopy, and incident photon-to-electron conversion efficiency and intensity-modulated photovoltage spectroscopy/intensity-modulated photocurrent spectroscopy analyses. TBW200 is further treated with a graft-copolymer-directed organized mesoporous TiO2 to increase the surface area and interconnectivity of TBWs. As a result, the energy-conversion efficiency of the ssDSSC increases to 6.7% at 100 mW cm(-2) , which is among the highest values for N719-dye-based ssDSSCs. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Solid-State Nuclear Power (United States)

    George, Jeffrey A.


    A strategy for "Solid-State" Nuclear Power is proposed to guide development of technologies and systems into the second 50 years of nuclear spaceflight. The strategy emphasizes a simple and highly integrated system architecture with few moving parts or fluid loops; the leverage of modern advances in materials, manufacturing, semiconductors, microelectromechanical and nanotechnology devices; and the targeted advancement of high temperature nuclear fuels, materials and static power conversion to enable high performance from simple system topologies.

  4. Advances in Solid State Physics

    CERN Document Server

    Haug, Rolf


    The present volume 47 of the Advances in Solid State Physics contains the written version of a large number of the invited talks of the 2007 Spring Meeting of the Arbeitskreis Festkörperphysik which was held in Regensburg, Germany, from March 26 to 30, 2007 in conjunction with the 71st Annual Meeting of the Deutsche Physikalische Gesellschaft.It gives an overview of the present status of solid state physics where low-dimensional systems such as quantum dots and quantum wires are dominating. The importance of magnetic materials is reflected by the large number of contributions in the part dealing with ferromagnetic films and particles. One of the most exciting achievements of the last couple of years is the successful application of electrical contacts to and the investigation of single layers of graphene. This exciting physics is covered in Part IV of this book. Terahertz physics is another rapidly moving field which is presented here by five contributions. Achievements in solid state physics are only rarely...

  5. Synthesis, IR and NMR spectral correlations in some symmetrical ...

    African Journals Online (AJOL)

    A series of diimines have been synthesized by coupling of diamine with substituted benzaldehydes. The purities of these diimines were checked by their analytical and spectroscopic data. The spectral frequencies νCN (cm-1), NMR chemical shifts (δ, ppm) of C-H and C=N of these diimines have been correlated with ...

  6. Multinuclear solid-state nuclear magnetic resonance of inorganic materials

    CERN Document Server

    MacKenzie, Kenneth J D


    Techniques of solid state nuclear magnetic resonance (NMR) spectroscopy are constantly being extended to a more diverse range of materials, pressing into service an ever-expanding range of nuclides including some previously considered too intractable to provide usable results. At the same time, new developments in both hardware and software are being introduced and refined. This book covers the most important of these new developments. With sections addressed to non-specialist researchers (providing accessible answers to the most common questions about the theory and practice of NMR asked by novices) as well as a more specialised and up-to-date treatment of the most important areas of inorganic materials research to which NMR has application, this book should be useful to NMR users whatever their level of expertise and whatever inorganic materials they wish to study.

  7. A Novel Solid State Ultracapacitor (United States)

    Cortes-Pena, A. Y.; Rolin, T. D.; Hill, C. W.


    Novel dielectric materials were researched to develop an internal barrier layer capacitor that is fully solid state. These materials included reduced nanoparticles of barium titanate that were coated with various atomic layer deposited oxides. The nanoparticle powders were then densified into pellets and characterized using a dielectric test fixture over a frequency range of 20 Hz to 2 MHz. Densification and sintering were evaluated using scanning electron microscopic techniques. Ultimately, the samples showing the most promising electrical characteristics of permittivity, dissipation factor and equivalent series resistance were chosen to manufacture devices for subsequent testing.

  8. Solid-state quantum metamaterials (United States)

    Wilson, Richard; Everitt, Mark; Saveliev, Sergey; Zagoskin, Alexandre


    Quantum metamaterials provide a promising potential test bed for probing the quantum-classical transition. We propose a scalable and feasible architecture for a solid-state quantum metamaterial. This consists of an ensemble of superconducting flux qubits inductively coupled to a superconducting transmission line. We make use of fully quantum mechanical models which account for decoherence, input and readout to study the behaviour of prototypical 1D and 2D quantum metamaterials. In addition to demonstrating some of the novel phenomena that arise in these systems, such as ``quantum birefringence,'' we will also discuss potential applications.

  9. The Oxford solid state basics

    CERN Document Server

    Simon, Steven H


    The study of solids is one of the richest, most exciting, and most successful branches of physics. While the subject of solid state physics is often viewed as dry and tedious this new book presents the topic instead as an exciting exposition of fundamental principles and great intellectual breakthroughs. Beginning with a discussion of how the study of heat capacity of solids ushered in the quantum revolution, the author presents the key ideas of the field while emphasizing the deepunderlying concepts. The book begins with a discussion of the Einstein/Debye model of specific heat, and the Drude

  10. Solid State Theory An Introduction

    CERN Document Server

    Rössler, Ulrich


    Solid-State Theory - An Introduction is a textbook for graduate students of physics and material sciences. It stands in the tradition of older textbooks on this subject but takes up new developments in theoretical concepts and materials which are connected with such path breaking discoveries as the Quantum-Hall Effects, the high-Tc superconductors, and the low-dimensional systems realized in solids. Thus besides providing the fundamental concepts to describe the physics of electrons and ions of which the solid consists, including their interactions and the interaction with light, the book casts a bridge to the experimental facts and opens the view into current research fields.

  11. Solid State Li-ion Batteries (United States)


    like FeS2 (8, 9), FeS (10), nano-Si (11- 13), Li4Ti5O12 (14-17), graphite (18, 19), Li4.4GexSi1-x (20), α- Fe2O3 (21) and Sn-based glasses like SnO...Br2O3 (22) or SnS-P2S5 (23). FeS2, FeS, L4Ti5O12, α- Fe2O3 , and Sn-based glasses all have average operating voltages that are too high to make them useful...Solid State Ionics, 158, 269 (2003). 19. Y. Seino, K. Takada, B.-C. Kim, L. Zhang, N. Ohta, H. Wada, M. Osada and T. Sasaki, “ Synthesis of

  12. On the Floquet–Magnus expansion: Applications in solid-state nuclear magnetic resonance and physics

    Energy Technology Data Exchange (ETDEWEB)

    Mananga, Eugene Stephane, E-mail: [Harvard Medical School and Massachusetts General Hospital, Center for Advanced Medical Imaging Sciences, Division of Nuclear Medicine and Molecular Imaging Physics, Department of Radiology, 55 Fruit Street, Boston, Massachusetts 02114 (United States); Charpentier, Thibault, E-mail: [Commissariat à l’Energie Atomique, IRAMIS, Service interdisciplinaire sur les systèmes moléculaires et matériaux, CEA/CNRS UMR 3299, 91191, Gif-sur-Yvette (France)


    Theoretical approaches are useful and powerful tools for more accurate and efficient spin dynamics simulation to understand experiments and devising new RF pulse sequence in nuclear magnetic resonance. Solid-state NMR is definitely a timely topic or area of research, and not many papers on the respective theories are available in the literature of nuclear magnetic resonance or physics reports. This report presents the power and the salient features of the promising theoretical approach called Floquet–Magnus expansion that is helpful to describe the time evolution of the spin system at all times in nuclear magnetic resonance. The report presents a broad view of algorithms of spin dynamics, based on promising and useful theory of Floquet–Magnus expansion. This theory provides procedures to control and describe the spin dynamics in solid-state NMR. Major applications of the Floquet–Magnus expansion are illustrated by simple solid-state NMR and physical applications such as in nuclear, atomic, molecular physics, and quantum mechanics, NMR, quantum field theory and high energy physics, electromagnetism, optics, general relativity, search of periodic orbits, and geometric control of mechanical systems. The aim of this report is to bring to the attention of the spin dynamics community, the bridge that exists between solid-state NMR and other related fields of physics and applied mathematics. This review article also discusses future potential theoretical directions in solid-state NMR.

  13. Contamination and solid state welds.

    Energy Technology Data Exchange (ETDEWEB)

    Mills, Bernice E.


    Since sensitivity to contamination is one of the verities of solid state joining, there is a need for assessing contamination of the part(s) to be joined, preferably nondestructively while it can be remedied. As the surfaces that are joined in pinch welds are inaccessible and thus provide a greater challenge, most of the discussion is of the search for the origin and effect of contamination on pinch welding and ways to detect and mitigate it. An example of contamination and the investigation and remediation of such a system is presented. Suggestions are made for techniques for nondestructive evaluation of contamination of surfaces for other solid state welds as well as for pinch welds. Surfaces that have good visual access are amenable to inspection by diffuse reflection infrared Fourier transform (DRIFT) spectroscopy. Although other techniques are useful for specific classes of contaminants (such as hydrocarbons), DRIFT can be used most classes of contaminants. Surfaces such as the interior of open tubes or stems that are to be pinch welded can be inspected using infrared reflection spectroscopy. It must be demonstrated whether or not this tool can detect graphite based contamination, which has been seen in stems. For tubes with one closed end, the technique that should be investigated is emission infrared spectroscopy.

  14. Solid-state proton conductors

    Energy Technology Data Exchange (ETDEWEB)

    Jewulski, J.R.; Osif, T.L.; Remick, R.J.


    The purpose of this program was to survey the field of solid-state proton conductors (SSPC), identify conductors that could be used to develop solid-state fuel cells suitable for use with coal derived fuel gases, and begin the experimental research required for the development of these fuel cells. This document covers the following topics: the history of developments and current status of the SSPC, including a review of proton conducting electrolyte structures, the current status of the medium temperature SSPC development, electrodes for moderate temperature (SSPC) fuel cell, basic material and measurement techniques applicable for SSPC development, modeling and optimization studies. Correlation and optimization studies, to include correlation studies on proton conduction and oxide cathode optimization for the SSPC fuel cell. Experiments with the SSPC fuel cells including the fabrication of the electrolyte disks, apparatus for conducting measurements, the strontium-cerium based electrolyte, the barium-cerium based electrolyte with solid foil electrodes, the barium-cerium based electrolyte with porous electrodes, and conduction mechanisms. 164 refs., 27 figs., 13 tabs.

  15. Advances in Solid State Physics

    CERN Document Server

    Haug, Rolf


    The present volume 48 of the Advances in Solid State Physics contains the written version of a large number of the invited talks of the 2008 Spring Meeting of the DPG section Condensed Matter Physics (Sektion kondensierte Materie der DPG) which was held in Berlin, Germany, and gives a nice overview of the present status of condensed matter physics. Low-dimensional systems are dominating the field and especially nanowires and quantum dots. In recent years one learned how to produce nanowires directly during a growth process. Therefore, a number of articles is related to such nanowires. In nanoparticles and quantum dots, the dimensionality is further reduced and we learn more and more how to produce such systems in a defined way and what effects result from the confinement in all three dimensions. Spin effects and magnetism is another important field of present-day research in solid state physics. The third chapter covers this physics. The growing interest into organic materials and biological systems is reflec...

  16. Solid state reaction synthesis and optical spectroscopy of ferroelectric (Gd{sub 1-x}Ln{sub x}){sub 2}(MoO{sub 4}){sub 3}; with Ln = Yb or Tm

    Energy Technology Data Exchange (ETDEWEB)

    Lin Zhoubin; Han Xiumei [Instituto de Ciencia de Materiales de Madrid, Consejo Superior de Investigaciones Cientificas, c/Sor Juana Ines de la Cruz 3, 28049 Madrid (Spain); Zaldo, Carlos, E-mail: cezaldo@icmm.csic.e [Instituto de Ciencia de Materiales de Madrid, Consejo Superior de Investigaciones Cientificas, c/Sor Juana Ines de la Cruz 3, 28049 Madrid (Spain)


    A solid state synthesis route was used to prepare (Gd{sub 1-x}Ln{sub x}){sub 2}(MoO{sub 4}){sub 3}, Ln = Yb or Tm, compounds with ferroelectric Pba2 crystal structure. It has been observed that this phase is the only one crystallized during 1123 K annealing for x {<=} 0.12 for Yb and x {<=} 0.3 for Tm. Above these concentration limits the simultaneous formation of trihydrated Ln{sub 2}(MoO{sub 4}){sub 3}, Ln = Yb or Tm, is observed. Up to these concentrations Yb and Tm incorporations do not degrade the SHG efficiency. The position of Yb{sup 3+} and Tm{sup 3+} energy levels involved in laser emission processes were determined by 5 K spectroscopy. The 300 K pumping and emission spectral distributions and excited level lifetime have been determined with the purpose of future applications as self-activated periodically poled ferroelectric laser and non-linear media.

  17. Solid State Division: Progress report for period ending September 30, 1987

    Energy Technology Data Exchange (ETDEWEB)

    Green, P.H.; Watson, D.M. (eds.)


    This paper contains a collection of articles on research done at the Solid State Division of ORNL. General topics covered are: theoretical solid state physics; neutron scattering; physical properties of superconductors and ceramics; synthesis and characterization of solids; ion beam and laser processing; and surface and defect studies. (LSP)

  18. Solid State Lighting Program (Falcon)

    Energy Technology Data Exchange (ETDEWEB)

    Meeks, Steven


    Over the past two years, KLA-Tencor and partners successfully developed and deployed software and hardware tools that increase product yield for High Brightness LED (HBLED) manufacturing and reduce product development and factory ramp times. This report summarizes our development effort and details of how the results of the Solid State Light Program (Falcon) have started to help HBLED manufacturers optimize process control by enabling them to flag and correct identified killer defect conditions at any point of origin in the process manufacturing flow. This constitutes a quantum leap in yield management over current practice. Current practice consists of die dispositioning which is just rejection of bad die at end of process based upon probe tests, loosely assisted by optical in-line monitoring for gross process deficiencies. For the first time, and as a result of our Solid State Lighting Program, our LED manufacturing partners have obtained the software and hardware tools that optimize individual process steps to control killer defects at the point in the processes where they originate. Products developed during our two year program enable optimized inspection strategies for many product lines to minimize cost and maximize yield. The Solid State Lighting Program was structured in three phases: i) the development of advanced imaging modes that achieve clear separation between LED defect types, improves signal to noise and scan rates, and minimizes nuisance defects for both front end and back end inspection tools, ii) the creation of defect source analysis (DSA) software that connect the defect maps from back-end and front-end HBLED manufacturing tools to permit the automatic overlay and traceability of defects between tools and process steps, suppress nuisance defects, and identify the origin of killer defects with process step and conditions, and iii) working with partners (Philips Lumileds) on product wafers, obtain a detailed statistical correlation of automated

  19. Solid state synthesis and sintering of monazite-type ceramics: application to minor actinides conditioning; Synthese par voie solide et frittage de ceramiques a structure monazite. Application au conditionnement des actinides mineurs

    Energy Technology Data Exchange (ETDEWEB)

    Bregiroux, D


    In the framework of the French law of 1991 concerning the nuclear waste management, several studies are undertaken to develop specific crystalline conditioning matrices. Monazite, a rare earth (TR{sup 3+}) orthophosphate with a general formula TR{sup 3+}PO{sub 4}, is a natural mineral containing significant amount of thorium and uranium. Monazite has been proposed as a host matrix for the minor actinides (Np, Am and Cm) specific conditioning, thanks to its high resistance to self irradiation and its low solubility. Its is now of prime importance to check the conservation of these properties on synthesized materials, which implies to master all the stages of the elaboration process, from the powder synthesis to the sintering of controlled microstructure pellets. This work can be divided into two main parts: The first part deals with the synthesis by high temperature solid state route of TR{sup 3+}PO{sub 4} powders (with TR{sup 3+} = La{sup 3+} to Gd{sup 3+}, Pu{sup 3+} and Am{sup 3+}). The chemical reactions occurring during the firing of starting reagents are described in the case of monazite with only one or several cations. From these results, a protocol of synthesis is described. The incorporation of tetravalent cations (Ce{sup 4+}, U{sup 4+}, Pu{sup 4+}) in the monazite structure was also studied. The second part of the present work deals with the elaboration of controlled density and microstructure monazite pellets and their related mechanical and thermal properties. The study of crushing and sintering is presented. For the first time, experimental results are confronted with theoretical models in order to deduce the densification and grain growth mechanisms. By the comprehension of the various physicochemical phenomena occurring during the various stages of the monazite pellets elaboration process (powder synthesis, crushing, sintering...), this work allowed the development of a protocol of elaboration of controlled microstructure monazite TR{sup 3+}PO{sub 4

  20. Inside Solid State Drives (SSDs)

    CERN Document Server

    Micheloni, Rino; Eshghi, Kam


    Solid State Drives (SSDs) are gaining momentum in enterprise and client applications, replacing Hard Disk Drives (HDDs) by offering higher performance and lower power. In the enterprise, developers of data center server and storage systems have seen CPU performance growing exponentially for the past two decades, while HDD performance has improved linearly for the same period. Additionally, multi-core CPU designs and virtualization have increased randomness of storage I/Os. These trends have shifted performance bottlenecks to enterprise storage systems. Business critical applications such as online transaction processing, financial data processing and database mining are increasingly limited by storage performance. In client applications, small mobile platforms are leaving little room for batteries while demanding long life out of them. Therefore, reducing both idle and active power consumption has become critical. Additionally, client storage systems are in need of significant performance improvement as well ...

  1. Modeling solid-state precipitation

    CERN Document Server

    Nebylov, AlexanderKozeschnik, Ernst


    Over recent decades, modeling and simulation of solid-state precipitation has attracted increased attention in academia and industry due to their important contributions in designing properties of advanced structural materials and in increasing productivity and decreasing costs for expensive alloying. In particular, precipitation of second phases is an important means for controlling the mechanical-technological properties of structural materials. However, profound physical modeling of precipitation is not a trivial task. This book introduces you to the classical methods of precipitation modeling and to recently-developed advanced, computationally-efficient techniques. If you're a research professional, academic, or student, you'll learn: nucleation theory, precipitate growth, calculation of interfacial energies. advanced techniques for technologically relevant multicomponent systems and complex thermo-mechanical treatments. numerical approaches using evolution equations and discrete particle size distribu...

  2. Solid-State Random Lasers

    CERN Document Server

    Noginov, Mikhail A


    Random lasers are the simplest sources of stimulated emission without cavity, with the feedback provided by scattering in a gain medium. First proposed in the late 60’s, random lasers have grown to a large research field. This book reviews the history and the state of the art of random lasers, provides an outline of the basic models describing their behavior, and describes the recent advances in the field. The major focus of the book is on solid-state random lasers. However, it also briefly describes random lasers based on liquid dyes with scatterers. The chapters of the book are almost independent of each other. So, the scientists or engineers interested in any particular aspect of random lasers can read directly the relevant section. Researchers entering the field of random lasers will find in the book an overview of the field of study. Scientists working in the field can use the book as a reference source.

  3. The effect of drug binding on specific sites in transmembrane helices 4 and 6 of the ABC exporter MsbA studied by DNP-enhanced solid-state NMR. (United States)

    Spadaccini, Roberta; Kaur, Hundeep; Becker-Baldus, Johanna; Glaubitz, Clemens


    MsbA, a homodimeric ABC exporter, translocates its native substrate lipid A as well as a range of smaller, amphiphilic substrates across the membrane. Magic angle sample spinning (MAS) NMR, in combination with dynamic nuclear polarization (DNP) for signal enhancement, has been used to probe two specific sites in transmembrane helices 4 and 6 of full length MsbA embedded in lipid bilayers. Significant chemical shift changes in both sites were observed in the vanadate-trapped state compared to apo state MsbA. The reduced spectral line width indicates a more confined conformational space upon trapping. In the presence of substrates Hoechst 33342 and daunorubicin, further chemical shift changes and line shape alterations mainly in TM6 in the vanadate trapped state were detected. These data illustrate the conformational response of MsbA towards the presence of drugs during the catalytic cycle. This article is part of a Special Issue entitled: Beyond the Structure-Function Horizon of Membrane Proteins edited by Ute Hellmich, Rupak Doshi and Benjamin McIlwain. Copyright © 2017 Elsevier B.V. All rights reserved.

  4. Solid State Ionics Advanced Materials for Emerging Technologies (United States)

    Chowdari, B. V. R.; Careem, M. A.; Dissanayake, M. A. K. L.; Rajapakse, R. M. G.; Seneviratne, V. A.


    Keynote lecture. Challenges and opportunities of solid state ionic devices / W. Weppner -- pt. I. Ionically conducting inorganic solids. Invited papers. Multinuclear NMR studies of mass transport of phosphoric acid in water / J. R. P. Jayakody ... [et al.]. Crystalline glassy and polymeric electrolytes: similarities and differences in ionic transport mechanisms / J.-L. Souquet. 30 years of NMR/NQR experiments in solid electrolytes / D. Brinkmann. Analysis of conductivity and NMR measurements in Li[symbol]La[symbol]TiO[symbol] fast Li[symbol] ionic conductor: evidence for correlated Li[symbol] motion / O. Bohnké ... [et al.]. Transport pathways for ions in disordered solids from bond valence mismatch landscapes / S. Adams. Proton conductivity in condensed phases of water: implications on linear and ball lightning / K. Tennakone -- Contributed papers. Proton transport in nanocrystalline bioceramic materials: an investigative study of synthetic bone with that of natural bone / H. Jena, B. Rambabu. Synthesis and properties of the nanostructured fast ionic conductor Li[symbol]La[symbol]TiO[symbol] / Q. N. Pham ... [et al.]. Hydrogen production: ceramic materials for high temperature water electrolysis / A. Hammou. Influence of the sintering temperature on pH sensor ability of Li[symbol]La[symbol]TiO[symbol]. Relationship between potentiometric and impedance spectroscopy measurements / Q. N. Pham ... [et al.]. Microstructure chracterization and ionic conductivity of nano-sized CeO[symbol]-Sm[symbol]O[symbol] system (x=0.05 - 0.2) prepared by combustion route / K. Singh, S. A. Acharya, S. S. Bhoga. Red soil in Northern Sri Lanka is a natural magnetic ceramic / K. Ahilan ... [et al.]. Neutron scattering of LiNiO[symbol] / K. Basar ... [et al.]. Preparation and properties of LiFePO[symbol] nanorods / L. Q. Mai ... [et al.]. Structural and electrochemical properties of monoclinic and othorhombic MoO[symbol] phases / O. M. Hussain ... [et al.]. Preparation of Zircon (Zr

  5. Crystal structure solid-state cross polarization magic angle spinning 13C NMR correlation in luminescent d10 metal-organic frameworks constructed with the 1,2-Bis(1,2,4-triazol-4-yl)ethane ligand. (United States)

    Habib, Hesham A; Hoffmann, Anke; Höppe, Henning A; Steinfeld, Gunther; Janiak, Christoph


    Hydrothermal reactions of 1,2-bis(1,2,4-triazol-4-yl)ethane (btre) with copper(II), zinc(II), and cadmium(II) salts have yielded the dinuclear complexes [Zn2Cl4(mu2-btre)2] (1) and [Zn2Br4(mu2-btre)2] (2), the one-dimensional coordination polymer infinity1[Zn(NCS)2(2-btre)] (3), the two-dimensional networks infinity2[Cu2(mu2-Cl)2(mu4-btre)] (4), infinity2[Cu2(mu2-Br)2(mu4-btre)] (5), and infinity2{[Cd6(mu3-OH)2(mu3-SO4)4(mu4-btre)3(H2O)6](SO4).6H2O} (6), and the three-dimensional frameworks infinity3{[Cu(mu4-btre)]ClO4.0.25H2O} (7), 3{[Zn(mu4-btre)(mu2-btre)](ClO4)2} (8), infinity3{[Cd(mu4-btre)(mu2-btre)](ClO4)2} (9), and infinity3[Cu2(mu2-CN)2(mu4-btre)] (10, 2-fold 3D interpenetrated framework). The copper-containing products 4, 5, 7, and 10 contain the metal in the +1 oxidation state, from a simultaneous redox and self-assembly reaction of the Cu(II) starting materials. The cyanide-containing framework 10 has captured the CN- ions from the oxidative btre decomposition. The perchlorate frameworks 7, 8, or 9 react in an aqueous NH4+PF6- solution with formation of the related PF6--containing frameworks. The differences in the metal-btre bridging mode (mu2-kappaN1:N1', mu2-kappaN1:N2 or mu4-kappaN1:N2:N1':N2') and the btre ligand symmetry can be correlated with different signal patterns in the 13C cross polarization magic angle spinning (CPMAS) NMR spectra. Compounds 2, 4, 5 and 7 to 10 exhibit fluorescence at 403-481 nm upon excitation at 270-373 nm which is not seen in the free btre ligand.

  6. High Energy Solid State Laser Research Facility (United States)

    Federal Laboratory Consortium — A suite of laboratories with advanced spectroscopic and laser equipment, this facility develops materials and techniques for advanced solid state high energy lasers....

  7. Solid State Division Progress Report for period ending March 31, 1986

    Energy Technology Data Exchange (ETDEWEB)

    Green, P.H.; Watson, D.M. (eds.)


    This report is divided into: theoretical solid-state physics, surface and near-surface properties of solids, defects in solids, transport properties of solids, neutron scattering, and synthesis and properties of novel materials. (DLC)

  8. Green Synthesis of Platinum Nanoparticles by Electroreduction of a K{sub 2}PtCl{sub 6} Solid-State Precursor and Its Electrocatalytic Effects on H{sub 2}O{sub 2} Reduction

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Kyungtae; Jin, Sungho; Chang, Seungcheol; Park, Deogsu [Pusan National Univ., Busan (Korea, Republic of)


    A new synthesis route for Pt nanoparticles by direct electrochemical reduction of a solid-state Pt ion precursor (K{sub 2}PtCl{sub 6}) is demonstrated. Solid K{sub 2}PtCl{sub 6}-supported polyethyleneimine (PEI) coatings on the surface of glassy carbon electrode were prepared by simple mixing of solid K{sub 2}PtCl{sub 6} into a 1.0% PEI solution. The potential cycling or a constant potential in a PBS (pH 7.4) medium were applied to reduce the solid K{sub 2}PtCl{sub 6} precursor. The reduction of Pt(IV) began at around -0.2 V and the reduction potential was ca. -0.4 V. A steady state current was achieved after 10 potential cycling scans, indicating that continuous formation of Pt nanoparticles by electrochemical reduction occurred for up to 10 cycles. After applying the reduction potential of -0.6 V for 300 s, Pt nanoparticles with diameters ranging from 0.02-0.5 μm were observed, with an even distribution over the entire glassy carbon electrode surface. Characteristics of the Pt nanoparticles, including their performance in electrochemical reduction of H{sub 2}O{sub 2} are examined. A distinct reduction peak observed at about -0.20 V was due to the electrocatalytic reduction of H{sub 2}O{sub 2} by Pt nanoparticles. From the calibration plot, the linear range for H{sub 2}O{sub 2} detection was 0.1-2.0 mM and the detection limit for H{sub 2}O{sub 2} was found to be 0.05 mM.

  9. Solid state radiative heat pump (United States)

    Berdahl, Paul H.


    A solid state radiative heat pump (10, 50, 70) operable at room temperature ( K.) utilizes a semiconductor having a gap energy in the range of 0.03-0.25 eV and operated reversibly to produce an excess or deficit of charge carriers as compared to thermal equilibrium. In one form of the invention (10, 70) an infrared semiconductor photodiode (21, 71) is used, with forward or reverse bias, to emit an excess or deficit of infrared radiation. In another form of the invention (50), a homogeneous semiconductor (51) is subjected to orthogonal magnetic and electric fields to emit an excess or deficit of infrared radiation. Three methods of enhancing transmission of radiation through the active surface of the semiconductor are disclosed. In one method, an anti-reflection layer (19) is coated into the active surface (13) of the semiconductor (11), the anti-reflection layer (19) having an index of refraction equal to the square root of that of the semiconductor (11). In the second method, a passive layer (75) is spaced from the active surface (73) of the semiconductor (71) by a submicron vacuum gap, the passive layer having an index of refractive equal to that of the semiconductor. In the third method, a coupler (91) with a paraboloid reflecting surface (92) is in contact with the active surface (13, 53) of the semiconductor (11, 51), the coupler having an index of refraction about the same as that of the semiconductor.


    Directory of Open Access Journals (Sweden)



    Full Text Available EthylendiammoniumSO4•SnBu2Cl2•1/4ethylendiammoniumCl2 (A, 2ethylendiammoniumSO4•SnBu2Cl2 (B and Cy2NH2SO4H•Cy2NH2SnBu2Cl3 (C complexes have been obtained on allowing ethylendiammoniumSO4 and Cy2NH2HSO4 to react respectively with SnBu2Cl2 in specific ratios. The molecular structures of these compounds have been determined on the basis of infrared and NMR data. The suggested structures are dimeric and tetrameric, the tin atom being hexacoordinated, the sulphate anions behaving as a monochelating ligand or non-coordinating and only involved in hydrogen bonds. The hydrogenosulfate is a non-sigma coordinating anion but only involved in hydrogen bonds of acetic acid type or NH…O bonds. The presence of dimeric [(SnBu2Cl32]2- in one of the structures is noteworthy. The key role of the cations involved in hydrogen bonds is outlined.

  11. 13 C solid-state NMR study of the 13 C-labeled peptide, (E)8 GGLGGQGAG(A)6 GGAGQGGYGG as a model for the local structure of Nephila clavipes dragline silk (MaSp1) before and after spinning. (United States)

    Yazawa, Koji; Yamaguchi, Erika; Knight, David; Asakura, Tetsuo


    We prepared the water soluble model peptide, (E)(8) GGLGGQGAG(A)(6) GGAGQGGYGG, to throw light on the local structure of spidroin 1 (MaSpl) protein in spider dragline silk of Nephila clavipes before and after spinning. Solution (13) C NMR showed that the conformation of the peptide in aqueous solution was essentially random coil. Solid-state NMR was used to follow conformation-dependent (13) C chemical shifts in (13) C selectively labeled versions of the peptide. The peptide lyophilized from an aqueous solution at neutral pH (hereafter referred to as "without acid treatment)"was used to mimic the state of the spidroin stored in the spider's silk gland while the peptide precipitated from the acidic solution ("with acid treatment") was used to simulate the role of acid treatment in inducing conformation change in the natural spinning process. In without acid treatment, the fraction of random coil conformation was lowest in the N-terminal region (residues 15-18) when compared with the C-terminus. The conformational change produced by the acid treatment occurred in the sequence, G(15) AG(A)(6) GGAG(27), interposed between pairs of Gly residues pairs, Gly(12,13), and Gly(29,30). The acid treated peptide showed a remarkable decrease in the fraction of random coil conformation from A(20) to A(23) in the poly-Ala region when compared with the peptide without acid treatment. These observations taken together suggest that the peptide can be used as a model for studying the localization of the conformation change in spider silk fibroin in the natural spinning and the role of acid treatment in this process. Copyright © 2011 Wiley Periodicals, Inc.

  12. Spying on the boron–boron triple bond using spin–spin coupling measured from 11B solid-state NMR spectroscopy† †Electronic supplementary information (ESI) available: Experimental and computational details. See DOI: 10.1039/c5sc00644a Click here for additional data file. (United States)

    Perras, Frédéric A.; Ewing, William C.; Dellermann, Theresa; Böhnke, Julian; Ullrich, Stefan; Schäfer, Thomas


    There is currently tremendous interest in the previously documented example of a stable species exhibiting a boron–boron triple bond (Science, 2012, 336, 1420). Notably, it has recently been stated using arguments based on force constants that this diboryne may not, in reality, feature a boron–boron triple bond. Here, we use advanced solid-state NMR and computational methodology in order to directly probe the orbitals involved in multiple boron–boron bonds experimentally via analysis of 11B–11B spin–spin (J) coupling constants. Computationally, the mechanism responsible for the boron–boron spin–spin coupling in these species is found to be analogous to that for the case of multiply-bonded carbon atoms. The trend in reduced J coupling constants for diborenes and a diboryne, measured experimentally, is in agreement with that known for alkenes and alkynes. This experimental probe of the electronic structure of the boron–boron multiple bond provides strong evidence supporting the originally proposed nature of the bonds in the diboryne and diborenes, and demonstrates that the orbitals involved in boron–boron bonding are equivalent to those well known to construct the multiple bonds between other second-row elements such as carbon and nitrogen. PMID:29142694

  13. Revealing the Local Proton Network through Three-Dimensional 13C/1H Double-Quantum/1H Single-Quantum and 1H Double-Quantum/13C/1H Single-Quantum Correlation Fast Magic-Angle Spinning Solid-State NMR Spectroscopy at Natural Abundance. (United States)

    Malon, Michal; Pandey, Manoj Kumar; Nishiyama, Yusuke


    1H double quantum (DQ)/1H single quantum (SQ) correlation solid-state NMR spectroscopy is widely used to obtain internuclear 1H-1H proximities, especially at fast magic-angle spinning (MAS) rate (>60 kHz). However, to date, 1H signals are not well-resolved because of intense 1H-1H homonuclear dipolar interactions even at the attainable maximum MAS frequencies of ∼100 kHz and/or under 1H-1H homonuclear dipolar decoupling irradiations. Here we introduce novel three-dimensional (3D) experiments to resolve the 1H DQ/1H SQ correlation peaks using the additional 13C dimension. Although the low natural abundance of 13C (1.1%) significantly reduces the sensitivities, the 1H indirect measurements alleviate this issue and make this experiment possible even in naturally abundant samples. The two different implementations of 13C/1H DQ/1H SQ correlations and 1H DQ/13C/1H SQ correlations are discussed and demonstrated using l-histidine·HCl·H2O at natural abundance to reveal the local 1H-1H networks near each 13C. In addition, the complete 1H resonance assignments are achieved from a single 3D 13C/1H DQ/1H SQ experiment. We have also demonstrated the applicability of our proposed method on a biologically relevant molecule, capsaicin.

  14. Synthesis and NMR Spectral Analysis of Amine Heterocycles: The Effect of Asymmetry on the [superscript 1]H and [superscript 13]C NMR Spectra of N,O-Acetals (United States)

    Saba, Shahrokh; Ciaccio, James A.; Espinal, Jennifer; Aman, Courtney E.


    The stereochemical investigation is conducted to give students the combined experience of chemical synthesis of amines and N-heterocycles and structural stereochemical analysis using NMR spectroscopy. Students are introduced to the concept of topicity-stereochemical relationships between ligands within a molecule by synthesizing N,O-acetals.

  15. Macroscopic modelling of solid-state fermentation

    NARCIS (Netherlands)

    Hoogschagen, M.J.


    Solid-state fermentation is different from the more well known process of liquid fermentation because no free flowing water is present. The technique is primarily used in Asia. Well-known products are the foods tempe, soy sauce and saké. In industrial solid-state fermentation, the substrate usually

  16. Nylon 6 polymerization in the solid state

    NARCIS (Netherlands)

    Gaymans, R.J.; Amirtharaj, John; Kamp, Henk


    The postcondensation of nylon 6 in the solid state was studied. The reactions were carried out on fine powder in a fluidized bed reactor in a stream of dry nitrogen in the temperature range 110-205°C and during 1-24 h. The solid-state polymerization (SSP) did not follow melt kinetics, but was found

  17. Solid-state polymeric dye lasers

    CERN Document Server

    Singh, S; Sridhar, G; Muthuswamy, V; Raja, K


    This paper presents a review of the organic solid-state polymer materials, which have become established as a new laser media. The photostability of these materials is discussed. Different types of solid-state lasers built around these materials are also reviewed.

  18. Quantum Computing in Solid State Systems

    CERN Document Server

    Ruggiero, B; Granata, C


    The aim of Quantum Computation in Solid State Systems is to report on recent theoretical and experimental results on the macroscopic quantum coherence of mesoscopic systems, as well as on solid state realization of qubits and quantum gates. Particular attention has been given to coherence effects in Josephson devices. Other solid state systems, including quantum dots, optical, ion, and spin devices which exhibit macroscopic quantum coherence are also discussed. Quantum Computation in Solid State Systems discusses experimental implementation of quantum computing and information processing devices, and in particular observations of quantum behavior in several solid state systems. On the theoretical side, the complementary expertise of the contributors provides models of the various structures in connection with the problem of minimizing decoherence.

  19. Solid State Reactor Final Report

    Energy Technology Data Exchange (ETDEWEB)

    Mays, G.T.


    The Solid State Reactor (SSR) is an advanced reactor concept designed to take advantage of Oak Ridge National Laboratory's (ORNL's) recently developed graphite foam that has enhanced heat transfer characteristics and excellent high-temperature mechanical properties, to provide an inherently safe, self-regulated, source of heat for power and other potential applications. This work was funded by the U.S. Department of Energy's Nuclear Energy Research Initiative (NERI) program (Project No. 99-064) from August 1999 through September 30, 2002. The initial concept of utilizing the graphite foam as a basis for developing an advanced reactor concept envisioned that a suite of reactor configurations and power levels could be developed for several different applications. The initial focus was looking at the reactor as a heat source that was scalable, independent of any heat removal/power conversion process. These applications might include conventional power generation, isotope production and destruction (actinides), and hydrogen production. Having conducted the initial research on the graphite foam and having performed the scoping parametric analyses from neutronics and thermal-hydraulic perspectives, it was necessary to focus on a particular application that would (1) demonstrate the viability of the overall concept and (2) require a reasonably structured design analysis process that would synthesize those important parameters that influence the concept the most as part of a feasible, working reactor system. Thus, the application targeted for this concept was supplying power for remote/harsh environments and a design that was easily deployable, simplistic from an operational standpoint, and utilized the new graphite foam. Specifically, a 500-kW(t) reactor concept was pursued that is naturally load following, inherently safe, optimized via neutronic studies to achieve near-zero reactivity change with burnup, and proliferation resistant. These four major areas

  20. Silicon solid state devices and radiation detection

    CERN Document Server

    Leroy, Claude


    This book addresses the fundamental principles of interaction between radiation and matter, the principles of working and the operation of particle detectors based on silicon solid state devices. It covers a broad scope with respect to the fields of application of radiation detectors based on silicon solid state devices from low to high energy physics experiments including in outer space and in the medical environment. This book covers stateof- the-art detection techniques in the use of radiation detectors based on silicon solid state devices and their readout electronics, including the latest developments on pixelated silicon radiation detector and their application.

  1. Solid-state devices and applications

    CERN Document Server

    Lewis, Rhys


    Solid-State Devices and Applications is an introduction to the solid-state theory and its devices and applications. The book also presents a summary of all major solid-state devices available, their theory, manufacture, and main applications. The text is divided into three sections. The first part deals with the semiconductor theory and discusses the fundamentals of semiconductors; the kinds of diodes and techniques in their manufacture; the types and modes of operation of bipolar transistors; and the basic principles of unipolar transistors and their difference with bipolar transistors. The s


    Directory of Open Access Journals (Sweden)

    Sutopo Hadi


    Full Text Available he synthesis of two stable platinum(IV complexes containing methoxo ligand, [Pt(CH32(OCH3(OHpy2] (1 and fac-[Pt(CH32(OCH3(H2O3] (2, has been successfully performed. Complex 1 was prepared by oxidative addition reaction of cis-[Pt(CH32py2] with dry methanol, and a subsequent reaction of 1 with 70 % HClO4 in water produced the platinum complex 2. The stability of complex 2 in acidic aqueous solution was investigated and monitored with 1H and 195Pt NMR. The platinum complex 2 was found to be quite stable toward hydrolysis and no -hydride elimination was observed. Keywords: Methoxoplatinum(IV, NMR, complex stability, hydrolysis

  3. Diamond Deposition and Defect Chemistry Studied via Solid State NMR (United States)


    NAME(S) AND AOORESS(ES) 10. SPONSORING; MONITORING Max N. Yoder, ONR-3140, Room 607 AGENCY REPORT NUMBER ___ Department of the Navy Office of Naval...1985) 750. (1980) 60. 42 H. Rosenberger, G. Scheler and E. Kunstner, Fuel, 67 (1988) 508. 24 W. F. Banholzer and T. R. Anthony, Thin Solid Films, in the

  4. Solid State NMR Characterization and Adsorption Properties of ...

    African Journals Online (AJOL)


    Properties of Lignocellulose-Clinoptilolite Composites. Prepared with Siloxanes ... bDeparment of Chemistry and Polymer Science, University of Stellenbosch, Private Bag X1, Matieland, 7602, Stellenbosch, South Africa. cDeparment of ... mechanical, optical, electrical and thermal properties compared to those of the starting ...

  5. Solid State NMR Characterization and Adsorption Properties of ...

    African Journals Online (AJOL)

    This study reports the preparation of lignocellulose-clinoptilolite composites by means of N-terminated siloxanes as coupling agents, after acid hydrolysis. Reactions were carried out in the presence of dibutyltin dilaurate as catalyst by reacting lignocellulose modified with the coupling agents and clinoptilolite at 140 °C ...

  6. Solid State NMR Characterization and Adsorption Properties of ...

    African Journals Online (AJOL)


    South Africa) was filtered (Whatman filter paper, 150 mm ø) and oven-dried in an open vessel for 48 h at ... first with cold and then with hot deionized water, until all traces of acid were removed and the AgNO3 ...... Gas/solid systems with special reference to the determination of sur- face area and porosity, Pure App. Chem., ...

  7. Synthesis, Crystal Structure, NMR Studies, and Thermal Stability of Mixed Iron-Indium Phosphates with Quasi-One-Dimensional Frameworks. (United States)

    Tang, X.; Jones, A.; Lachgar, A.; Gross, B. J.; Yarger, J. L.


    The hydrothermal synthesis, single-crystal structure analysis, spectroscopic studies, and thermal stability of the compounds Ca(2)(In(1)(-)(x)()Fe(x)())(PO(4))(HPO(4))(2).H(2)O (0 Solid state magic angle spinning (MAS) (31)P NMR of Ca(2)In(PO(4))(HPO(4))(2).H(2)O confirms two phosphorous moieties in roughly a 2:1 ratio. A CP-MAS buildup study yielded polarization transfer rates (T(IS)(-)(1)) of 2128 and 1597 s(-)(1) for the HPO(4) (-2.4 ppm) and PO(4) (-0.9 ppm) sites, respectively. A (1)H-(31)P WISE experiment indicates the presence of motional narrowing and hydrogen exchange between the water molecules and hydroxyl protons.

  8. Rare-earth tricyanomelaminates [NH(4)]Ln[HC(6)N(9)](2)[H(2)O](7)H(2)O (Ln=La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy): structural investigation, solid-state NMR spectroscopy, and photoluminescence. (United States)

    Nag, Abanti; Lotsch, Bettina V; Schmedt Auf der Günne, Jörn; Oeckler, Oliver; Schmidt, Peter J; Schnick, Wolfgang


    The rare-earth tricyanomelaminates, [NH(4)]Ln[HC(6)N(9)](2)[H(2)O](7)xH(2)O (LnTCM; Ln=La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy), have been synthesized through ion-exchange reactions. They have been characterized by powder as well as single-crystal X-ray diffraction analysis, vibrational spectroscopy, and solid-state (1)H, (13)C, and (15)N MAS NMR spectroscopy. The X-ray powder pattern common to all nine rare-earth tricyanomelaminates LnTCM (Ln=La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy) indicates that they are isostructural. The single-crystal X-ray diffraction pattern of LnTCM is indicative of non-merohedral twinning. The crystals are triclinic and separation of the twin domains as well as refinement of the structure were successfully carried out in the space group P1 for LaTCM (LaTCM; P1, Z=2, a=7.1014(14), b=13.194(3), c=13.803(3) A, alpha=90.11(3), beta=77.85(3), gamma=87.23(3) degrees , V=1262.8(4) A(3)). In the crystal structure, each Ln(3+) is surrounded by two nitrogen atoms from two crystallographically independent tricyanomelaminate moieties and seven oxygen atoms from crystal water molecules. The positions of all of the hydrogen atoms of the ammonium ions and water molecules could not be located from difference Fourier syntheses. The presence of [NH(4)](+) ions as well as two NH groups belonging to two crystallographically independent monoprotonated tricyanomelaminate moieties has only been confirmed by subjecting LaTCM to solid-state (1)H, (13)C, and (15)N{(1)H} cross-polarization (CP) MAS NMR and advanced CP experiments such as cross-polarization combined with polarization inversion (CPPI). The (1)H 2D double-quantum single-quantum homonuclear correlation (DQ SQ) spectrum and the (15)N{(1)H} 2D CP heteronuclear-correlation (HETCOR) spectrum have revealed the hydrogen-bonded (N--HN) dimer of monoprotonated tricyanomelaminate moieties as well as H-bonding through [NH(4)](+) ions and H(2)O molecules. The structures of the other eight rare-earth tricyanomelaminates (Ln

  9. Solid state nuclear magnetic resonance studies of prion peptides and proteins

    Energy Technology Data Exchange (ETDEWEB)

    Heller, Jonathan [Univ. of California, Berkeley, CA (United States)


    High-resolution structural studies using x-ray diffraction and solution nuclear magnetic resonance (NMR) are not feasible for proteins of low volubility and high tendency to aggregate. Solid state NMR (SSNMR) is in principle capable of providing structural information in such systems, however to do this efficiently and accurately, further SSNMR tools must be developed This dissertation describes the development of three new methods and their application to a biological system of interest, the priori protein (PrP).

  10. Materials for solid state lighting

    Energy Technology Data Exchange (ETDEWEB)

    Johnson, S.G.; Simmons, J.A.


    Dramatic improvement in the efficiency of inorganic and organic light emitting diodes (LEDs and OLEDs) within the last decade has made these devices viable future energy efficient replacements for current light sources. However, both technologies must overcome major technical barriers, requiring significant advances in material science, before this goal can be achieved. Attention will be given to each technology associated with the following major areas of material research: (1) material synthesis, (2) process development, (3) device and defect physics, and (4) packaging. The discussion on material synthesis will emphasize the need for further development of component materials, including substrates and electrodes, necessary for improving device performance. The process technology associated with the LEDs and OLEDs is very different, but in both cases it is one factor limiting device performance. Improvements in process control and methodology are expected to lead to additional benefits of higher yield, greater reliability and lower costs. Since reliability and performance are critical to these devices, an understanding of the basic physics of the devices and device failure mechanisms is necessary to effectively improve the product. The discussion will highlight some of the more basic material science problems remaining to be solved. In addition, consideration will be given to packaging technology and the need for the development of novel materials and geometries to increase the efficiencies and reliability of the devices. The discussion will emphasize the performance criteria necessary to meet lighting applications, in order to illustrate the gap between current status and market expectations for future product.

  11. Solid State Lighting Reliability Components to Systems

    CERN Document Server

    Fan, XJ


    Solid State Lighting Reliability: Components to Systems begins with an explanation of the major benefits of solid state lighting (SSL) when compared to conventional lighting systems including but not limited to long useful lifetimes of 50,000 (or more) hours and high efficacy. When designing effective devices that take advantage of SSL capabilities the reliability of internal components (optics, drive electronics, controls, thermal design) take on critical importance. As such a detailed discussion of reliability from performance at the device level to sub components is included as well as the integrated systems of SSL modules, lamps and luminaires including various failure modes, reliability testing and reliability performance. This book also: Covers the essential reliability theories and practices for current and future development of Solid State Lighting components and systems Provides a systematic overview for not only the state-of-the-art, but also future roadmap and perspectives of Solid State Lighting r...

  12. Nanorod Array Solid State Neutron Detectors Project (United States)

    National Aeronautics and Space Administration — In this Phase I SBIR project, Synkera proposes to develop and commercialize solid-state neutron detectors of a unique architecture that will enable sensor modules...

  13. Endohedrally filled [Ni@Sn9](4-) and [Co@Sn9](5-) clusters in the neat solids Na12Ni(1-x)Sn17 and K(13-x)Co(1-x)Sn17: crystal structure and 119Sn solid-state NMR spectroscopy. (United States)

    Hlukhyy, Viktor; Stegmaier, Saskia; van Wüllen, Leo; Fässler, Thomas F


    A systematic approach to the formation of endohedrally filled atom clusters by a high-temperature route instead of the more frequent multistep syntheses in solution is presented. Zintl phases Na12Ni(1-x)Sn17 and K(13-x)Co(1-x)Sn17, containing endohedrally filled intermetalloid clusters [Ni@Sn9](4-) or [Co@Sn9](5-) beside [Sn4](4-), are obtained from high-temperature reactions. The arrangement of [Ni@Sn9](4-) or [Co@Sn9](5-) and [Sn4](4-) clusters, which are present in the ratio 1:2, can be regarded as a hierarchical replacement variant of the hexagonal Laves phase MgZn2 on the Mg and Zn positions, respectively. The alkali-metal positions are considered for the first time in the hierarchical relationship, which leads to a comprehensive topological parallel and a better understanding of the composition of these compounds. The positions of the alkali-metal atoms in the title compounds are related to the known inclusion of hydrogen atoms in the voids of Laves phases. The inclusion of Co atoms in the {Sn9} cages correlates strongly with the number of K vacancies in K(13-x)Co(1-x)Sn17 and K(5-x)Co(1-x)Sn9, and consequently, all compounds correspond to diamagnetic valence compounds. Owing to their diamagnetism, K(13-x)Co(1-x)Sn17, and K(5-x)Co(1-x)Sn9, as well as the d-block metal free binary compounds K12Sn17 and K4Sn9, were characterized for the first time by (119)Sn solid-state NMR spectroscopy. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Solid-State Fermentation: An Overview


    Bhargav, Samir; Panda, Bibhu Prasad; Ali, Mohd.; Javed, Saleem


    Solid-state fermentation (ssf) is defined as the growth of microbes without free flowing aqueous phase. The ssf is alternative to submerged fermentation for production of value added products like antibiotics, single cell protein, PUFA’s, enzymes, organic acids, biopesticides, biofuel and aroma production. However, the advantages of ssf in various processes are found to be greater than in submerged fermentation. This paper reviews the advantages of solid-state fermentation over submerged in p...

  15. Solid State Physics Introduction to the Theory

    CERN Document Server

    Patterson, James D


    Learning Solid State Physics involves a certain degree of maturity, since it involves tying together diverse concepts from many areas of physics. The objective is to understand, in a basic way, how solid materials behave. To do this one needs both a good physical and mathematical background. One definition of Solid State Physics is it is the study of the physical (e.g. the electrical, dielectric, magnetic, elastic, and thermal) properties of solids in terms of basic physical laws. In one sense, Solid State Physics is more like chemistry than some other branches of physics because it focuses on common properties of large classes of materials. It is typical that Solid State Physics emphasizes how physics properties link to electronic structure. We have retained the term Solid State Physics, even though Condensed Matter Physics is more commonly used. Condensed Matter Physics includes liquids and non-crystalline solids such as glass, which we shall not discuss in detail. Modern Solid State Physics came of age in ...

  16. Method for increasing β-SiC yield on solid state reaction of coal fly ...

    Indian Academy of Sciences (India)


    analyzed by XRD with Cu-Kα radiation, FTIR spectrometer and SEM fitted with EDAX. The results show that the amount of relative β-SiC is increased with the number of cycling synthesis. Keywords. SiC; cycling synthesis; solid state reaction. 1. Introduction. Fly ash, a waste product of coal combustion in thermal power plants ...

  17. Probing hydrogen in ZnO nanorods using solid-state 1H nuclear magnetic resonance

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Li Q.; Exarhos, Gregory J.; Windisch, Charles F.; Yao, Chunhua; Pederson, Larry R.; Zhou, Xiao Dong


    We have developed a low-temperature reflux method to synthesize large quantities of well-dispersed free-standing ZnO nanorods using a simple and mild aqueous solution route. In this approach, different surfactants were used to control nanostructure morphologies. Bound proton states in these ZnO nanorods were characterized for the first time by high resolution solid-state 1H magic angle spinning (MAS) NMR. In contrast to commercially available ZnO nano- or micro-particles, our uniform ZnO nanorods show a surprisingly sharp 1H NMR resonance. The feature is maintained upon heating to 500 oC, which suggests that an unusually stable proton species exists, most likely associated with lattice defects within the ZnO framework. Work here has demonstrated a new approach for probing a small amount of proton species associated with defects in nano-crystalline solids using high resolution solid-state 1H MAS NMR.

  18. Solid state physics principles and modern applications

    CERN Document Server

    Quinn, John J


    This book provides the basis for a two-semester graduate course on solid-state physics. The first half presents all the knowledge necessary for a one-semester survey of solid-state physics, but in greater depth than most introductory solid state physics courses. The second half includes most of the important research over the past half-century, covering both the fundamental principles and most recent advances. This new edition includes the latest developments in the treatment of strongly interacting two-dimensional electrons and discusses the generalization from small to larger systems. The book provides explanations in a class-tested tutorial style, and each chapter includes problems reviewing key concepts and calculations. The updated exercises and solutions enable students to become familiar with contemporary research activities, such as the electronic properties of massless fermions in graphene and topological insulators.

  19. Driver circuit for solid state light sources (United States)

    Palmer, Fred; Denvir, Kerry; Allen, Steven


    A driver circuit for a light source including one or more solid state light sources, a luminaire including the same, and a method of so driving the solid state light sources are provided. The driver circuit includes a rectifier circuit that receives an alternating current (AC) input voltage and provides a rectified AC voltage. The driver circuit also includes a switching converter circuit coupled to the light source. The switching converter circuit provides a direct current (DC) output to the light source in response to the rectified AC voltage. The driver circuit also includes a mixing circuit, coupled to the light source, to switch current through at least one solid state light source of the light source in response to each of a plurality of consecutive half-waves of the rectified AC voltage.

  20. Physics of Nanostructured Solid State Devices

    CERN Document Server

    Bandyopadhyay, Supriyo


    Physics of Nanostructured Solid State Devices introduces readers to theories and concepts such as semi-classical and quantum mechanical descriptions of electron transport, methods for calculations of band structures in solids with applications in calculation of optical constants, and other advanced concepts.  The information presented here will equip readers with the necessary tools to carry out cutting edge research in modern solid state nanodevices. This book also: Covers sophisticated models of charge transport including the drift-diffusion model, Boltzmann transport model and various quantum transport models Discusses the essential elements of quantum mechanics necessary for an understanding of nanostructured solid state devices Presents band structure calculation methods based on time-independent perturbation theory Discusses theory of optical transitions and optical devices employing quantum-confined structures such as quantum wells,wires and dots Elucidates quantum mechanics of electrons in a magneti...